J. Phys. Chem. A 2012,116, 6792-6797

A review of advanced and practical lithium battery materialsRotem Marom,*S.Francis Amalraj,Nicole Leifer,David Jacob and Doron AurbachReceived 3rd December 2010,Accepted 31st January 2011DOI:10.1039/c0jm04225kPresented herein is a discussion of the forefront in research and development of advanced electrode materials and electrolyte solutions for the next generation of lithium ion batteries.The main challenge of the field today is in meeting the demands necessary to make the electric vehicle fully commercially viable.This requires high energy and power densities with no compromise in safety.Three families of advanced cathode materials (the limiting factor for energy density in the Li battery systems)are discussed in detail:LiMn 1.5Ni 0.5O 4high voltage spinel compounds,Li 2MnO 3–LiMO 2high capacity composite layered compounds,and LiMPO 4,where M ¼Fe,Mn.Graphite,Si,Li x TO y ,and MO (conversion reactions)are discussed as anode materials.The electrolyte is a key component that determines the ability to use high voltage cathodes and low voltage anodes in the same system.Electrode–solution interactions and passivation phenomena on both electrodes in Li-ion batteries also play significant roles in determining stability,cycle life and safety features.This presentation is aimed at providing an overall picture of the road map necessary for the future development of advanced high energy density Li-ion batteries for EV applications.IntroductionOne of the greatest challenges of modern society is to stabilize a consistent energy supply that will meet our growing energy demands.A consideration of the facts at hand related to the energy sources on earth reveals that we are not encountering an energy crisis related to a shortage in total resources.For instancethe earth’s crust contains enough coal for the production of electricity for hundreds of years.1However the continued unbridled usage of this resource as it is currently employed may potentially bring about catastrophic climatological effects.As far as the availability of crude oil,however,it in fact appears that we are already beyond ‘peak’production.2As a result,increasing oil shortages in the near future seem inevitable.Therefore it is of critical importance to considerably decrease our use of oil for propulsion by developing effective electric vehicles (EVs).EV applications require high energy density energy storage devices that can enable a reasonable driving range betweenDepartment of Chemistry,Bar-Ilan University,Ramat-Gan,52900,Israel;Web:http://www.ch.biu.ac.il/people/aurbach.E-mail:rotem.marom@live.biu.ac.il;aurbach@mail.biu.ac.ilRotem MaromRotem Marom received her BS degree in organic chemistry (2005)and MS degree in poly-mer chemistry (2007)from Bar-Ilan University,Ramat Gan,Israel.She started a PhD in electrochemistry under the supervision of Prof.D.Aurbach in 2010.She is currently con-ducting research on a variety of lithium ion battery materials for electric vehicles,with a focus on electrolyte solutions,salts andadditives.S :Francis AmalrajFrancis Amalraj hails from Tamil Nadu,India.He received his MSc in Applied Chemistry from Anna University.He then carried out his doctoral studies at National Chemical Laboratory,Pune and obtained his PhD in Chemistry from Pune University (2008).He is currently a postdoctoral fellow in Prof.Doron Aurbach’s group at Bar-Ilan University,Israel.His current research interest focuses on the synthesis,electrochemical and transport properties of high ener-getic electrode materials for energy conversion and storage systems.Dynamic Article Links CJournal ofMaterials ChemistryCite this:DOI:10.1039/c0jm04225k /materialsFEATURE ARTICLED o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225KView Onlinecharges and maintain acceptable speeds.3Other important requirements are high power density and acceptable safety features.The energy storage field faces a second critical chal-lenge:namely,the development of rechargeable systems for load leveling applications (e.g.storing solar and wind energy,and reducing the massive wasted electricity from conventional fossil fuel combustion plants).4Here the main requirements are a very prolonged cycle life,components (i.e.,relevant elements)abun-dant in high quantities in the earth’s crust,and environmentally friendly systems.Since it is not clear whether Li-ion battery technology can contribute significantly to this application,battery-centered solutions for this application are not discussedherein.In fact,even for electrical propulsion,the non-petroleum power source with the highest energy density is the H 2/O 2fuel cell (FC).5However,despite impressive developments in recent years in the field,there are intrinsic problems related to electrocatalysis in the FCs and the storage of hydrogen 6that will need many years of R&D to solve.Hence,for the foreseeable future,rechargeable batteries appear to be the most practically viable power source for EVs.Among the available battery technologies to date,only Li-ion batteries may possess the power and energy densities necessary for EV applications.The commonly used Li-ion batteries that power almost all portable electronic equipment today are comprised of a graphite anode and a LiCoO 2cathode (3.6V system)and can reach a practical energy density of 150W h kg À1in single cells.This battery technology is not very useful for EV application due to its limited cycle life (especially at elevated temperatures)and prob-lematic safety features (especially for large,multi-cell modules).7While there are ongoing developments in the hybrid EV field,including practical ones in which only part of the propulsion of the car is driven by an electrical motor and batteries,8the main goal of the battery community is to be able to develop full EV applications.This necessitates the development of Li-ion batteries with much higher energy densities compared to the practical state-of-the-art.The biggest challenge is that Li-ion batteries are complicated devices whose components never reach thermodynamic stability.The surface chemistry that occurs within these systems is very complicated,as described briefly below,and continues to be the main factor that determines their performance.9Nicole Leifer Nicole Leifer received a BS degree in chemistry from MIT in 1998.After teaching high school chemistry and physics for several years at Stuyvesant High School in New York City,she began work towards her PhD in solid state physics from the City University of New York Grad-uate Center.Her research con-sisted primarily of employing solid state NMR in the study of lithium ion electrode materialsand electrode surfacephenomena with Prof.Green-baum at Hunter College andProf.Grey at Stony Brook University.After completing her PhD she joined Prof.Doron Aurbach for a postdoctorate at Bar-Ilan University to continue work in lithium ion battery research.There she continues her work in using NMR to study lithium materials in addition to new forays into carbon materials’research for super-capacitor applications with a focus on enhancement of electro-chemical performance through the incorporation of carbonnanotubes.David Jacob David Jacob earned a BSc from Amravati University in 1998,an MSc from Pune University in 2000,and completed his PhD at Bar-Ilan University in 2007under the tutelage of Professor Aharon Gedanken.As part of his PhD research,he developed novel methods of synthesizing metal fluoride nano-material structures in ionic liquids.Upon finishing his PhD he joined Prof.Doron Aurbach’s lithium ionbattery group at Bar-Ilan in2007as a post-doctorate and during that time developed newformulations of electrolyte solutions for Li-ion batteries.He has a great interest in nanotechnology and as of 2011,has become the CEO of IsraZion Ltd.,a company dedicated to the manufacturing of novelnano-materials.Doron Aurbach Dr Doron Aurbach is a full Professor in the Department of Chemistry at Bar-Ilan Univer-sity (BIU)in Ramat Gan,Israel and a senate member at BIU since 1996.He chaired the chemistry department there during the years 2001–2005.He is also the chairman of the Israeli Labs Accreditation Authority.He founded the elec-trochemistry group at BIU at the end of 1985.His groupconducts research in thefollowing fields:Li ion batteries for electric vehicles and for otherportable uses (new cathodes,anodes,electrolyte solutions,elec-trodes–solution interactions,practical systems),rechargeable magnesium batteries,electronically conducting polymers,super-capacitors,engineering of new carbonaceous materials,develop-ment of devices for storage and conversion of sustainable energy (solar,wind)sensors and water desalination.The group currently collaborates with several prominent research groups in Europe and the US and with several commercial companies in Israel and abroad.He is also a fellow of the ECS and ISE as well as an associate editor of Electrochemical and Solid State Letters and the Journal of Solid State Electrochemistry.Prof.Aurbach has more than 350journals publications.D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225KAll electrodes,excluding 1.5V systems such as LiTiO x anodes,are surface-film controlled (SFC)systems.At the anode side,all conventional electrolyte systems can be reduced in the presence of Li ions below 1.5V,thus forming insoluble Li-ion salts that comprise a passivating surface layer of particles referred to as the solid electrolyte interphase (SEI).10The cathode side is less trivial.Alkyl carbonates can be oxidized at potentials below 4V.11These reactions are inhibited on the passivated aluminium current collectors (Al CC)and on the composite cathodes.There is a rich surface chemistry on the cathode surface as well.In their lithiated state,nucleophilic oxygen anions in the surface layer of the cathode particles attack electrophilic RO(CO)OR solvents,forming different combinations of surface components (e.g.ROCO 2Li,ROCO 2M,ROLi,ROM etc.)depending on the electrolytes used.12The polymerization of solvent molecules such as EC by cationic stimulation results in the formation of poly-carbonates.13The dissolution of transition metal cations forms surface inactive Li x MO y phases.14Their precipitation on the anode side destroys the passivation of the negative electrodes.15Red-ox reactions with solution species form inactive LiMO y with the transition metal M at a lower oxidation state.14LiMO y compounds are spontaneously delithiated in air due to reactions with CO 2.16Acid–base reactions occur in the LiPF 6solutions (trace HF,water)that are commonly used in Li-ion batteries.Finally,LiCoO 2itself has a rich surface chemistry that influences its performance:4LiCo III O 2 !Co IV O 2þCo II Co III 2O 4þ2Li 2O !4HF4LiF þ2H 2O Co III compounds oxidize alkyl carbonates;CO 2is one of the products,Co III /Co II /Co 2+dissolution.14Interestingly,this process seems to be self-limiting,as the presence of Co 2+ions in solution itself stabilizes the LiCoO 2electrodes,17However,Co metal in turn appears to deposit on the negative electrodes,destroying their passivation.Hence the performance of many types of electrodes depends on their surface chemistry.Unfortunately surface studies provide more ambiguous results than bulk studies,therefore there are still many open questions related to the surface chemistry of Li-ion battery systems.It is for these reasons that proper R&D of advanced materials for Li-ion batteries has to include bulk structural and perfor-mance studies,electrode–solution interactions,and possible reflections between the anode and cathode.These studies require the use of the most advanced electrochemical,18structural (XRD,HR microscopy),spectroscopic and surface sensitive analytical techniques (SS NMR,19FTIR,20XPS,21Raman,22X-ray based spectroscopies 23).This presentation provides a review of the forefront of the study of advanced materials—electrolyte systems,current collectors,anode materials,and finally advanced cathodes materials used in Li-ion batteries,with the emphasis on contributions from the authors’group.ExperimentalMany of the materials reviewed were studied in this laboratory,therefore the experimental details have been provided as follows.The LiMO 2compounds studied were prepared via self-combus-tion reactions (SCRs).24Li[MnNiCo]O 2and Li 2MnO 3$Li/MnNiCo]O 2materials were produced in nano-andsubmicrometric particles both produced by SCR with different annealing stages (700 C for 1hour in air,900 C or 1000 C for 22hours in air,respectively).LiMn 1.5Ni 0.5O 4spinel particles were also synthesized using SCR.Li 4T 5O 12nanoparticles were obtained from NEI Inc.,USA.Graphitic material was obtained from Superior Graphite (USA),Timcal (Switzerland),and Conoco-Philips.LiMn 0.8Fe 0.2PO 4was obtained from HPL Switzerland.Standard electrolyte solutions (alkyl carbonates/LiPF 6),ready to use,were obtained from UBE,Japan.Ionic liquids were obtained from Merck KGaA (Germany and Toyo Gosie Ltd.,(Japan)).The surface chemistry of the various electrodes was charac-terized by the following techniques:Fourier transform infrared (FTIR)spectroscopy using a Magna 860Spectrometer from Nicolet Inc.,placed in a homemade glove box purged with H 2O and CO 2(Balson Inc.air purification system)and carried out in diffuse reflectance mode;high-resolution transmission electron microscopy (HR-TEM)and scanning electron microscopy (SEM),using a JEOL-JEM-2011(200kV)and JEOL-JSM-7000F electron microscopes,respectively,both equipped with an energy dispersive X-ray microanalysis system from Oxford Inc.;X-ray photoelectron spectroscopy (XPS)using an HX Axis spectrom-eter from Kratos,Inc.