Synergetic effects for p-nitrophenol degradation were observed in the combination of two-advanced oxidation processes, UV/Fe3+ and electrocatalysis. The enhancement of removal rate for p-nitrophenol and COD was aroun...Synergetic effects for p-nitrophenol degradation were observed in the combination of two-advanced oxidation processes, UV/Fe3+ and electrocatalysis. The enhancement of removal rate for p-nitrophenol and COD was around 123% and 278%, respectively. The possible contributions for the synergetic effects were the electrochemically regeneration of ferric ion and the role of the oxygen that formed on the anode.展开更多
Porous photocatalysts are promising materials capable of simultaneously adsorbing and oxidizing/reducing target species,showing great potentials in environmental remediation and energy generation.This review offered a...Porous photocatalysts are promising materials capable of simultaneously adsorbing and oxidizing/reducing target species,showing great potentials in environmental remediation and energy generation.This review offered a comprehensive overview of the recent progress in design,fabrication,and applications of porous photocatalysts,including carbon-based semiconductors,metal oxides/sulfides,metal–organic frameworks,and adsorbent–photocatalyst hybrids.The fundamental understanding of the structure–performance relationships of porous materials together with the in-depth insights into the synergetic effects between adsorption and photocatalysis was presented.The strategies to further improve the photocatalytic activity of porous photocatalysts were proposed.This review would provide references and outlooks of constructing efficient porous materials for adsorptive and photocatalytic removal of pollutants and energy production.展开更多
An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis.This platform utilizing cadmium sulfide semiconductor...An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis.This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and nickel complexes as transition metal catalysts provided a variety of organophosphorus compounds from readily available aryl and vinyl halides,as well as aryl triflates,with generally a good-to-excellent reaction efficiency(31 examples,46%-98%yields).The current protocol features mild reaction conditions,a broad substrate scope,recyclability of photocatalysts,and inexpensive catalysts,thus defining the practical and economic proprieties of the present catalyst system.展开更多
The integration of distributed generation brings in new challenges for the operation of distribution networks,including out-of-limit voltage and power flow control.Soft open points(SOP)are new power electronic devices...The integration of distributed generation brings in new challenges for the operation of distribution networks,including out-of-limit voltage and power flow control.Soft open points(SOP)are new power electronic devices that can flexibly control active and reactive power flows.With the exception of active power output,photovoltaic(PV)devices can provide reactive power compensation through an inverter.Thus,a synergetic optimization operation method for SOP and PV in a distribution network is proposed.A synergetic optimization model was developed.The voltage deviation,network loss,and ratio of photovoltaic abandonment were selected as the objective functions.The PV model was improved by considering the three reactive power output modes of the PV inverter.Both the load fluctuation and loss of the SOP were considered.Three multi-objective optimization algorithms were used,and a compromise optimal solution was calculated.Case studies were conducted using an IEEE 33-node system.The simulation results indicated that the SOP and PVs complemented each other in terms of active power transmission and reactive power compensation.Synergetic optimization improves power control capability and flexibility,providing better power quality and PV consumption rate.展开更多
The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added valu...The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.展开更多
Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catal...Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catalyst (Fe-PEI-CN) by codoping graphitic carbon nitride (CN) with polyethyleneimine ethoxylated (PEI) and Fe species, which demonstrated high activity during p-chlorophenol (p-ClPhOH) degradation via H_(2)O_(2) from the photocatalytic process. The relationship between the catalytic efficiency and the structure was explored using diff erent characterization methods. The Fe modification of CN was achieved through Fe-N coordination, which ensured high dispersion of Fe species and strong stability against leaching during liquid- phase reactions. The Fe modification initiated the Fenton reaction by activating H_(2)O_(2) into ·OH radicals for deep degradation of p-ClPhOH. In addition, it eff ectively