(England)with monochromic Al K a (1486.6eV)X-ray beam radiation;solid state 7Li magic angle spinning (MAS)NMR performed at 194.34MHz on a Bruker Avance 500MHz spectrometer in 3.2mm rotors at spinning speeds of 18–22kHz;single pulse and rotor synchronized Hahn echo sequences were used,and the spectra were referenced to 1M LiCl at 0ppm;MicroRaman spectroscopy with a spectrometerfrom Jobin-Yvon Inc.,France.We also used M €ossbauer spec-troscopy for studying the stability of LiMPO 4compounds (conventional constant-acceleration spectrometer,room temperature,50mC:57Co:Rh source,the absorbers were put in Perspex holders.In situ AFM measurements were carried out using the system described in ref.25.The following electrochemical measurements were posite electrodes were prepared by spreading slurries comprising the active mass,carbon powder and poly-vinylidene difluoride (PVdF)binder (ratio of 75%:15%:10%by weight,mixed into N -methyl pyrrolidone (NMP),and deposited onto aluminium foil current collectors,followed by drying in a vacuum oven.The average load was around 2.5mg active mass per cm 2.These electrodes were tested in two-electrode,coin-type cells (Model 2032from NRC Canada)with Li foil serving as the counter electrode,and various electrolyte puter-ized multi-channel battery analyzers from Maccor Inc.(USA)and Arbin Inc.were used for galvanostatic measurements (voltage vs.time/capacity,measured at constant currents).Results and discussionOur road map for materials developmentFig.1indicates a suggested road map for the direction of Li-ion research.The axes are voltage and capacity,and a variety of electrode materials are marked therein according to their respective values.As is clear,the main limiting factor is the cathode material (in voltage and capacity).The electrode mate-rials currently used in today’s practical batteries allow forD o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Ka nominal voltage of below 4V.The lower limit of the electro-chemical window of the currently used electrolyte solutions (alkyl carbonates/LiPF 6)is approximately 1.5V vs.Li 26(see later discussion about the passivation phenomena that allow for the operation of lower voltage electrodes,such as Li and Li–graphite).The anodic limit of the electrochemical window of the alkyl carbonate/LiPF 6solutions has not been specifically determined but practical accepted values are between 4.2and 5V vs.Li 26(see further discussion).With some systems which will be discussed later,meta-stability up to 4.9V can be achieved in these standard electrolyte solutions.Electrolyte solutionsThe anodic stability limits of electrolyte solutions for Li-ion batteries (and those of polar aprotic solutions in general)demand ongoing research in this subfield as well.It is hard to define the onset of oxidation reactions of nonaqueous electrolyte solutions because these strongly depend on the level of purity,the presence of contaminants,and the types of electrodes used.Alkyl carbonates are still the solutions of choice with little competition (except by ionic liquids,as discussed below)because of the high oxidation state of their central carbon (+4).Within this class of compounds EC and DMC have the highest anodic stability,due to their small alkyl groups.An additional benefit is that,as discussed above,all kinds of negative electrodes,Li,Li–graphite,Li–Si,etc.,develop excellent passivation in these solutions at low potentials.The potentiodynamic behavior of polar aprotic solutions based on alkyl carbonates and inert electrodes (Pt,glassy carbon,Au)shows an impressive anodic stability and an irreversible cathodic wave whose onset is $1.5vs.Li,which does not appear in consequent cycles due to passivation of the anode surface bythe SEI.The onset of these oxidation reactions is not well defined (>4/5V vs.Li).An important discovery was the fact that in the presence of Li salts,EC,one of the most reactive alkyl carbonates (in terms of reduction),forms a variety of semi-organic Li-con-taining salts that serve as passivation agents on Li,Li–carbon,Li–Si,and inert metal electrodes polarized to low potentials.Fig.2and Scheme 1indicates the most significant reduction schemes for EC,as elucidated through spectroscopic measure-ments (FTIR,XPS,NMR,Raman).27–29It is important to note (as reflected in Scheme 1)that the nature of the Li salts present greatly affects the electrode surface chemistry.When the pres-ence of the salt does not induce the formation of acidic species in solutions (e.g.,LiClO 4,LiN(SO 2CF 3)2),alkyl carbonates are reduced to ROCO 2Li and ROLi compounds,as presented in Fig. 2.In LiPF 6solutions acidic species are formed:LiPF 6decomposes thermally to LiF and PF 5.The latter moiety is a Lewis acid which further reacts with any protic contaminants (e.g.unavoidably present traces of water)to form HF.The presence of such acidic species in solution strongly affects the surface chemistry in two ways.One way is that PF 5interactswithFig.1The road map for R&D of new electrode materials,compared to today’s state-of-the-art.The y and x axes are voltage and specific capacity,respectively.Fig.2A schematic presentation of the CV behavior of inert (Pt)elec-trodes in various families of polar aprotic solvents with Li salts.26D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Kthe carbonyl group and channels the reduction process of EC to form ethylene di-alkoxide species along with more complicated alkoxy compounds such as binary and tertiary ethers,rather than Li-ethylene dicarbonates (see schemes in Fig.2);the other way is that HF reacts with ROLi and ROCO 2Li to form ROH,ROCO 2H (which further decomposes to ROH and CO 2),and surface LiF.Other species formed from the reduction of EC are Li-oxalate and moieties with Li–C and C–F bonds (see Scheme 1).27–31Efforts have been made to enhance the formation of the passivation layer (on graphite electrodes in particular)in the presence of these solutions through the use of surface-active additives such as vinylene carbonate (VC)and lithium bi-oxalato borate (LiBOB).27At this point there are hundreds of publica-tions and patents on various passivating agents,particularly for graphite electrodes;their further discussion is beyond the scope of this paper.Readers may instead be referred to the excellent review by Xu 32on this subject.Ionic liquids (ILs)have excellent qualities that could render them very relevant for use in advanced Li-ion batteries,including high anodic stability,low volatility and low flammability.Their main drawbacks are their high viscosities,problems in wetting particle pores in composite structures,and low ionic conductivity at low temperatures.Recent years have seen increasing efforts to test ILs as solvents or additives in Li-ion battery systems.33Fig.3shows the cyclic voltammetric response (Pt working electrodes)of imidazolium-,piperidinium-,and pyrrolidinium-based ILs with N(SO 2CF 3)2Àanions containing LiN(SO 2CF 3)2salt.34This figure reflects the very wide electrochemical window and impressive anodic stability (>5V)of piperidium-and pyr-rolidium-based ILs.Imidazolium-based IL solutions have a much lower cathodic stability than the above cyclic quaternary ammonium cation-based IL solutions,as demonstrated in Fig.3.The cyclic voltammograms of several common electrode mate-rials measured in IL-based solutions are also included in the figure.It is clearly demonstrated that the Li,Li–Si,LiCoO 2,andLiMn 1.5Ni 0.5O 4electrodes behave reversibly in piperidium-and pyrrolidium-based ILs with N(SO 2CF 3)2Àand LiN(SO 2CF 3)2salts.This figure demonstrates the main advantage of the above IL systems:namely,the wide electrochemical window with exceptionally high anodic stability.It was demonstrated that aluminium electrodes are fully passivated in solutions based on derivatives of pyrrolidium with a N(SO 2CF 3)2Àanion and LiN(SO 2CF 3)2.35Hence,in contrast to alkyl carbonate-based solutions in which LiN(SO 2CF 3)2has limited usefulness as a salt due to the poor passivation of aluminium in its solutions in the above IL-based systems,the use of N(SO 2CF 3)2Àas the anion doesn’t limit their anodic stability at all.In fact it was possible to demonstrate prototype graphite/LiMn 1.5Ni 0.5O 4and Li/L-iMn 1.5Ni 0.5O 4cells operating even at 60 C insolutionsScheme 1A reaction scheme for all possible reduction paths of EC that form passivating surface species (detected by FTIR,XPS,Raman,and SSNMR 28–31,49).Fig.3Steady-state CV response of a Pt electrode in three IL solutions,as indicated.(See structure formulae presented therein.)The CV presentations include insets of steady-state CVs of four electrodes,as indicated:Li,Li–Si,LiCoO 2,and LiMn 1.5Ni 0.5O 4.34D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Kcomprising alkyl piperidium-N(SO2CF3)2as the IL solvent and Li(SO2CF3)2as the electrolyte.34Challenges remain in as far as the use of these IL-based solutions with graphite electrodes.22Fig.4shows the typical steady state of the CV of graphite electrodes in the IL without Li salts.The response in this graph reflects the reversible behavior of these electrodes which involves the insertion of the IL cations into the graphite lattice and their subsequent reduction at very low potentials.However when the IL contains Li salt,the nature of the reduction processes drastically changes.It was recently found that in the presence of Li ions the N(SO2CF3)2Àanion is reduced to insoluble ionic compounds such as LiF,LiCF3, LiSO2CF3,Li2S2O4etc.,which passivate graphite electrodes to different extents,depending on their morphology(Fig.4).22 Fig.4b shows a typical SEM image of a natural graphite(NG) particle with a schematic view of its edge planes.Fig.4c shows thefirst CVs of composite electrodes comprising NG particles in the Li(SO2CF3)2/IL solution.These voltammograms reflect an irreversible cathodic wave at thefirst cycle that belongs to the reduction and passivation processes and their highly reversible repeated Li insertion into the electrodes comprising NG. Reversible capacities close to the theoretical ones have been measured.Fig.4d and e reflect the structure and behavior of synthetic graphiteflakes.The edge planes of these particles are assumed to be much rougher than those of the NG particles,and so their passivation in the same IL solutions is not reached easily. Their voltammetric response reflects the co-insertion of the IL cations(peaks at0.5V vs.Li)together with Li insertion at the lower potentials(<0.3V vs.Li).Passivation of this type of graphite is obtained gradually upon repeated cycling(Fig.4e), and the steady-state capacity that can be obtained is much lower than the theoretical one(372mA h gÀ1).Hence it seems that using graphite particles with suitable morphologies can enable their highly reversible and stable operation in cyclic ammonium-based ILs.This would make it possible to operate high voltage Li-ion batteries even at elevated temperatures(e.g. 4.7–4.8V graphite/LiMn1.5Ni0.5O4cells).34 The main challenge in thisfield is to demonstrate the reasonable performance of cells with IL-based electrolytes at high rates and low temperatures.To this end,the use of different blends of ILs may lead to future breakthroughs.Current collectorsThe current collectors used in Li-ion systems for the cathodes can also affect the anodic stability of the electrolyte solutions.Many common metals will dissolve in aprotic solutions in the potential ranges used with advanced cathode materials(up to5V vs.Li). Inert metals such as Pt and Au are also irrelevant due to cost considerations.Aluminium,however,is both abundantand Fig.4A collection of data related to the behavior of graphite electrodes in butyl,methyl piperidinium IL solutions.22(a)The behavior of natural graphite electrodes in pure IL without Li salt(steady-state CV is presented).(b)The schematic morphology and a SEM image of natural graphite(NG)flakes.(c)The CV response(3first consecutive cycles)of NG electrodes in IL/0.5lithium trifluoromethanesulfonimide(LiTFSI)solution.(d and e)Same as(b and c)but for synthetic graphiteflakes.DownloadedbyBeijingUniversityofChemicalTechnologyon24February211Publishedon23February211onhttp://pubs.rsc.org|doi:1.139/CJM4225Kcheap and functions very well as a current collector due to its excellent passivation properties which allow it a high anodic stability.The question remains as to what extent Al surfaces can maintain the stability required for advanced cathode materials (up to 5V vs.Li),especially at elevated temperatures.Fig.5presents the potentiodynamic response of Al electrodes in various EC–DMC solutions,considered the alkyl carbonate solvent mixture with the highest anodic stability,at 30and 60 C.37The inset to this picture shows several images in which it is demonstrated that Al surfaces are indeed active and develop unique morphologies in the various solutions due to their obvious anodic processes in solutions,some of which lead to their effective passivation.The electrolyte used has a critical impact on the anodic stability of the Al.In general,LiPF 6solutions demonstrate the highest stability even at elevated temperatures due to the formation of surface AlF 3and even Al(PF 6)3.Al CCs in EC–DMC/LiPF 6solutions provide the highest anodic stability possible for conventional electrode/solution systems.This was demonstrated for Li/LiMn 1.5Ni 0.5O 4spinel (4.8V)cells,even at 60 C.36This was also confirmed using bare Al electrodes polarized up to 5V at 60 C;the anodic currents were seen to decay to negligible values due to passivation,mostly by surface AlF 3.37Passivation can also be reached in Li(SO 2CF 3),LiClO 4and LiBOB solutions (Fig.5).Above 4V (vs.Li),the formation of a successful passivation layer on Al CCs is highly dependent on the electrolyte formula used.The anodic stability of EC–DMC/LiPF 6solutions and Al current collectors may be further enhanced by the use of additives,but a review of additives in itself deserves an article of its own and for this readers are again referred to the review by Xu.32When discussing the topic of current collectors for Li ion battery electrodes,it is important to note the highly innovative work on (particularly anodic)current collectors by Taberna et al.on nano-architectured Cu CCs 47and Hu et al.who assembled CCs based on carbon nano-tubes for flexible paper-like batteries,38both of whom demonstrated suberb rate capabilities.39AnodesThe anode section in Fig.1indicates four of the most promising groups of materials whose Li-ion chemistry is elaborated as follows:1.Carbonaceous materials/graphite:Li ++e À+C 6#LiC 62.Sn and Si-based alloys and composites:40,41Si(Sn)+x Li ++x e À#Li x Si(Sn),X max ¼4.4.3.Metal oxides (i.e.conversion reactions):nano-MO +2Li ++2e À#nano-MO +Li 2O(in a composite structure).424.Li x TiO y electrodes (most importantly,the Li 4Ti 5O 12spinel structure).43Li 4Ti 5O 12+x Li ++x e À#Li 4+x Ti 5O 12(where x is between 2and 3).Conversion reactions,while they demonstrate capacities much higher than that of graphite,are,practically speaking,not very well-suited for use as anodes in Li-ion batteries as they generally take place below the thermodynamic limit of most developed electrolyte solutions.42In addition,as the reactions require a nanostructuring of the materials,their stability at elevated temperatures will necessarily be an issue because of the higher reactivity (due to the 1000-fold increase in surface area).As per the published research on this topic,only a limited meta-stability has been demonstrated.Practically speaking,it does not seem likely that Li batteries comprising nano-MO anodes will ever reach the prolonged cycle life and stability required for EV applications.Tin and silicon behave similarly upon alloying with Li,with similar stoichiometries and >300%volume changes upon lith-iation,44but the latter remain more popular,as Si is much more abundant than Sn,and Li–Si electrodes indicate a 4-fold higher capacity.The main approaches for attaining a workable revers-ibility in the Si(Sn)–Li alloying reactions have been through the use of both nanoparticles (e.g.,a Si–C nanocomposites 45)and composite structures (Si/Sn–M1–M2inter-metalliccompounds 44),both of which can better accommodate these huge volume changes.The type of binder used in composite electrodes containing Si particles is very important.Extensive work has been conducted to determine suitable binders for these systems that can improve the stability and cycle life of composite silicon electrodes.46As the practical usage of these systems for EV applications is far from maturity,these electrodes are not dis-cussed in depth in this paper.However it is important to note that there have been several recent demonstrations of how silica wires and carpets of Si nano-rods can act as much improved anode materials for Li battery systems in that they can serveasFig.5The potentiodynamic behavior of Al electrodes (current density measured vs.E during linear potential scanning)in various solutions at 30and 60 C,as indicated.The inset shows SEM micrographs of passivated Al surfaces by the anodic polarization to 5V in the solutions indicated therein.37D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225K。

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APPL PHYSIOL JOURNAL OF APPLIED PHYSIOLOGYJ CLIN ENDOCR METAB JOURNAL OF CLINICAL ENDOCRINOLOGY AND METABOLISM J CLIN MICROBIOL JOURNAL OF CLINICAL MICROBIOLOGYJ COMP NEUROL JOURNAL OF COMPARATIVE NEUROLOGYJ IMMUNOL JOURNAL OF IMMUNOLOGYJ INFECT DIS JOURNAL OF INFECTIOUS DISEASESJ MED CHEM JOURNAL OF MEDICINAL CHEMISTRYJ NEUROCHEM JOURNAL OF NEUROCHEMISTRYJ NEUROPHYSIOL JOURNAL OF NEUROPHYSIOLOGYJ NUTR JOURNAL OF NUTRITIONJ PHARMACOL EXP THER JOURNAL OF PHARMACOLOGY AND EXPERIMENTAL THERAPE J PHYSIOL-LONDON JOURNAL OF PHYSIOLOGY-LONDONJ UROLOGY JOURNAL OF UROLOGYJ VIROL JOURNAL OF VIROLOGYKIDNEY INT KIDNEY INTERNATIONALNEUROIMAGE NEUROIMAGENEUROSCIENCE NEUROSCIENCEPEDIATRICS PEDIATRICSRADIOLOGY RADIOLOGYTRANSPLANTATION TRANSPLANTATIONVIROLOGY VIROLOGYNATURE NATUREP NATL ACAD SCI USA PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES SCIENCE SCIENCEANN NY ACAD SCI ANNALS OF THE NEW YORK ACADEMY OF SCIENCESISSN大类名称复分大类分区是否top期刊2009年影响因子1680-7316地学1Y 4.881 0003-0007地学1Y 6.123 0930-7575地学1Y 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2.874 0928-4249农林科学1Y 3.579 0044-8486农林科学2Y 1.925 0706-652X农林科学2Y 1.951 0378-1127农林科学2Y 1.950 0003-1488农林科学2Y 1.714 0032-079X农林科学2Y 2.517 1526-5161社会科学1Y 4.000 0012-9682社会科学1Y 4.000 0304-4076社会科学2Y 1.902 0002-9297生物1Y12.303 0066-4154生物1Y29.875 1056-8700生物1Y18.955 1936-122X生物1Y19.304 1081-0706生物1Y19.571 1543-592X生物1Y8.190 0066-4170生物1Y11.271 0066-4197生物1Y13.235 1527-8204生物1Y11.568 0066-4227生物1Y12.804 0066-4286生物1Y11.212 1543-5008生物1Y23.460 0092-8674生物1Y31.152 1931-3128生物1Y13.021 1550-4131生物1Y17.350 1934-5909生物1Y23.563 1040-9238生物1Y10.216 0960-9822生物1Y10.992 0955-0674生物1Y14.153 0959-437X生物1Y8.987 1369-5266生物1Y10.333 0959-440X生物1Y9.344 1534-5807生物1Y13.363 0890-9369生物1Y12.075 1088-9051生物1Y11.342 0021-9525生物1Y9.575 1092-2172生物1Y12.585 1097-2765生物1Y14.608 1744-4292生物1Y12.125 1465-7392生物1Y19.527 1552-4450生物1Y16.058 1061-4036生物1Y34.284 1548-7091生物1Y16.874 1471-0056生物1Y27.822 1740-1526生物1Y17.644 1471-0072生物1Y42.198 1545-9985生物1Y12.2731040-4651生物1Y9.293 1544-9173生物1Y12.916 1553-7390生物1Y9.532 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重庆医科大学申报教授专业技术职务任职资格评审综合情况(公示)表填表时间：2016 年6月12日填报单位: 重庆医科大学基础医学院学科: 生物化学与分子生物学
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3.20.01489 5.62318>10.00.013647.55389.40.008828.821867 5.10.27819 4.24368.40.00872 6.542227 5.50.53637 3.497299.90.01888.1211078 4.40.37491 5.1891191 2.40.20333 4.012473 1.80.05534 3.461368.20.03818 3.07130997.70.83183 2.99465 5.90.01757 3.141169 1.40.00944 3.344569 4.20.12336 3.006377.20.00647 2.73229 1.90.00155 3.27323 3.90.00716 4.441557.70.01045 2.068458 1.40.02121 2.833576 6.70.15215 2.032167.90.00342 3.148457 3.60.07856 2.503112 4.60.01202 1.97501 6.90.05008 1.9062220.00197 2.73916>10.00.003282.792Eigenfactor®Metrics286 2.60.0208 2.0046>10.00.00142 1.13896 2.80.01517 2.301119.20.00397 3.974>10.00.00086 1.894 44940.03848 1.5233>10.00.00076 2.537437.60.01013 2.301 63220.04884 2.393 2150.003483173 4.80.28954 1.5629>10.00.00211 3.009 138 5.80.01695 1.794 1015 1.70.02966 1.597 508.20.01226 2.37 160850.18182 1.40244 5.40.01448 3.213188.30.00431 2.295 107.10.00156 2.34 674 6.40.06437 1.6 1916 4.10.1766 1.469 480 5.40.05059 1.419 284>10.00.04014 1.60356 1.20.00194 1.703 617 3.70.05475 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2597.10.02119 1.078 877 4.30.068460.99799 1.40.001410.915 449 6.30.028910.786 16157.50.18356 1.081 22860.020170.96535 1.90.00176 1.224 1160 3.80.055440.914 201 6.30.017610.949 426 4.10.025740.772 2120 3.70.074070.708 1016 5.80.054290.757 321 5.50.013530.63690 3.30.006210.726 184 4.80.010070.73123>10.00.00228 1.513 610 3.80.032170.72 842 5.40.057730.829 213 5.40.01270.77439 2.40.001731002 4.80.033670.729 208 4.30.00930.537 5247.60.043570.93 116>10.00.02104 1.812 173>10.00.013330.936 589 5.30.032210.807 108 6.10.009190.931 487 4.70.03951 1.142 76450.047770.779 1666 5.20.091160.854 193 1.80.004620.921 120 2.20.004670.894 3338.70.027140.756 4327.10.027040.625 19520.003610.533 194 6.90.011710.909 2597.30.013360.716 266 6.80.026850.752 87080.070140.869 2187.70.01310.75610 5.60.00062 1.012 4189.20.026590.815 622 5.20.034970.666 1709.90.01712 1.222 178 5.80.009120.836 907.70.00320.65258>10.00.01221 1.371 4877.30.041850.896 187 5.60.009820.662 338 6.50.019280.711 443 6.30.026840.651 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chemical-reaction-engineeri ng-3ed-edition作者-octave-Levenspiel-课后习题答案Corresponding Solutions for Chemical Reaction EngineeringCHAPTER 1 OVERVIEW OF CHEMICAL REACTION ENGINEERING (1)CHAPTER 2 KINETICS OF HOMOGENEOUS REACTIONS (3)CHAPTER 3 INTERPRETATION OF BATCH REACTOR DATA (7)CHAPTER 4 INTRODUCTION TO REACTOR DESIGN (20)CHAPTER 5 IDEAL REACTOR FOR A SINGLE REACTOR (23)CHAPTER 6 DESIGN FOR SINGLE REACTIONS (27)CHAPTER 10 CHOOSING THE RIGHT KIND OF REACTOR (34)CHAPTER 11 BASICS OF NON-IDEAL FLOW (36)CHAPTER 18 SOLID CATALYZED REACTIONS (45)Chapter 1 Overview of Chemical Reaction Engineering1.1 Municipal waste water treatment plant. Consider a municipal water treatment plant for a small community (Fig.P1.1). Waste water, 32000 m 3/day, flows through the treatment plant with a mean residence time of 8 hr, air is bubbled through the tanks, and microbes in the tank attack and break down the organic material (organic waste) +O 2 −−−→−microbes CO 2 + H 2OA typical entering feed has a BOD (biological oxygen demand) of 200 mg O 2/liter, while the effluent has a megligible BOD. Find the rate of reaction, or decrease in BOD in the treatment tanks.Figure P1.1Solution:)/(1017.2)/(75.183132/100010001)0200()(313200031320001343333s m mol day m mol day molgm L mg g L mg day day m dayday m VdtdN r A A ⋅⨯=⋅=-⨯⨯⨯-⨯-=-=--1.2 Coal burning electrical power station. Large central power stations (about 1000 MW electrical) using fluiding bed combustors may be built some day (see Fig.P1.2). These giants would be fed 240 tons of coal/hr (90% C, 10%H 2), 50% of which would burn within the battery of primary fluidized beds, the other 50% elsewhere in the system. One suggested design would use a battery of 10 fluidized beds, each 20 m long, 4 m wide, and containing solids to a depth of 1 m. Find the rate of reaction within theWaste Waste Clean200 mgMean residenZerobeds, based on the oxygen used.Solution:380010)1420(m V =⨯⨯⨯=)/(9000101089.05.01024033hr bed molc hrkgckgcoal kgc hr coal t N c ⋅-=⨯-=⨯⨯⨯-=∆∆ )/(25.111900080011322hr m kmolO t N V r r c c O ⋅=-⨯-=∆∆-=-=)/(12000412000190002hr bed mol dt dO ⋅=+⨯= )/(17.4800)/(105.113422s m mol hr bed mol dt dO V r O ⋅=⋅⨯==-Chapter 2 Kinetics of Homogeneous Reactions2.1 A reaction has the stoichiometric equation A + B =2R . What is the order of reaction?Solution: Because we don’t know whether it is an elementary reaction or not, we can’t tell the index of the reaction.2.2 Given the reaction 2NO 2 + 1/2 O 2 = N 2O 5 , what is the relation between the ratesof formation and disappearance of the three reaction components? Solution: 522224O N O NO r r r =-=-2.3 A reaction with stoichiometric equation 0.5 A + B = R +0.5 S has the following rateexpression-r A = 2 C 0.5 A C BWhat is the rate expression for this reaction if the stoichiometric equation is written asA + 2B = 2R + SSolution: No change. The stoichiometric equation can’t effect the rate equation, so it doesn’t change.2.4 For the enzyme-substrate reaction of Example 2, the rate of disappearance ofsubstrate is given by-r A =A06]][[1760C E A + , mol/m 3·sWhat are the units of the two constants? Solution: ][]6[]][][[][03A A C E A k s m mol r +=⋅=- 3/][]6[m mol C A ==∴sm mol m mol m mol s m mol k 1)/)(/(/][3333=⋅⋅=2.5 For the complex reaction with stoichiometry A + 3B → 2R + S and withsecond-order rate expression-r A = k 1[A][B]are the reaction rates related as follows: r A = r B = r R ? If the rates are not so related, then how are they related? Please account for the sings , + or - .Solution: R B A r r r 2131=-=-2.6 A certain reaction has a rate given by-r A = 0.005 C 2 A , mol/cm 3·min If the concentration is to be expressed in mol/liter and time in hours, what wouldbe the value and units of the rate constant?Solution:min)()(3'⋅⨯-=⋅⨯-cm molr hr L mol r A A 22443'300005.0106610)(minAA A A A C C r r cm mol mol hr L r =⨯⨯=⋅⨯=-⋅⋅⋅=-∴ AA A A A C C cmmol mol L C cmmolC L mol C 33'3'10)()(=⋅⋅=∴⨯=⨯2'42'32'103)10(300300)(AA A A C C C r --⨯=⨯==-∴ 4'103-⨯=∴k2.7 For a gas reaction at 400 K the rate is reported as -dtdp A= 3.66 p 2 A , atm/hr (a) What are the units of the rate constant?(b) What is the value of the rate constant for this reaction if the rate equation isexpressed as-r A = - dtdN V A1 = k C2 A , mol/m 3·s Solution:(a) The unit of the rate constant is ]/1[hr atm ⋅ (b) dtdN V r AA 1-=-Because it’s a gas reaction occuring at the fined terperatuse, so V=constant, and T=constant, so the equation can be reduced to22)(66.366.3)(1RT C RTP RT dt dP RT dt dP VRT V r A A A A A ==-=-=-22)66.3(A A kC C RT ==So we can get that the value of1.12040008205.066.366.3=⨯⨯==RT k2.9 The pyrolysis of ethane proceeds with an activation energy of about 300 kJ/mol.How much faster the decomposition at 650℃ than at 500℃?Solution:586.7)92311731()10/(314.8/300)11(3211212=-⋅⋅=-==KK K mol kJ mol kJ T T R E k k Ln r r Ln7.197012=∴r r2.11 In the mid-nineteenth century the entomologist Henri Fabre noted that French ants (garden variety) busily bustled about their business on hot days but were rather sluggish on cool days. Checking his results with Oregon ants, I findRunning speed, m/hr150160230295370Temperatu re, ℃13 16 22 24 28 What activation energy represents this change in bustliness? Solution:RTE RTE RTE ek eak t cons ion concentrat f let ion concentrat f ek r ---=⋅⋅=⋅='00tan )()(RET Lnk Lnr A 1'-=∴ Suppose Tx Lnr y A 1,==, so ,REslope -= intercept 'Lnk =)/(1-⋅h m r A 150 160 230 295 370 A Lnr-3.1780 -3.1135 -2.7506 -2.5017 -2.2752CT o / 13 16 22 24 28 3101-⨯T3.4947 3.4584 3.3881 3.3653 3.3206-y = 5417.9x - 15.686R2 = 0.9712340.00330.003350.00340.003450.00351/T-L n r-y = -5147.9 x + 15.686Also K REslope 9.5147-=-=, intercept 'Lnk == 15.686 , mol kJ K mol J K E /80.42)/(3145.89.5147=⋅⨯-=Chapter 3 Interpretation of Batch Reactor Data3.1 If -r A = - (dC A /dt) =0.2 mol/liter·sec when C A = 1 mol/liter, what is the rate ofreaction when C A = 10 mol/liter? Note: the order of reaction is not known.Solution: Information is not enough, so we can’t answer this kind of question.3.2 Liquid a sedomposes by first-order kinetics, and in a batch reactor 50% of A isconverted in a 5-minute run. How much longer would it take to reach 75% conversion?Solution: Because the decomposition of A is a 1st -order reaction, so we can express the rate equation as:A A kC r =-We know that for 1st -order reaction, kt C C LnAAo=, 11kt C C LnA Ao =, 22kt C CLn A Ao = Ao A C C 5.01=, Ao A C C 25.02=So 21)24(1)(11212Ln kLn Ln k C C Ln C C Ln k t t A Ao A Ao =-=-=- equ(1) min 521)(111===Ln kC C Ln k t A Ao equ(2) So m in 5112==-t t t3.3 Repeat the previous problem for second-order kinetics. Solution: We know that for 2nd -order reaction, kt C C A A =-011, So we have two equations as follow:min 511211101k kt C C C C C AoAo Ao A A ===-=-, equ(1)2123)1(31411kt kt C C C C C AoAo Ao Ao A ===-=-, equ(2) So m in 15312==t t , m in 1012=-t t3.4 A 10-minute experimental run shows that 75% of liquid reactant is converted to product by a 21-order rate. What would be the fraction converted in a half-hour run?Solution: In a-21order reaction: 5.0AA A kC dt dC r =-=-, After integration, we can get:5.015.02A Ao C C kt -=, So we have two equations as follow:min)10(5.0)41(15.05.05.05.015.0k kt C C C C C Ao Ao AoA Ao ===-=-, equ(1) min)30(25.025.0k kt C C A Ao ==-, equ(2)Combining these two equations, we can get:25.05.1kt C Ao =, but this means 05.02<A C , whichis impossible, so we can conclude that less than half hours, all the reactant is consumed up. So the fraction converted 1=A X .3.5 In a hmogeneous isothermal liquid polymerization, 20% of the monomer disappears in 34 minutes for initial monomer concentration of 0.04 and also for 0.8 mol/liter. What rate equation represents the disappearance of the monomer?Solution: The rate of reactant is independent of the initial concentration of monomers, so we know the order of reaction is first-order,monomer monomer kC r =-And k C C Lnoomin)34(8.0= 1min 00657.0-=kmonomer monomer C r )min 00657.0(1-=-3.6 After 8 minutes in a batch reactor, reactant (C A0 = 1 mol/liter) is 80% converted; after 18 minutes, conversion is 90%. Find a rate equation to represent this reaction. Solution:In 1st order reaction, 43.1511111111212==--=Ln Ln X Lnk X Ln k t t A A , dissatisfied.In 2nd order reaction, 49/4/912.0111.01)11(1)11(11212==--=--=Ao Ao Ao Ao Ao Ao Ao A Ao A C C C C C C C C k C C k t t, satisfied.According to the information, the reaction is a 2nd -order reaction.3.7 nake-Eyes Magoo is a man of habit. For instance, his Friday evenings are all alike —into the joint with his week’s salary of ＄180, steady gambling at “2-up” for two hours, then home to his family leaving ＄45 behind. Snake Eyes’s betting pattern is predictable. He always bets in amounts proportional to his cash at hand, and his losses are also predictable —at a rate proportional to his cash at hand. This week Snake-Eyes received a raise in salary, so he played for three hours, but as usual went home with ＄135. How much was his raise? Solution:180=Ao n , 13=A n , h t 2=,135'=A n , h t 3;=, A A kn r α-So we obtain kt n n LnAAo=, ''')()(tn n Ln t n n Ln AAo A Ao= 3135213180'Ao n Ln Ln =, 28'=An3.9 The first-order reversible liquid reactionA ↔ R , C A0 = 0.5 mol/liter, C R0=0takes place in a batch reactor. After 8 minutes, conversion of A is 33.3% while equilibrium conversion is 66.7%. Find the equation for the this reaction. Solution: Liquid reaction, which belongs to constant volume system,1st order reversible reaction, according to page56 eq. 53b, we obtain121112102110)(1)(-+-+=+-==⎰⎰AX A A tX k k k k Lnk k X k k k dX dt t Amin 8sec 480==t , 33.0=A X , so we obtain eq(1)33.0)(1min8sec 480211121k k k k Ln k k +-+= eq(1) Ae AeAe c X X M C C k k K -+===1Re 21, 0==AoRo C C M , so we obtain eq(2) 232132121=-=-==AeAe c X X k k K ,212k k =∴ eq(2)Combining eq(1) and eq(2), we obtain1412sec 108.4m in 02888.0---⨯==k 14121sec 1063.9m in 05776.02---⨯===k kSo the rate equation is )(21A Ao A AA C C k C k dtdC r --=-=- )(sec 1063.9sec 108.401414A A A C C C -⨯-⨯=----3.10 Aqueous A reacts to form R (A→R) and in the first minute in a batch reactor itsconcentration drops from C A0 = 2.03 mol/liter to C Af = 1.97 mol/liter. Find the rate equation from the reaction if the kinetics are second-order with respect to A.Solution: It’s a irreversible second -order reaction system, according to page44 eq 12, we obtainmin 103.2197.111⋅=-k , so min015.01⋅=mol Lkso the rate equation is 21)min 015.0(A A C r -=-3.15 At room temperature sucrose is hydrolyzed by the catalytic action of the enzymesucrase as follows:Aucrose −−→−sucraseproductsStarting with a sucrose concentration C A0 = 1.0 millimol/liter and an enzyme concentrationC E0= 0.01 millimol/liter, the following kinetic data are obtained in a batch reactor (concentrations calculated from optical rotation measurements):Determine whether these data can be reasonably fitted by a knietic equation of the Michaelis-Menten type, or-r A =MA E A C C C C k +03 where C M = Michaelis constantIf the fit is reasonable, evaluate the constants k 3 and C M . Solve by the integral method.Solution: Solve the question by the integral method:AA M A A Eo A A C k Ck C C C C k dt dC r 5431+=+=-=-, M Eo C C k k 34=, MC k 15= AAo A Ao A Ao C C C C Lnk k k C C t -⋅+=-4451hrt ,AC ,mmol /L A Ao AAo C C C C Ln-AAo C C t -1 0.84 1.0897 6.25 20.681.20526.25C A , millimol /liter0.84 0.68 0.53 0.38 0.27 0.16 0.09 0.04 0.018 0.006 0.0025t,hr 1 2 3 4 5 6 7 8 9 10 113 0.53 1.3508 6.38304 0.38 1.5606 6.45165 0.27 1.7936 6.8493 6 0.16 2.1816 7.14287 0.09 2.6461 7.69238 0.04 3.3530 8.33339 0.018 4.0910 9.1650 10 0.006 5.1469 10.0604 110.00256.006511.0276Suppose y=A Ao C C t-, x=AAo A Ao C C C C Ln-, thus we obtain such straight line graphy = 0.9879x + 5.0497R 2 = 0.99802468101201234567Ln(Cao/Ca)/(Cao-Ca)t /(C a o -C a )9879.0134===Eo M C k C k Slope , intercept=0497.545=k k So )/(1956.00497.59879.015L mmol k C M ===, 14380.1901.09879.01956.0-=⨯==hr C C k k Eo M3.18 Enzyme E catalyzes the transformation of reactant A to product R as follows: A −−→−enzyme R, -r A =min22000⋅+liter molC C C A E AIf we introduce enzyme (C E0 = 0.001 mol/liter) and reactant (C A0 = 10mol/liter) into a batch rector and let the reaction proceed, find the time needed for the concentration of reactant to drop to 0.025 mol/liter. Note that the concentration of enzyme remains unchanged during the reaction.. Solution:510001.020021+=⨯+=-=-AA A A A C C C dC dt r Rearranging and integrating, we obtain:10025.0025.0100)(510)510(⎥⎦⎤⎢⎣⎡-+=+-==⎰⎰A Ao A Ao A A tC C C C Ln dC C dt t min 79.109)(5025.01010=-+=A Ao C C Ln3.20 M.Hellin and J.C. Jungers, Bull. soc. chim. France, 386(1957), present the data in Table P3.20 on thereaction of sulfuric acid with diethylsulfate in a aqueous solution at22.9℃:H 2SO 4 + (C 2H 5)2SO 4 → 2C 2H 5SO 4HInitial concentrations of H 2SO 4 and (C 2H 5)2SO 4 are each 5.5 mol/liter. Find a rate equation for this reaction.Table P3.20 t, minC 2H 5SO 4H , mol/li ter t, minC 2H 5SO 4H , mol/li ter1804.1141 1.18 194 4.31 48 1.38 212 4.45 55 1.63 267 4.86 75 2.24 318 5.15 96 2.75 368 5.32 127 3.31 379 5.35 146 3.76 410 5.42 1623.81∞(5.80)Solution: It’s a constant -volume system, so we can use X A solving the problem: i) We postulate it is a 2nd order reversible reaction system R B A 2⇔+ The rate equation is: 221R B A A A C k C C k dtdC r -=-=- L mol C C Bo Ao /5.5==, )1(A Ao A X C C -=, A A Ao Bo B C X C C C =-=, A Ao R X C C 2=When ∞=t , L mol X C C Ae Ao /8.52Re == So 5273.05.528.5=⨯=Ae X , L mol X C C C Ae Ao Be Ae /6.2)5273.01(5.5)1(=-⨯=-== After integrating, we obtaint C X k X X X X X LnAo AeA Ae A Ae Ae )11(2)12(1-=--- eq (1)The calculating result is presented in following Table.t,mi nLmol C R /,Lmol C A /,AXAAe AAe Ae X X X X X Ln---)12()1(AeAX X Ln -0 0 5.5 0 0 041 1.18 4.91 0.10730.2163 -0.227548 1.38 4.81 0.12540.2587 -0.271755 1.63 4.685 0.14820.3145 -0.329975 2.24 4.38 0.20360.4668 -0.488196 2.75 4.125 0.25 0.6165 -0.642712 7 3.31 3.8450.30090.8140 -0.845614 6 3.76 3.620.34181.0089 -1.044916 2 3.81 3.5950.34641.0332 -1.069718 0 4.11 3.4450.37361.1937 -1.233119 4 4.31 3.3450.39181.3177 -1.359121 2 4.45 3.2750.40451.4150 -1.4578267 4.86 3.07 0.4418 1.7730 -1.8197 318 5.15 2.925 0.4682 2.1390 -2.1886 368 5.32 2.84 0.4836 2.4405 -2.4918 379 5.35 2.825 0.4864 2.5047 -2.5564 4105.42 2.79 0.4927 2.6731 -2.7254 ∞5.82.60.5273——Draw AAe AAe Ae X X X X X Ln---)12(~ t plot, we obtain a straight line:y = 0.0067x - 0.0276R 2= 0.998800.511.522.530100200300400500tL n0067.0)11(21=-=Ao AeC X k Slope ,min)/(10794.65.5)15273.01(20067.041⋅⨯=⨯-=∴-mol L kWhen approach to equilibrium, BeAe c C C C k k K 2Re 21==, so min)/(10364.18.56.210794.642242Re 12⋅⨯=⨯⨯==--mol L C C C k k Be Ae So the rate equation ism in)/()10364.110794.6(244⋅⨯-⨯=---L mol C C C r R B A Aii) We postulate it is a 1st order reversible reaction system, so the rate equation isR A AA C k C k dtdC r 21-=-=- After rearranging and integrating, we obtaint k X X X Ln AeAe A '11)1(=-eq (2) Draw )1(AeAX X Ln -~ t plot, we obtain another straight line: -y = 0.0068x - 0.0156R 2 = 0.998600.511.522.530100200300400500x-L n0068.0'1-==AeX k Slope ,So 13'1m in 10586.35273.00068.0--⨯-=⨯-=k133Re '1'2min 10607.18.56.210586.3---⨯-=⨯⨯-==C C k k AeSo the rate equation ism in)/()10607.110586.3(33⋅⨯+⨯-=---L mol C C r R A AWe find that this reaction corresponds to both a 1st and 2nd order reversible reaction system, by comparing eq.(1) and eq.(2), especially when X Ae =0.5 , the two equations are identical. This means these two equations would have almost the same fitness of data when the experiment data of the reaction show that X Ae =0.5.(The data that we use just have X Ae =0.5273 approached to 0.5, so it causes to this.)3.24 In the presence of a homogeneous catalyst of given concentration, aqueous reactant A is converted to product at the following rates, and C A alone determines this rate:C A ,mol/liter1 2 4 6 7 9 12-r A , mol/liter·hr0.06 0.1 0.25 1.0 2.0 1.0 0.5We plan to run this reaction in a batch reactor at the same catelyst concentration as used in getting the above data. Find the time needed to lower the concentration of A from C A0 = 10 mol/liter to C Af = 2 mol/liter.Solution: By using graphical integration method, we obtain that the shaped area is 50 hr.04812162002 4 68 10 12 14Ca-1/Ra3.31 The thermal decomposition of hydrogen iodide 2HI → H 2 + I 2is reported by M.Bodenstein [Z.phys.chem.,29,295(1899)] as follows:T,℃ 508427 393 356 283k,cm 3/mol·s0.10590.003100.00058880.9×10-60.942×10-6Find the complete rate equation for this reaction. Use units of joules, moles, cm 3,and seconds.According to Arrhenius’ Law,k = k 0e -E/R Ttransform it,- In(k) = E/R·(1/T) －In(k 0)Drawing the figure of the relationship between k and T as follows:y = 7319.1x - 11.567R 2= 0.987904812160.0010.0020.0030.0041/T-L n (k )From the figure, we getslope = E/R = 7319.1 intercept = - In(k 0) = -11.567E = 60851 J/mol k 0 = 105556 cm 3/mol·sFrom the unit [k] we obtain the thermal decomposition is second-order reaction, so the rate expression is- r A = 105556e -60851/R T ·C A 2Chapter 4 Introduction to Reactor Design4.1 Given a gaseous feed, C A0 = 100, C B0 = 200, A +B→ R + S, X A = 0.8. Find X B ,C A ,C B . Solution: Given a gaseous feed, 100=Ao C , 200=Bo C , S R B A +→+0=A X , find B X , A C , B C0==B A εε, 202.0100)1(=⨯=-=A Ao A X C C4.02008.01001=⨯⨯==Bo A Ao B C X bC X 1206.0200)1(=⨯=-=B Bo B X C C4.2 Given a dilute aqueous feed, C A0 = C B0 =100, A +2B→ R + S, C A = 20. Find X A , X B , C B .Solution: Given a dilute aqueous feed, 100==Bo Ao C C ,S R B A +→+2, 20=A C , find A X , B X , B CAqueous reaction system, so 0==B A εε When 0=A X , 200=V When 1=A X , 100=VSo 21-=A ε, 41-==Ao Bo A B bC C εε8.01002011=-=-=Ao A A C C X , 16.11008.010012>=⨯⨯=⋅=Bo A Ao B C X C a b X , which is impossible. So 1=B X , 100==Bo B C C4.3 Given a gaseous feed, C A0 =200, C B0 =100, A +B→ R, C A = 50. Find X A , X B , C B . Solution: Given a gaseous feed, 200=Ao C , 100=Bo C ,R B A →+, 50=A C .find A X , B X , B C75.02005011=-=-=Ao A A C C X , 15.1>==BoAAo B C X bC X , which is impossible. So 100==Bo B C C4.4 Given a gaseous feed, C A0 = C B0 =100, A +2B→ R, C B = 20. Find X A , X B , C A . Solution: Given a gaseous feed, 100=+Bo Ao C C ，R B A →+2, 20=Bo C , Find A X , B X , A C0=B X , 200100100=+=B A V ,1=B X 15010050=+=R A V25.0200200150-=-=B ε, 5.01002110025.0-=⨯⨯-=-A ε842.02025.010020100=⨯--=B X , 421.0100842.010021=⨯⨯=A X34.73421.05.01421.0110011=⨯--⨯=+-=A A A AoA X X C C ε4.6 Given a gaseous feed, T 0 =1000 K, π0＝5atm, C A0=100, C B0=200, A +B→5R,T =400K, π=4atm, C A =20. Find X A , X B , C B .Solution: Given a gaseous feed, K T o 1000=, atm 50=π, 100=Ao C , 200=Bo CR B A 5→+, K T 400=, atm 4=π, 20=A C , find A X , B X , B C .1300300600=-=A ε, 2==Ao Bo AB bC C a εε,5.0410********=⨯⨯=ππT T According to eq page 87,818.05.010020115.0100201110000=⨯⨯+⨯-=+-=ππεππT T C C T T C C X Ao A AAo A A409.0200818.0100=⨯==Bo A Ao B aC X bC X130818.011200)818.0100200(1)(0=⨯+⨯-=+-=A A Ao A Ao Bo B X C T T X a b C C C εππ4.7 A Commercial Popcorn Popping Popcorn Popper. We are constructing a 1-literpopcorn to be operatedin steady flow. First tests in this unit show that 1 liter/min of raw corn feed stream produces 28 liter/minof mixed exit stream. Independent tests show that when raw corn pops its volumegoes from 1 to 31.With this information determine what fraction of raw corn is popped in the unit.Solution: 301131=-=A ε, ..1u a C Ao =, ..281281u a C C Ao A ==%5.462813012811=⨯+-=+-=∴AA Ao A Ao A C C C C X εChapter 5 Ideal Reactor for a single Reactor5.1 Consider a gas-phase reaction 2A → R + 2S with unknown kinetics. If a spacevelocity of 1/min is needed for 90% conversion of A in a plug flow reactor, find the corresponding space-time and mean residence time or holding time of fluid in the plug flow reactor.Solution: min 11==sτ,Varying volume system, so t can’t be found.5.2 In an isothermal batch reactor 70% of a liquid reactant is converted in 13 min.What space-time and space-velocity are needed to effect this conversion in a plug flow reactor and in a mixed flow reactor? Solution: Liquid reaction system, so 0=A ε According to eq.4 on page 92, min 130=-=⎰AX AAAo r dC C t Eq.13, AAAo A A Ao R F M r X C r C C -=--=..τ, R F M ..τ can’t be cert ain. Eq.17, ⎰-=AX AAAo R F P r dX C 0..τ, so m in 13...==R B R F P t τ5.4 We plan to replace our present mixed flow reactor with one having double thebolume. For the same aqueous feed (10 mol A/liter) and the same feed rate find the new conversion. The reaction are represented byA → R, -r A = kC 1.5 ASolution: Liquid reaction system, so 0=A εA A Ao Ao r X C F V -==τ, 5.1)]1([)(A Ao A A Ao A Ao X C k X r C C C -=-- Now we know: V V 2=', Ao Ao F F =', Ao Ao C C =', 7.0=A X So we obtain5.15.15.15.1)1()2)1(2A Ao A A Ao A Ao Ao X kC X X kC X F VF V -='-'==''52.8)7.01(7.02)1(5.15.1=-⨯='-'∴A AX X794.0='A X5.5 An aqueous feed of A and B (400liter/min, 100 mmol A/liter, 200 mmol B/liter) isto be converted to product in a plug flow reactor. The kinetics of the reaction is represented byA +B→ R, -r A = 200C A C Bmin⋅liter molFind the volume of reactor needed for 99.9% conversion of A to product.Solution: Aqueous reaction system, so 0=A εAccording to page 102 eq.19,⎰⎰-=-==Af AfX AA X A A AoAo Ao r dX r dC C C t F V 001⎰-==AfX AAAo or dX C Vντ, m in /400liter o =ν, L r dX r dX C V AAX A A o Ao Af3.1244001.0999.000=-⨯=-=∴⎰⎰ν5.9 A specific enzyme acts as catalyst in the fermentation of reactant A. At a givenenzyme concentration in the aqueous feed stream (25 liter/min) find the volume of plug flow reactor needed for 95% conversion of reactant A (C A0 =2 mol/liter ). The kinetics of the fermentation at this enzyme concentration is given byA −−→−enzymeR , -r A = litermolC C A A ⋅+min 5.011.0Solution: P.F.R, according to page 102 eq.18, aqueous reaction, 0=ε⎰-=A X AA Ao r dX F V 0 )11(21251.05.010A AX A A A Ao X X Ln dX C C F V A+-⨯=+=∴⎰\L Ln4.986)95.005.01(125=+=5.11 Enzyme E catalyses the fermentation of substrate A (the reactant) to product R.Find the size of mixed flow reactor needed for 95% conversion of reactant in a feed stream (25 liter/min ) of reactant (2 mol/liter) and enzyme. The kinetics of the fermentation at this enzyme concentration are given byA −−→−enzyme R , -r A =litermolC C A A ⋅+min 5.011.0Solution: min /25L o =ν, L mol C Ao /2=, m in /50mol F Ao =, 95.0=A X Constant volume system, M.F.R., so we obtainmin 5.199205.05.01205.01.095.02=⨯⨯+⨯⨯⨯=-==AAAo or X C Vντ,39875.4min /25min 5.199m L V o =⨯==τν5.14 A stream of pure gaseous reactant A (C A0 = 660 mmol/liter) enters a plug flowreactor at a flow rate of F A0 = 540 mmol/min and polymerizes the as follows3A → R, -r A = 54min⋅liter mmolHow large a reactor is needed to lower the concentration of A in the exitstream to C Af = 330 mmol/liter?Solution: 321131-=-=A ε, 75.0660330321660330111=⨯--=+-=Ao A A Ao A A C C C C X ε 0-order homogeneous reaction, according to page 103 eq.20A Ao AoAooX C F VC kVkk ===ντ So we obtainL X k C C F V A Ao Ao Ao 5.75475.05401=⨯==5.16 Gaseous reactant A decomposes as follows:A → 3 R, -r A = (0.6min -1)C AFind the conversion of A in a 50% A – 50% inert feed (υ0 = 180 liter/min, C A0 =300 mmol/liter) to a 1 m 3 mixed flow reactor.Solution: 31m V =, M.F.R. 1224=-=A εAccording to page 91 eq.11, AAAoAAo AAAo oX X C X C r X C V+-=-==116.0ντmin/1801000)1(6.0)1(L LX X X A A A =-+=So we obtain 667.0=A XChapter 6 Design for Single Reactions6.1 A liquid reactant stream (1 mol/liter) passes through two mixed flow reactors in aseries. The concentration of A in the exit of the first reactor is 0.5 mol/liter. Find the concentration in the exit stream of the second reactor. The reaction is second-order with respect to A and V 2/V 1 =2.Solution:V 2/V 1 = 2, τ1 =011υV =A A A r C C --10 , 2τ = 022υV = 221A A A r C C --C A0=1mol/l , C A1=0.5mol/l , 0201υυ=, -r A1=kC 2 A1 ,-r A2=kC 2 A2 (2nd-order) , 2×2110A A A kC C C -=2221A A A kC C C - So we obtain 2×(1-0.5)/(k0.52)=(0.5-C A2)/(kC A22)C A2= 0.25 mol/l6.2 Water containing a short-lived radioactive species flows continuously through awell-mixed holdup tank. This gives time for the radioactive material to decay into harmless waste. As it now operates, the activity of the exit stream is 1/7 of the feed stream. This is not bad, but we’d like to lower it still more.One of our office secretaries suggests that we insert a baffle down the middle ofthe tank so that the holdup tank acts as two well-mixed tanks in series. Do you think this would help? If not, tell why; if so calculate the expected activity of the exit stream compared to the entering stream.Solution: 1st-order reaction, constant volume system. From the information offeredabout the first reaction,we obtain1τ=01100117171A A A A A A C k C C kC C C V ⋅-=-=υ If a baffle is added,022220212122212υυτττV V +=+==011υV =2222221210A A A A A A kC C C kC C C -+-=007176A A kC C =6/k …… ①。

专利名称：Chemical sensor using eddy current orresonant electromagnetic circuit detection 发明人：Howard P. Groger,Russell J. Churchill,James Kelsch申请号：US08/179679申请日：19940111公开号：US05514337A公开日：19960507专利内容由知识产权出版社提供摘要：An instrument is applied to the measurement of chemical species and concentration through the use of a chemically-sensitive coating on the eddy current coil or in the vicinity of the eddy current coil which produces a change in impedance of the probe through induced eddy currents in the coating. An eddy current or resonance circuit chemical detector is a non-contact sensor for measuring chemical species identity and concentration. The chemical detector is resilient and does not require reference electrodes. The chemical sensor is selective as a result of data available on the change in vector impedance of the probe, the change in resonant frequency of the tuned circuit, and the availability of data to construct a vector response from multiple probes having differing chemistries. The probe is used in extreme temperatures.申请人：AMERICAN RESEARCH CORPORATION OF VIRGINIA代理人：James Creighton Wray更多信息请下载全文后查看。

大 学 化 学Univ. Chem. 2024, 39 (4), 163收稿：2023-08-31；录用：2023-10-16；网络发表：2023-11-15*通讯作者，Email:************.cn基金资助：山东大学青年学者未来计划；山东大学实验室建设与管理研究项目(sy20232204)•专题• doi: 10.3866/PKU.DXHX202308117 ZIF-67/氧化亚铜复合材料的制备及其光增强电催化性能研究 ——推荐一个综合性物理化学实验林猛*，陈涵睿，徐聪聪山东大学化学与化工学院，济南 250100摘要：大学物理化学实验多以经典的基础理论验证性实验为主，自主设计性、综合性实验缺乏。

依托于山东大学化学实验教学中心现有的仪器设备及实验条件，设计了制备钴基金属有机框架/氧化亚铜微纳米复合材料，并研究其光增强电催化析氧性能的综合性物理化学实验。

本实验涉及物质合成、结构成分分析、产品性能表征、实验结果处理等方面，在启发学生发现物质结构与性能之间内在规律的同时，巩固了学生对前期所学理论及实验知识的掌握，调动了学生学习的积极性和主动性，提升了学生解决问题和灵活运用知识的能力。

关键词：综合性物理化学实验；光增强；电催化析氧反应；半导体；ZIF-67中图分类号：G64；O64Preparation and Study of Photo-Enhanced Electrocatalytic Oxygen Evolution Performance of ZIF-67/Copper(I) Oxide Composite:A Recommended Comprehensive Physical Chemistry ExperimentMeng Lin *, Hanrui Chen, Congcong XuSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.Abstract: University physical chemistry experiments mainly focuse on classical foundational theory verification experiments, with a lack of independent design and comprehensive experiments. Based on the existing instruments and experimental conditions of the Center for Experimental Chemistry Education of Shandong University, a comprehensive physical chemistry experiment was designed to prepare cobalt-based metal-organic framework/copper(I) oxide micro-nano composites and study the photo-enhanced electrochemical oxygen evolution catalytic performance. This experiment involves aspects such as material synthesis, structural characterization, performance evaluation, and result analysis. It not only inspires students to discover the inherent laws between material structure and properties, but also consolidates their previous theoretical and experimental knowledge, mobilizes students’ enthusiasm and initiative in learning, and enhances their ability to solve problems and flexibly apply knowledge.Key Words: Comprehensive physical chemistry experiment; Photo-enhancement;Electrocatalytic oxygen evolution reaction; Semiconductor; ZIF-671 引言物理化学实验是物理化学教学的重要组成部分，它综合了化学领域中各分支学科所需的基本研究方法和实验技能，是培养学生物理化学基本素养和动手能力的重要教学环节，对提升学生的逻辑思维和科研能力具有重要作用[1]。

中国环境科学 2007,27(1)：67~70 China Environmental Science 纳滤膜对脂肪族及杂环有机物的截留特性李鑫玮,祝万鹏∗,韩文亚(清华大学环境科学与工程系,北京 100084)摘要：分别选用NF90、NF270和NF-型号的纳滤膜测定了20种脂肪族及杂环有机物的截留率(R),并分析了纳滤膜截留效果的影响因素.结果表明,脂肪族及杂环有机物的R受到分子结构和膜特性的影响:对于同分异构体,分枝结构越多,R越高;环状有机物与分子量相近的直链有机物相比,R明显偏高;孔径越小的纳滤膜R越高.利用遗传算法(GA)结合偏最小二乘回归(PLS)和人工神经网络法(ANN)建立了脂肪族及杂环物质的R与其结构的定量关系模型,2种方法建立的模型相关系数可分别达到0.8809和0.9944,通过2种模型进一步分析了R的影响规律,并对几种物质的R进行了有效的预测.从预测结果来看,GA-ANN模型的预测精度要好于GA-PLS模型.关键词：纳滤膜；脂肪族及杂环有机物；定量构效关系中图分类号：TU991.2 文献标识码：A 文章编号：1000-6923(2007)01-0067-04Rejection characteristics of aliphatic and heterocyclic organisms by nanofiltration membranes. LI Xin-wei, ZHU Wan-peng*, HAN Wen-ya (Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, China). China Environmental Science, 2007,27(1)：67~70Abstract：Nanofiltration membrane NF90, NF270 and NF- modes were selected separately to determine the rejection rates of 20 kinds of aliphatic and heterocyclic organism (AHO); and the influence factors of nanofiltration rejection effect were analyzed. The rejection rates of AHO were influenced by the molecular structures and characteristics of membranes. On the isomers, the more the branch structures, the higher the rejection rates; the cyclic organism compared with the straight chain organism of similar molecular weights, the rejection rates were higher obviously; the smaller the pore radius of the membrane, the higher the rejection rate. The quantitative structure-property relationships (QSPR) model with the rejection rate of AHO was established, utilizing least square regression (PLS) and artificial neural networks (ANN) combined with genetic algorithm (GA); the correlation coefficients of model established by these two techniques could reach 0.8809 and 0.9944 respectively. Through these two models, the influence rule of the rejection rates was further analyzed and the rejection rates of certain AHO were predicted effectively. According to the predicted results, the precision in predicting by GA-ANN model was better than that by GA-PLS.Key words：nanofiltration membranes；aliphatic and heterocyclic organisms；quantitative structure-property relationships近年来,纳滤膜已广泛地应用于降低水源水的色度、硬度和去除饮用水中的有机物(TOC)、三卤代烷(THMs)前体物等[1-5].但目前的研究涉及到的有机物种类有限,对有机物的纳滤截留效果影响因素的研究还有待深入.本实验选用20种脂肪族及杂环有机物作为模型污染物,测定了3种不同纳滤膜对各种物质的截留率(R),并利用遗传算法(GA)分别结合偏最小二乘回归法(PLS)和人工神经网络法(ANN),建立了脂肪族及杂环有机物R与其结构的定量关系模型,探讨影响脂肪族及杂环有机物R的因素,并对几种物质的R进行预测. 1试验装置与方法试验装置如图1所示.纳滤膜组件为日本日东电工公司的C70-F型圆形平板膜组件.高压泵将温度恒定的水样输送到纳滤膜组件,透过液和浓缩液均返回到料液桶以维持水样浓度的恒定,试验压力和流量通过阀门调节.试验分别选用美国陶氏化学公司的NF90、NF270、NF-纳滤膜,有效膜面积均为3.35×10-3m2.收稿日期：2006-05-24基金项目：国家自然科学基金资助项目(50238020)* 责任作者, 教授, zwp-den@68 中 国 环 境 科 学 27卷纳滤膜的性能参数如表1所示. 图1 试验装置示意Fig.1 Apparatus diagram for experiment1.料液桶2.恒温水浴3.三柱塞高压泵 4,5阀门 6.压力表7.转子流量计 8.纳滤膜组件表1 纳滤膜的性能参数Table 1 Properties of nanofiltration membranes纳滤膜 膜的材质截留分子量孔径(nm)NF90 聚酰胺复合膜 90 0.29 NF270 聚酰胺复合膜 150 0.36 NF-聚哌嗪酰胺复合膜 150 0.37水样均为去离子水配水,配水中只含一种脂肪族或杂环化合物,浓度均为10mg/L.水样的体积为5L.水样的温度恒定在25,℃进水流量为6L/min,操作压力为1.0MPa.R 由下式计算:R (%)＝(1-C p /C r )×100%式中:C p 和C r 分别为透过液和浓缩液中有机物的浓度,均由TOC 仪(TOC-V WP,岛津,日本)测定. 2 结果与讨论2.1 分子结构与膜特性对R 的影响由表2可见,在试验所选的有机物中,丁醇有4种同分异构体(正丁醇、异丁醇、仲丁醇和叔丁醇);戊醇有2种同分异构体(正戊醇和异戊醇).对于丁醇,R 最低的是正丁醇,最高的是叔丁醇,异丁醇和仲丁醇的R 居中.对于戊醇,正戊醇的R 明显低于异戊醇.可见,对于脂肪族有机物的同分异构体,分枝结构越多,R 越高;而直链分子的R 最低.这种现象不仅体现在同分异构体上,即使直链分子的分子量比带支链分子的分子量大,R 也可能较低,如3种膜对正丁醇的R 均低于异丙醇.由于直链分子没有分枝结构,空间位阻与带有支链的分子相比较小,导致其更容易进入并通过膜孔,从而使其R 较低.表2 纳滤膜对脂肪族及杂环物质的R 试验值Table 2 Experimental data for the rejection ratesof AHO by nanofiltration membranesR (%)序号有机物分子量NF90 NF270NF-1 异丙醇 60 77.7 38.6 42.92 乙二醇 6251.6 21.1 22.8 3 四氢呋喃 72 63.5 35.1 37.6 4 正丁醇 7458.7 23.2 30.0 5 异丁醇 74 87.5 52.1 57.4 6 仲丁醇 7484.2 47.2 52.9 7叔丁醇 74 95.7 76.1 81.78 1,4-二氧六环88 87.8 52.9 58.89 正戊醇 88 68.9 25.7 25.9 10 异戊醇 8889.8 49.2 53.1 11 丙三醇 92 89.8 58.7 63.3 12 环己酮 9890.4 67.7 73.5 13 环己醇 100 94.9 66.4 78.514 1,6-己二醇118 86.9 53.2 56.215 正辛醇 130 61.5 28.8 34.7 16 己二酸 14697.1 96.5 96.8 17 酒石酸 150 94.9 93.4 94.7 18 山梨醇 18296.0 91.9 94.4 19 柠檬酸 192 98.4 96.3 97.2 20十二酸 20094.0 81.1 82.4试验选用的几种环状有机物,分别为四氢呋喃、1,4-二氧六环、环己醇、环己酮,以便和链状有机物的截留效果作对比.由表2可见,环状有机物与分子量相近的直链有机物相比, R 明显偏高.其中环己醇,环己酮的R 甚至明显高于分子量更大的正辛醇.这种环状有机物R 高于分子量相近的直链有机物R 的现象与分枝结构的影响类似,也可以用空间位阻效应来解释.环状有机物的空间位阻大于直链有机物的空间位阻,导致环状有机物更难于进入并通过膜孔,因此环状结构有利于提高纳滤膜的R .纳滤膜对有机物的截留效果与膜的孔径大1期李鑫玮等：纳滤膜对脂肪族及杂环有机物的截留特性69小等物化性质有关[6-10].由表2可见,NF90膜对每种脂肪族及杂环物质的R均明显高于NF270膜和NF-膜,结合表1可以看出,孔径对脂肪族及杂环物质R有很大影响,孔径越小的纳滤膜R越高.NF-膜对脂肪族及杂环有机物的R比NF270膜略高一些,2种膜的孔径基本相等,差别主要在膜分离层的材质上.2.2定量构效的关系在相同的工艺条件下,有机物的纳滤膜截留效果主要决定于它的分子结构,如果能掌握两者之间的定量关系,则有可能通过有机物的分子结构参数预测其纳滤膜R.分别采用GA结合PLS和ANN对18种脂肪族及杂环物质建立定量构效关系模型,并用其他2种有机物(酒石酸,正辛醇)对模型进行检验.建模过程通过在MATLAB6.5软件平台上编程实现.通过ChemOffice2004软件计算和查阅Beilstein数据库得到了13种分子结构描述符用于建立模型,包括辛醇/水分配系数(log P)、分子折射系数(CMR)、偶极矩(µ)、平均分子极化率(α)、氧原子所带最大净电荷(q O-)、分子量(M w)、分子长度(L)以及分子连接性指数等.2.2.1GA结合GA-PLS建模通过GA-PLS建立的回归模型(表3).各分子结构参数均已经过标准化处理,因此回归系数的绝对值越大,分子结构参数对R的影响越大.从相关系数上看,该模型准确度较高.表3 GA-PLS模型Table 3 GA-PLS modes纳滤膜回归模型R2NF90 R=84.0500+9.0156(3χp v)+9.3837(3χc v) 0.7781NF270 R=57.3889+17.9802(M w)+10.1581(3χc v) 0.8809NF- R=61.4111-2.1093(log P)+18.9364(3χp v)+16.0763(3χc v)0.8597在NF90膜的回归模型中选入了三阶路径指数(3χp v);三阶簇指数(3χc v),在NF270膜的回归模型中,选入了3χc v以及M w,这几个参数分别表示分子的形状和大小,其中M w是分子大小的最简单的度量,3χc v指数与分子中分枝数目有关,3χp v包含有空间结构形态方面的信息[11].NF-膜的模型中选入了3个结构参数,但从系数上看,log P的回归系数很小,对R的影响相对较小,影响较大的仍是3χpv和3χcv.这表明对于脂肪族及杂环有机物,分子大小和形状对R的影响很显著.对于3种膜都有相同的规律,即3χp v、3χc v或M w值都与R呈正相关的关系.由2.1节可以看出,对于脂肪族及杂环有机物,分子的分枝结构、环状结构等因素对R的影响很大.2.2.2 GA-ANN建模本研究中采用了三层前馈BP人工神经网络,模型的输入层、隐含层和输出层节点数分别为3,3,1.将20种脂肪族及杂环物质分为3个部分,其中训练组取15个样本,确认组取3个样本(山梨醇,环己醇和仲丁醇),预测组取2个样本(酒石酸,正辛醇).训练组的作用是调整权值、偏置量;确认组的作用是判断网络何时达到最优能力,减小“训练过度”的影响;预测组用于评价被训练过的神经网络的总体性能.由于ANN是一种黑箱模型方法,因此自变量与因变量间很难用一个明确的非线性函数来表达.从表4中的相关系数可以看出, GA-ANN模型的准确度很高,预测能力很强.表4 GA-ANN模型的参数及相关系数Table 4 Parameters and correlation coefficients ofthe models of GA-ANN纳滤膜选入模型的参数R2NF90 M w,3χc v,L 0.9930 NF270 M w,3χp v,L 0.9892NF- M w,3χc v,L 0.9944 从选入模型的参数看,3种膜的模型均选取了表示分子空间大小和结构的参数,其中M w、3χcv、3χpv在GA-PLS模型中也被选入,而L对R的影响主要与纳滤膜的孔径筛分效应有关.与GA-PLS模型相比,2种模型选入的参数不尽相同,这是由模型的算法不同造成的.PLS是线性回归方法,而ANN是非线性方法.尽管选入的参数稍有差别,但在截留机理的解释上并不矛盾.70 中国环境科学27卷2.2.3 2种模型的预测能力 分别用2种模型预测酒石酸和正辛醇的R,结果如表5所示.表5 脂肪族有机物R的模型预测结果(%)Table 5 Predicted rejection rates of aliphatic organismsby two models (%)纳滤膜数值类型酒石酸正辛醇试验值 94.9 61.5 GA-PLS预测值 84.1 86.0 NF90GA-ANN预测值 95.4 65.4试验值 93.4 28.8 GA-PLS预测值 76.8 60.1 NF270GA-ANN预测值 97.4 35.2试验值 94.7 34.7 GA-PLS预测值 65.7 64.8 NF-GA-ANN预测值 97.5 37.9 由表5可见,GA-PLS模型对2种脂肪族有机物的预测值与试验值的相对误差范围是11.4%~ 108.7%,而GA-ANN模型对同样物质的预测值与试验值的相对误差范围是0.5%~22.2%,GA-ANN 模型准确度和预测能力要明显好于GA-PLS模型.ANN通过频繁调整网络中各层之间的权重、阈值等参数来充分提取训练集中化合物所表达的信息,是一种非线性研究方法,而PLS是一种线性回归方法.分子结构参数对R的影响并不是完全线性的,因此GA-ANN模型的相关系数更高,预测的准确度也更好一些.但GA-ANN模型不能明确给出回归关系式,且收敛慢,2种方法各有优缺点.由于2种模型均是在单一体系的基础上建立的,在复杂的混合体系下的预测能力还有待进一步研究和验证.但2种模型对于解释纳滤膜对脂肪族及杂环物质截留效果的影响因素起到了重要作用,为更准确地预测纳滤膜对水源水中有机物的R奠定了基础.3 结论3.1分子的分枝结构和环状结构对3种纳滤膜R的影响很大.孔径小的纳滤膜对脂肪族及杂环物质的R更高.3.2GA-PLS和GA-ANN 2种方法建立的定量构效关系模型均较理想.通过分析GA-PLS模型,可以看出3χp v、3χc v和M w值对脂肪族及杂环物质R影响较大,且都与R呈正相关的关系.3.3 GA-ANN模型的预测精度明显好于GA-PLS模型,这对于预测纳滤膜对水源水中有机物的R有重要意义.参考文献：[1] 薛罡,何圣兵,刘亚男.纳滤膜净化受污染地下水的效能与膜污染特性 [J]. 中国环境科学, 2006,26(Supp1.):36-39.[2] Visvanathan C, Marsono B D, Basu B. Removal of THMP bynanofiltration: Effects of interference parameters [J]. Water Research, 1998,32(12):3527-3538.[3] 何圣兵,王宝贞,王琳,等.活性炭-纳滤膜处理饮用水试验研究[J]. 中国给水排水,2003,19(13):67-68.[4] Orecki A, Tornaszewska M, Karakulski K, et al. Surface watertreatment by the nanofiltration method [J]. Desalination, 2004,162(1-3):47-54.[5] 俞三传,高从堦,张慧.纳滤膜技术和微污染水处理 [J]. 水处理技术, 2005,31(9):6-9.[6] Košutic K, Kunst B. Removal of organics from aqueous solutionsby commercial RO and NF membranes of characterized porosities [J]. Desalination, 2002,142(1):47-56.[7] 杨靖,陈杰瑢,余嵘.纳滤/反渗透分离中有机物的特征参数对截留率的影响研究 [J]. 膜科学与技术, 2006,26(2): 36-40. [8] Braeken L, Bettens B, Boussu K, et al. Transport mechanisms ofdissolved organic compounds in aqueous solution during nanofiltration [J]. Journal of Membrane Science, 2006,279(1-2): 311-319.[9] Yoon Y,Lueptow R M. Removal of organic contaminants by ROand NF membranes [J]. Journal of Membrane Science, 2005, 261(1-2):76-86.[10] Bellona C, Drewes J E. The role of membrane surface charge andsolute physico-chemical properties in the rejection of organic acids by NF membranes [J]. Journal of Membrane Science, 2005,249(1-2):227-234.[11] 王连生,支正良.分子连接性与分子结构-活性 [M]. 北京:中国环境科学出版社,1992.作者简介：李鑫玮(1981-),男,北京市人,清华大学环境科学与工程系硕士研究生,主要研究方向为有机污染物的纳滤分离过程.发表论文3篇.。

Photochromic bisthienylethene as multi-function switches He Tian*and Sheng WangReceived(in Cambridge,UK)13th July2006,Accepted6th September2006First published as an Advance Article on the web26th September2006DOI:10.1039/b610004jBisthienylethenes(BTEs)are one of the most promising families of photochromic compounds because of their fatigue resistance and thermally irreversible properties for use in optoelectronic devices such as ultrahigh-density optical data storage,molecular switches,logic gates,molecular wires,sensors,and so on.This article describes recent development of switchable photochromic bisthienylethene materials,especially multi-switchable bisthienylethene materials including multi-color photochromic materials,multi-switchable organogelators and liquid crystals.We also highlight our recent contributions in this field.IntroductionIn recent years,molecular switches have attracted considerable interest of researchers because they hold great promise as molecular electronic and photonic devices.In contrast to commonplace switches that turn electric appliances on and off, some molecular switches enable the storage of information at the molecular level,which has the potential to significantly influence the development of optoelectronic materials science and information technologies.1Usually,molecular switches act as switching units in various optoelectronic devices and functional materials are addressed by stimulating it with light, electricity or chemical reagents to specifically switch the physical properties between two states.Alternatively,a photo-switch exhibits two stable and selectively addressable states.Especially,photoinduced alteration of chemical and physical properties of photochromic molecules is of great interest because of its potential applications for ultrahigh-density optical data storage and photoregulated molecular switches.2Among various types of photochromic molecules, recent considerable interest has been focused on bisthienyl-ethenes which have excellent fatigue resistance and thermal stability in both isomeric forms,high cyclization and cycloreversion quantum yields,rapid response time,and reactivity in the solid state.3,4Photochromic bisthienylethene (BTE)derivatives undergo reversible photocyclization reac-tions between colourless ring-open and coloured ring-closed isomers when irradiated with the appropriate wavelengths of light(Scheme1).The thermal stability of the diarylethene in both the open-ring and closed-ring isomers makes it possible to demonstrate novel photo-switching effects,such as changes in fluorescent intensity and absorption spectra,electrochemical properties, optical rotation,magnetic properties,electron-transfer inter-action,refractive index,dielectric constant,geometrical structure,and so on.3–6These molecular property changes can be applied to design multi-stable switching materials including photo-switching copolymers,fluorescent molecular switches,photochromic chiral switches,photo-controlled conductivity switches and liquid-crystal switches.In this article,we describe recent development of switchable photochromic bisthienylethene molecular materials,especially multi-switchable bisthienylethene materials including multi-colour copolymers,multi-switchable organogelators and photochromic liquid crystals.We also present specific exam-ples from our own research and highlight our contributions in this field.Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology,Shanghai,200237, P.R.China.E-mail:tianhe@;Fax:+86-21-64252288; Tel:+86-21-64252756Prof.He Tian received his PhD degree in1989from East China University of Science&Technology(ECUST)(Shanghai, China).From1991to1993and in2000,Dr Tian did research on organic functional materials twice in Germany,both supported by the Alexander von Humboldt Foundation.Dr Tian became a full professor at ECUST in1994.In1999,he was appointed Cheung Kong Distinguished Professor by the Education Ministry of China.His current research interests include the syntheses of novel functional organic dyes or co-polymers and the development of interdisciplinary material science that determines the electronic and optical properties of the materials.Prof.Tian has published over180papers in international journals and four academic books(in Chinese).He has also been awarded28Chinese patents.Sheng Wang was born in1974and received his PhD degree in Applied Chemistry(June2006)from the East China University of Science&Technology(ECUST)supervised by Prof.Tian. Presently he works in Zhanjiang Normal University,Zhanjiang, China.His research interests are mainly focused on the development of photochromic materials and molecularswitches.Scheme1Photochromism of bisthienylethene(BTE). FEATURE ARTICLE /chemcomm|ChemCommMolecular switch with high fluorescent contrastFluorescent photochromic materials attract strong interest for their possible application in optical memory as well as in fluorescent probes.In particular,fluorescent diarylethenes,which show reversible change in fluorescent intensity along with the photochromic reaction,are useful non-destructive optical readout systems.7–9Understanding the fluorescent diarylethene photochromic reactions at single-molecule level will help to ultimately realize ultrahigh-density single molecule optical memory.9Irie and co-workers 10synthesized a photo-chromic diarylethene and fluorescent bis(phenylethynyl)an-thracene units are linked through an adamantyl spacer (Fig.1)and investigated the fluorescent photochromic reaction of the diarylethene derivatives.They observed digital fluorescence on/off switching between two discrete states at the single-molecule level upon irradiation with UV and visible light and the ‘‘on’’-and ‘‘off’’-times were dependent on the power of the UV and visible light.The fluorescent contrast in the single molecular level was controlled by the background noise.Neckers and co-workers 11reported a photochromic bisthie-nylethene moiety attached to fluorescent 4,4-difluoro-8-(49-iodophenyl)-1,3,5,7-tetramethyl-4-bora-3a ,4a -diaza-s -inda-cene (iodo-BODIPY)via a phenylacetylene linker.UV-light induced isomerization of the photochromic BTE unit results in a significant decrease in fluorescence intensity while the fluorescence can be also recovered with visible light irradia-tion.Fluorescence quenching in the photochromic isomeriza-tion process is caused generally by an intramolecular energy transfer mechanism.Switching of fluorescence is reversible and can be repeated many times without significant loss of its intensity.Regretfully,the highly fluorescent contrast signal was only observed in solution.Based on our previous work on photochromic BTEs,some new fluorescent switches with high contrast containing BTEs were developed,in which the absorption of the BTE unit should have large overlap with the emission of fluorescent chromophore.This would increase the energy transfer (FRET)efficiency,and consequently increase the fluorescent contrast of the binary states.We designed and synthesized a highly fluorescent contrast photochromic bisthienylethene-bridged naphthalimide (NA)dimer (abbreviated as BTE-NA shownin Scheme 2).12Scheme 2presents the optical switching function of BTE-NA.The open and closed isomers of BTE-NA represent ‘‘1’’and ‘‘0’’binary digital codes.It exhibits good photo-regulating luminescence with very high contrast (85:1)in poly(methyl methacrylate)(PMMA)doped films.The strong fluorescence emission with high-contrast switching in the solid film could increase the density of the stored information.We also demonstrated its use in rewritable optical two-dimensional recording (Fig.2).Reversible,high-degree fluorescence modulation of a naphthalimide (NA)chromo-phore was realized by photoisomerization of the BTE subunit in polymer matrices.Considering its high-contrast photo-switchable fluorescence feature and the inherent characteristics of pristine bisthienylethene,BTE-NA can be suggested as a promising candidate for erasable optical data storage.12Another approach to develop fluorescent photochromic switches is to shift the luminescent wavelength into the near-IR region.For example,a new coplanar binuclear porphyrazine bearing six bis(trimethylthiophenyl)photochromic functional-ities at the periphery was synthesized in our lab recently,13shown in Scheme 3,which undergoes open-to-closed ring or closed-to-open ring photoisomerization in different quantum yields by irradiation with 365or 730nm light.The photo-cyclization of any BTE unit on this macrocycle wouldquenchFig.1The single molecular level fluorescent switch prepared by Irie and co-workers.10Scheme 2Structures and photo-switching behaviour ofBTE-NA.Fig.2Fluorescence image generated from 365-nm irradiation (5min)of the BTE-NA doped PMMA film through a dot-patterned contact mask.The light regions indicate luminescence,and the dark regions are non-luminescent (l ex :442nm).effectively the luminescence of the system.The compound also showed high extinction coefficients,which should be improved for BTE unit inherent characteristics,and near-IR lumines-cence regulation with photochromic reaction in a reversible manner by the photoisomerization of the BTE moiety,which would also be useful for fluorescent probes and optical readouts for erasable memory media.Some scientists have made an effort on increasing of fluorescence efficiency of BTEs.Kim and co-workers 14synthe-sized a new fluorescent photochromic diarylethene system by the oxidation of 1,2-bis(2-methyl-1-benzothiophene-3-yl)perfluorocyclopentene (BTF6)and the fluorescence quantum yield of its sulfonyl derivative 1,2-bis(2-methyl-1-benzothio-phene-1,1-dioxide-3-yl)perfluorocyclopentene (BTFO4)increased following photo-cyclization,opposite to that found for BTF6(Scheme 4).The oxidation of the sulfide groups of the benzothiophene rings of BTF6transformed the c-isomer from a very weak emitter to a highly fluorescent chromophore.Overall,the results of this study provide a new design synthetic strategy for the design of highly fluorescent materials with potential applications in non-destructive photo-chromic read-outs.Photochromic polymeric switchesIn usual one-component photochromic systems,they inter-convert between only two states:the ‘‘colourless’’and ‘‘coloured’’.On the other hand,in multi-component systems comprised of different kinds of photochromic units,reversible multi-state switching between several states can be realized by combination of the binary states of each component.In a two-component system,for example,four states could be produced,and eight states could be induced in a three-component system.Multi-component or multi-coloured sys-tems of diarylethenes were reported for the first time by Fernandez-Acebes and Lehn.15They demonstrated that the absorption properties of multi-component diarylethene mix-tures in solution as well as on silica-gel plates can be modulated by controlling different wavelength light.Irie and co-workers also reported a multi-component single crystal,which contains two or three types of compound that exhibit yellow,red,and blue colours;the crystal was expected to showa full range of colours upon photo-irradiation.16,17Another ideal approach to practical optical-electronic devices is the preparation of multi-component photochromic copolymers.Photochromic copolymers are the most promising solid materials in practical application because of their excellent rotating spread film property and photochromism in solid films.18Various types of one-component photochromic copolymers have been synthesized by radical polymerization,19oxidation polymerization,20Wittig polycondensation 21and ring-opening metathesis polymerization.22,23These photo-chromic copolymers show excellent photochromic properties in solution.We synthesized a two-component photochromic copolymer P(two-BTE-MMA)by radical polymerization (Fig.3).24We investigated multi-colour properties of P(two-BTE-MMA)in solution and in solid films,which exhibit multi-switchable photochromic behaviour with four states.This copolymer turned from colourless to a brick-brown colour upon irradiation with 402nm light.Then it turned back to its initial state upon irradiation with 521nm light.Upon further irradiation on colourless copolymer with 342nm light,it turned blue.When P(two-BTE-MMA)film was exposed simultaneously to 342and 402nm light,it turned bluish violet.Fig.4shows the multi-colour photochromic absorption changes upon irradiation with different light sources.Based on the experiments on P(two-BTE-MMA)it is inferred that the above colour changes originates from the photoreaction of the copolymer as shown in Scheme 5.When the two types of BTE units in P(two-BTE-MMA)were open-ring states (a(OO)),P(two-BTE-MMA)showsaScheme 3The photochromic process of a new binuclearporphyrazi-nato magnesium(II )complex.Scheme 4Molecular structures of BTF6and BTFO4as reported by Kim and co-workers.14Fig.3Two-component photochromic copolymerP(two-BTE-MMA).Fig.4Absorption changes of photochromic copolymer P(two-BTE-MMA)in a solid film upon irradiation with different wavelength light:(a)initial state,(b)402nm,(c)342nm,(d)342nm and 402nm.colourless initial state.Upon irradiation with 402nm light,the 2,3-bis(2,4,5-trimethyl-3-thienyl)-N -hydroxylpropylmaleiimide unit A in P(two-BTE-MMA)converts to its closed-ring form while the 1-(5-benzovinyl-2-methyl-3-thienyl)-2-(5-benzovinyl-(49-methacrylate propyl ether)-2-methyl-3-thienyl)cyclopen-tene unit B still remains in its open-ring state (b(CO));thus P(two-BTE-MMA)shows the colour of the closed isomers of A .Upon irradiation with 342nm light,the B unit in P(two-BTE-MMA)converts to its closed-ring isomer but the A unit is inactive to this irradiation wavelength;the state c(OC)thus shows the colour of the closed isomers of B .When the copolymer P(two-BTE-MMA)was exposed simultaneously to 342and 402nm light,it shows the colour of both closed-ring isomers A and B (d(CC))shown in Scheme 5.While the copolymer P(two-BTE-MMA)has still low photochromic content this copolymer provides a molecular design method for multi-switchable photochromic copolymers.This approach is more practical than doping several photo-active components in polymer matrices,or relying on the challenge of obtaining multi-component single crystals.Recently,Wigglesworth and Branda 25reported a family of multi-addressable,multi-coloured photo-responsible copoly-mers prepared by ring-opening metathesis polymerization (ROMP)(Fig.5),which could be interconverted between the several unique states.A three-component copolymer,for example,could be switched between the eight possible states.Because eachphotochromic diarylethene structure has unique absorption characteristics in both its ring-open and ring-closed states,the copolymers made up of them are multi-addressable.Copolymers CP 1,CP 2and CP 3(shown in Fig.5)contain two BTE units and can display four unique states.Copolymer CP 4contains three BTE units and can exhibit up to eight possible states in a single polymer.This type of material has potential application in multi-frequency optical data storage and display technologies.The photochromic conductivity of polymeric switching materials has also attracted considerable attention because of promising application in photovoltaic effects,non-linear-optical response,and photoconductivity.Recently,Irie and co-workers 26reported a novel photochromic conductivity switching copolymer (P(BTE-PF)shown in Fig.6)based on BTE and its photon-mode modulation in electric rge and twisted oligophenylene–fluorene (PF)units were introduced between diarylethene sites,and the separations on this copolymer main chain were as large as ca .4nm.The resulting co-polymer exhibits a high conductivity modulation,whose photochromic conversion ratio was as small as 35%in the solid film.The electrical conductivity can be switched quasi-reversibly many times by alternating irradiation with UV and visible light,so leading to potential as active materials in future photo-mode molecular memory and switching devices such as ‘‘photon mode’’RAM (random access memory).Kim and Lee synthesized 27a photochromic copolymer based on BTE and trimethylsilyl-substituted p -phenylene vinylene (TPV)(P(BTE-TPV)shown in Fig.7).The photo-isomerization of this copolymer was induced by incorporating a 2,3-bis(2-methylbenzo[b ]thiophen-3-yl)hexafluorocyclopen-tene unit,while TPV units directly connected to the diarylethene unit allowed the extension of p -electron deloca-lization.The conductivity of P(BTE-TPV)was significantly increased when the BTE unit was converted to a closed form (coloured)by irradiation with UV light.The conductivity switching was reversible by alternative irradiation of UVandScheme 5Photoreactions of copolymerP(two-BTE-MMA).Fig.5Structure of photochromic copolymers CP 1–CP 4prepared by Wigglesworth and Branda.25Fig.6Photoswitch conductivity of photochromic copolymer P(BTE-PF)reported by Irie and co-workers.26Fig.7The photochromic-conductivity process of polymer P(BTE-TPV)prepared by Kim and Lee.27visible light.In fact,in order to characterize clearly the photo-controlling conductivity of nanowires based on photochromic BTE,the photomodulating conductivity of a single BTE molecule attached on the surface of a gold electrode had been investigated by Feringa 9s group more recently.28Since photo-chromic BTE units have a limited photocyclization quantum yield,3it is hard to obtain excellent electron and energy transfer properties through the p -conjugation based on those photochromic polymeric or oligomeric nanowires.It is still a challenge to improve the on/off ratio for the photo-switchable polymers.Specifically,how to optically control such molecular wires (single molecule,oligomers and copolymers)by external stimuli becomes an important theme.Recently,our group 29synthesized a high-content pendant photochromic copolymer P(2-BTE-PF)with a BTE :fluorene mole ratio of 2:1(Fig.8)by typical palladium-catalyzed Suzuki coupling reaction,whose photochromic content was as high as 53wt%.P(2-BTE-PF)exhibits excellent photochro-mism both in solution and in solid films.Good-quality films of bulky material were obtained by spin-casting without a supporting polymer matrix.To further increase the number density of fluorescent BTE molecules in the polymer film and to also impart self processability,Park and co-workers 30designed and synthe-sized a novel class of ‘‘aggregation-induced enhanced emission’’(AIEE)-based fluorescent photochromic poly(DCS-BTE)(shown in Fig.9)by Knoevenagel condensa-tion,whose strong fluorescence in the neat polymer film could be photoswitched through highly efficient bistable photochro-mism (fluorescence switching ratio .10:1).Such a strongly enhanced fluorescence emission coupled with high-contrast photochromic switching in poly(DCS-BTE)film suggests their viable application to an erasable optical memory.Erasablefluorescence photo-imaging on the spin-coated poly(DCS-BTE)film was successfully demonstrated.Photochromic chiral switchesMolecules responsive to external stimuli are the basis for the studies of molecular switches and are the key elements in molecular level devices.If the output signals of molecular switches are chiral properties of molecular systems,they are regarded as chiral molecular switches.In fact,to understand,establish,and ultimately control chirality at the molecular and supramolecular level is one of the frontiers of molecular science.1,2The photo-regulation of chirality is fundamentally significant because it has the potential to influence novel liquid crystalline materials,non-destructive data storage,and cata-lytic asymmetric synthesis.In all cases,the combination of a high-performance photo-responsive molecular backbone and a chiral architecture that has an inherently large ability to interact and transfer its chirality to the environment is increasingly important to develop.Photochromic BTEs appropriately satisfy the demand because they undergo thermally irreversible photocyclization reactions with excellent photo-fatigue.They have been used with varying success in chiroptic applications.31–33Recently,Branda and co-workers 34reported a photo-responsive BTE derivative bearing chiral pinene-based arms (Fig.10),which underwent a stereo-selective photoinduced cyclization reaction to produce .98%of a single diastereomer.This system satisfies the requirements of a successful chiroptical photo-switch.It was thermally stable in both its states.It displays high stereo-selectivity in its photocyclization reactions,and it exhibits large changes in circular dichroism (CD)and ORD spectral properties.Feringa and co-workers 35,36reported the co-assembly of achiral with chiral diarylethene photochromic switches,accompanied by a dynamic selection and amplification in a supramolecular system (Fig.11).It exhibited the highly specific self-assembly features of low molecular weight gelators (LMWG)bearing multiple hydrogen bonding groups,which can be addressed and controlled by incorporation of a diarylethene photo-responsive unit.The co-assembly enables the transfer and propagation of chirality in the co-aggregate 9s supramolecular structure.Photochemical ring-closure can lock this chiral information at the molecular level.Diarylethene switches are presented in two,rapidly exchanging conforma-tions (P and M helicity).The photochemical ring-closure leads to the RR or SS enantiomers in equal amounts.It waspossibleFig.8A high-content pendant photochromic copolymer P(2-BTE-PF).Fig.9Photochromic reactions of poly(DCS-BTE)reported by Park and co-workers.30Fig.10Photochromic process of chiral switches prepared by Branda and co-workers.34to assemble cooperatively these chiral and achiral amide substituted perhydrodithienyl switches into supramolecular assemblies.The selection of only one of photoactive con-formers of the chiral switches 1o (and 2o )during aggregation controls the stereochemistry of achiral switch 3o ,resulting in chiral induction with up to eight-fold chiral amplification.Recently,we 37have synthesized a photochromic fluorescent organogel based on BTE bridged naphthalimides (abbreviated as BTE-NA-(chol)2,Scheme 6)and succeeded in constructing a multiple switching system responding to light,thermal stimuli,fluoride anions and proton stimuli.It exhibits excellent photochromic properties and defined thermoreversible proper-ties in an organogel system.The visual images of the BTE-NA-(chol)2gel with a network structure composed of fibrous aggregates were observed with a scanning electronic micro-scope (SEM)(Fig.12).At the same time,by taking advantage of the ability of F 2and protons to induce obviously different absorption and fluorescence spectra of BTE-NA-(chol)2in solution under sequential alternating UV/Vis light irradiation,a multiple switch was realized,which makes it promising for application in the fields of opto-and electronic smart materials,logic gates,fluorescence sensors and other molecular photonic devices.Interestingly,BTE-NA-(chol)2shows reversible chiral changes in the gel phase and in solution by light,F 2and proton stimulation.Fig.13shows the CD spectra changes of the BTE-NA-(chol)2gels with 365nm irradiation.The open form of BTE-NA-(chol)2gels has a weak negative Cotton effect at 410nm,Upon irradiation with 365nm light for 10min,a typically strong positive Cotton effect at 415nm was observed.It is inferred that the cholesterol chiral unit induced diarylethene chirality changes by irradiation with 365nm light.Fig.14shows the CD spectra changes of BTE-NA-(chol)2in THF solution (2.061024mol L 21)with 365nmirradiation,Fig.11The chiral diarylethene switches reported by Feringa and co-workers 35,36used for selection and amplification upon aggregation by hydrogen-bond formation;o =open form,c =closed form,UV:l =313nm,VIS:l .420nm.Scheme 6The structure and photochromic process of BTE-NA-(chol)2.Fig.12SEM images of BTE-NA-(chol)2gel (the gel was prepared from the toluene–ethanol (1:3v/v),[BTE-NA-(chol)2]=0.5wt%).Fig.13The CD spectra changes of BTE-NA-(chol)2gel with 365nm irradiation:(a)the open form of BTE-NA-(chol)2gel;(b)the closed form of BTE-NA-(chol)2gel.Fig.14The CD spectra changes of the BTE-NA-(chol)2in THF solution (2.061024mol L 21)with 365nm irradiation.(a)The open form of BTE-NA-(chol)2;(b)the closed form of BTE-NA-(chol)2;(c)the open form of BTE-NA-(chol)2upon titration with F 2;(d)BTE-NA-(chol)2upon titration with F 2followed by irradiation at 365nm;(e):BTE-NA-(chol)2upon titration with F 2,irradiation at 365nm,followed by titration with protons.F 2and proton stimulation.Two evident Cotton effects at 400nm and around 480nm were observed in the open form of BTE-NA-(chol)2in solution (Fig.14,curve (a)).Upon irradiation with 365nm light,the CD spectra changed (Fig.14,curve (b)).Upon titration with F 2of the open form of BTE-NA-(chol)2,the CD spectra changed again (Fig.14,curve (c));then upon irradiation with 365nm light,the CD spectra changed from curve (c)to curve (d);upon titration with protons the CD spectra changed to (e).From Fig.14,we can see that the CD spectra of BTE-NA-(chol)2shows sharp changes upon titration with F 2.There are two Cotton effects,one is a positive Cotton effect at 353nm (19M 21cm 21),the other is a negative Cotton effect at 450nm (234M 21cm 21).In addition,BTE-NA-(chol)2shows a reversible fluorescent organogelator molecular switch.Fig.15shows the fluorescent emission spectral changes of BTE-NA-(chol)2in a gel phase in which a weak fluorescence emission peak around 470nm is observed.Upon irradiation with 313nm light,the fluorescence intensity is gradually increased.The obvious fluorescence changes were observed by the naked eye (Fig.16).Molecular logic gates are increasingly important in attribut-ing chemical reactivity to molecular devices.Specific input signals of basic logic gates can be programmed into single molecules that generate readable output signals,such as fluorescence or UV/Vis light.38–41By taking advantage of BTE-NA-(chol)2multi-mode switching processes,a compli-cated molecular logic gate with four optical outputs respond-ing to four-inputs based on the truth table shown in Table 1is constructed,in which BTE-NA-(chol)2starts its switching characteristics with the initial state in the dark,i.e.,all inputs does not stimulate the system at initial step.The inputs I1,I2,I3and I4are UV light (365nm),visible light (¢510nm),fluoride ion and proton,respectively.The four optical outputs O1,O2,O3and O4are the absorption at 550nm,the fluorescence emission at 450nm,the absorption at 500nm and the fluorescence emission at 570nm,respectively.This first entry with an inputs string is 0000and the outputs string is 0000.Then the second entry starts with UV irradiation (I1on),which induces BTE-NA-(chol)2changing colour to red with strong fluorescence,i.e.O1and O2are both on,and this entry is with the input string of 1000and the output string of 1100.Then if I1(UV)is switched back to off in this case,the input string 0000is restored.However,the corresponding output string should remain as 1100,because that the molecular switch has memorized the influence of the input in the previous step (referred to ‘‘Memory 29entry’’in the truth Table).As mentioned above the memory state could be erased by the irradiation of visible light and BTE-NA-(chol)2returns its initial state,which is indicated by the fourth entry in the truth Table with the inputs string of 0100and outputs string of 0000.The molecular switch BTE-NA-(chol)2underwent a whole cycle responding to UV/visible irradiation,which are referred by the four entries in the truth Table.Besides UV/visible irradiation,this particular molecular switch has also ‘‘memory’’effect between solution and gel phases,if temperature acts as a thermal input (not shown in the truth Table).In addition,the four entries with I1(UV)and I2(Visible)both ‘‘on’’at the same time are meaningless for the photochromic system,these states are undefined on the output and therefore they are not listed in the truth Table.Two-photon absorption (TPA)is a nonlinear optical process in which a chromophore that would normally be excited by a single-photon of shorter wavelength is excited by two photons of longer wavelengths.Two-photon absorption (TPA)photo-chromic materials are one class of attractive TPAmaterials,Fig.15Fluorescent spectra (excited at 355nm)of the BTE-NA-(chol)2gel:the open-ring isomer (—)and the photostationary state (---)(0.5wt/v%)upon irradiation by 365nm light at room temperature.Inset curves show the fluorescent change value at maximum emission wavelength with irradiationtimes.Fig.16Fluorescent images of the BTE-NA-(chol)2gel:the open-ring isomer (a)and in the photostationary state (b)upon irradiation by 313nm light at room temperature.Table 1The truth tableEntryI1I2I3I4O1O2O3O4100000000210001100Memory 2900001100401000000500100011600010000710101111Memory 790010111190110001110010100001110011100Memory 119111。

聚多巴胺辅助的液相沉积法制备二氧化钛涂层毛细管柱及其在电色谱中的应用李向良;盛强;李雪松;王其伟;郭勇;刘淑娟【摘要】利用多巴胺的自氧化聚合反应在毛细管内壁引入聚多巴胺涂层,并以聚多巴胺涂层作为连接臂辅助二氧化钛前躯体氟钛酸铵液相沉积制备了二氧化钛涂层毛细管柱.该方法制备过程简单,条件温和,形成的涂层稳固.采用X射线光电子能谱(XPS)、扫描电镜(SEM)和测定电渗流变化对涂层性质进行了表征.选择5种阴离子、生物碱作为分离对象,考察了缓冲液组成、浓度和pH值等因素对该涂层柱毛细管电色谱分离性能的影响.结果显示,在优化条件下,5种阴离子及生物碱在该涂层毛细管柱上均能得到较好的分离.【期刊名称】《分析测试学报》【年(卷),期】2015(034)001【总页数】7页(P73-79)【关键词】聚多巴胺;二氧化钛;毛细管电色谱;无机阴离子;生物碱【作者】李向良;盛强;李雪松;王其伟;郭勇;刘淑娟【作者单位】中国石化胜利油田分公司地质科学研究院,山东东营257015;中国石化胜利油田分公司地质科学研究院,山东东营257015;中国石化胜利油田分公司地质科学研究院,山东东营257015;中国石化胜利油田分公司地质科学研究院,山东东营257015;中国科学院兰州化学物理研究所西北特色植物资源化学重点实验室甘肃省天然药物重点实验室,甘肃兰州730000;中国科学院兰州化学物理研究所西北特色植物资源化学重点实验室甘肃省天然药物重点实验室,甘肃兰州730000【正文语种】中文【中图分类】O657.8;TQ425.222毛细管电泳是近年发展起来的高效分离分析技术，具有分离效率高、分析速度快、样品及溶剂消耗量小、分离模式多等优点，因此被广泛用于样品的分离分析。

但该方法也存在不足，如对碱性化合物的分离存在严重吸附，某些阴离子的出峰时间长，甚至无法被检测。

金属氧化物涂层柱通过引入金属氧化物涂层，改变毛细管内表面带电状态，影响电渗流进而影响分离，可以作为毛细管区带电泳的一种改进。

V o l.26高等学校化学学报　N o.4　2005年4月 CH E M I CAL JOU RNAL O F CH I N ESE UN I V ER S IT IES 751～753　[研究简报]导电原子力显微镜对蛋白质在分子水平上的电学表征赵健伟1,王　楠2(1.南京大学化学化工学院,南京210093;2.重庆大学化学化工学院,重庆400044)关键词　导电原子力显微镜;蛋白质;介电强度中图分类号　O641 文献标识码　A 文章编号　025120790(2005)0420751203蛋白质电子传递的研究不仅对阐述生物能量传递具有重要的意义,而且有助于促进生物分子在分子电子器件中的应用.金属蛋白以其固有的电化学和电学特性,在光合作用和呼吸作用中起到重要作用.其中铜蓝蛋白具有良好的电化学性质和明确的分子结构,常常用作研究蛋白质电子传递的模型分子[1].很多具有微观尺度表征能力的分析仪器可用于研究表面吸附的蛋白质分子.扫描隧道显微术(STM)已成功地用于研究导电基底上的蛋白质单分子膜[2,3].然而,STM的工作原理使得真正意义上的金属2分子2金属结很难实现[4].导电原子力显微镜(C2A FM)由于以接触模式进行工作而避免了这个不足.它不仅可以在纳米尺度上表征表面形貌,而且还可以直接得到样品的电学性质[5～8].本文利用针尖组装的方法,从分子水平上研究了蛋白质的电学性质.1　实验部分1.1　试剂与仪器　铜蓝蛋白(A zu rin)由莱顿化学学院提供;接触模式C2A FM扫描管(M o lecu larI m aging,P icoSPM);导电针尖(M ik rom asch,A u Si3N4,弹性系数为210N m).1.2　实验过程　将清洁过的镀金探针在5mm o l L的铜蓝蛋白醋酸缓冲溶液(pH=4164)中浸泡3h 后,用超纯水冲洗.干燥后将针尖安装在C2A FM扫描管上,然后与新劈裂的高定向热解石墨(HO PG)基底相接触,施加偏压于高定向热解石墨.恒力下测定电流电压关系曲线(I2V曲线).测定不同外力下的I2V曲线时,每次施加压力后静置10s,再开始测量I2V曲线.在每个固定外力下,测定20条I2V曲线以得到电阻的平均值.实验在室温(20±2)℃和大气环境湿度为40%～50%下进行.2　结果与讨论2.1　蛋白质的导电行为和力的关系　实验中发现,当在针尖上施加一个大于5nN的正压力时,针尖2蛋白质2HO PG体系可形成良好的电接触,这样可测得相应的电流响应.图1给出了不同外力下铜蓝蛋白典型的电流2电压关系曲线.在电位扫描范围内,I2V曲线稳定,具有很好的重现性.蛋白质的电导或电阻可由其斜率求得.图2给出了蛋白质的电阻值(每个外力下的平均电阻由20条I2V曲线统计得到)和所受压力的关系.由图2中的数据误差可看出,利用针尖修饰的方法得到的电阻稳定性很好.对应每一个压力,电阻的标准偏差一般小于10%.从图3的实线还可看出,电阻随外力增大而减小.特别是当外力小于40 nN时,蛋白质的电阻和外力几乎呈指数关系(图3中的电流采用半对数坐标).当外加压力过大时,蛋白质被严重压缩.此时分子内的斥力将使蛋白质分子向外流动变形,直至蛋白质的结构被彻底破坏.本实验中,当外力为87nN时,在零偏压附近电流从-10nA跃变到10nA.当外力减小或重新使探针和基底接触时,这种现象依旧不变.表明在高外力作用下蛋白质结构收稿日期:2004204220.基金项目:国家自然科学基金(批准号:20435010)资助.联系人简介:赵健伟(1972年出生),男,教授,主要从事分子电化学和分子电子学研究.E2m ail:zhao j w@F ig .1　Prote i n I -V curves under var ious forceloads at a scan rate of 4V sFo rce loads are 610,1216,1911,2515,3119,3816,4511,5117,5812,6417,7112and 8710nN ,respectively F ig .2　Force dependence of the prote i n resist ance evaluated fro m the slopes of 20I -V curves for each force i n the low bi as reg i m e被完全破坏,导致探针和基底直接接触.这种临界外力可间接反映出生物分子的机械强度.多次测量得到铜蓝蛋白的临界外力在(80±20)nN 范围内.2.2　介电击穿现象　当针尖压力小于2nN 时,在-1～1V 的偏压范围内无电流通过蛋白质.作为一F ig .3　I -V characters at force lower than 2nNScan rate(V ・s -1):a .015;b .10;c .50;d .10.种生物分子的介电材料,蛋白质分子阻碍电子传递.然而,当偏压增大到一定程度时,观察到了蛋白质的介电击穿现象.正偏压扫描时典型的电流2电压曲线见图3.从每条曲线上都可得到一个电压阈值.从图3可看出,当电压未达到阈值之前,电路中无电流流过;在达到阈值的一瞬间,电流突然增大到仪器测量的最大极限(10nA ).当电压返向扫描经过阈值时,电流曲线并不能和原曲线重合,如图3曲线d 所示.在达到零偏压之前,电流始终大于10nA ,在低于零偏压时,电流突然减小到-10nA (仪器测量负方向的最大极限).这种现象被归结为介电击穿现象[6,9].另外,还研究了扫描速度和击穿电压的关系.图3记录了不同扫描速度下的电流2电压曲线,曲线a ,b 和c 对应的扫描速度分别为015,10和50V s .相应的击穿电压列于表1.Table 1　The ram p speed dependence of the breakdown volt age of prote i n under a force of 2nNScan rate(V ・s -1)B reakdow n vo ltage Samp le num ber 015(Po sitive )3132±01321010(Po sitive )3187±01331050(Po sitive )8112±1125510(N egative )-5119±013410 由表1可见,高扫描速度(50V s )将导致击穿电压明显增加.然而当扫描速度为015和10V s 时,虽然速度相差20倍,但I 2V 曲线并无明显差别.在对块体材料例如微米介电薄膜的介电击穿研究中,已得出结论,只有当介电薄膜两边积累足够多的电荷时,介电击穿现象才会发生[10,11].尽管块体材料和分子材料有着本质上的差别,但块体材料介电击穿的研究也预示着过量的电荷积累是导致蛋白质等分子材料介电击穿的重要原因之一.为了在蛋白质表面积累足够的电荷,必须有充足的时间使电荷注入到蛋白质中,否则就需要施加更高的偏压以提供足够的驱动力进行电荷注入.这就是高扫描速度下击穿电压增高的主要原因.然而,在015～10V s 范围内,击穿电压并无很大区别,表明10V s 的扫描速度可以提供足够的时间,使电荷在蛋白质中积累.根据击穿电压和蛋白质的空间尺寸(径向尺寸约3)257 高等学校化学学报V o l.26114GV m 之间.负偏压扫描时,可观察到与正偏压扫描时的类似现象,在偏压达到阈值后发生介电击穿.唯一的差别是击穿电压为-5119V ,其绝对值略大于正偏压扫描的击穿电压.参　考　文　献[1]　A dm an E .T ..A dvances in P ro tein Chem istry [J ],1991,42:145—197[2]　Ch i Q .J .,Zhang J .D .,A ndersen J .E .T .et a l ..Journal of Physical Chem istry B [J ],2001,105:4669—4679[3]　R inaldi R .,B iasco A .,M arucci o G .et a l ..A pp lied Physics L etters [J ],2003,82:472—474[4]　K remm er S .,T eichert C .,P isch ler E .et a l ..Surface and Interface A nalysis [J ],2002,33:168—172[5]　Kelley T .W .,Granstrom E .L .,F risbie C .D ..A dvanced M aterials [J ],1999,11(3):261—262[6]　Zhao J .W .,U o sak i K ..A pp lied Physics L etters [J ],2003,83:2034—2036[7]　Zhao J .W .,D avis J .J ..N ano techno logy [J ],2003,14:1023—1028[8]　Zhao J .W .,D avis J .J .,Sam son M ..J .Am .Chem .Soc .[J ],2004,126:5601—5609[9]　A ra M .,Graaf H .,T ada H ..A pp lied Physics L etters [J ],2002,80(14):2565—2567[10]　M barga S .O .,M alec D .,Zebouch iN .et a l ..Journal of E lectro statics [J ],1997,40(1):355—361[11]　L uo E .Z .,L in S .,X ie Z .et a l ..M aterials Characterizati on [J ],2002,48(2—3):205—210Electr ic ity Character iza tion of M eta lloprote i n a t M olecularL evel by Conducti ng A tom ic Force M icroscopyZHAO J ian 2W ei 13,W AN G N an2(1.D ep art m ent of Che m istry ,N anj ing U niversity ,N anj ing 210093,Ch ina ;2.D ep art m ent of Che m istry and Che m ical E ng ineering ,Chong qing U niversity ,Chong qing 400044,Ch ina )Abstract T he electric and dielectric p rop erties of m etallop ro tein ,azu rin ,w ere studied at real m o lecu lar level by u sing conducting atom ic fo rce m icro scopy (C 2A FM ).U nder a fo rce low er than 2nN ,dielectric b reakdow n w as ob served .W hen reliab le electrical con tact betw een electrodes and p ro tein is ach ieved under a fo rce greater than 5nN ,w ell 2behaved cu rren t 2vo ltage characters are revealed ,and dep enden t on the fo rce load .Keywords Conducting atom ic fo rce m icro scop y ;P ro tein ;D ielectric strength(Ed .:S ,X )欢迎订阅《Chem ica l Research i n Ch i nese Un iversities 》《Chem ical R esearch in Ch inese U niversities 》(高等学校化学研究,英文版)是中华人民共和国教育部委托吉林大学主办的化学学科综合性学术刊物,1984年创刊。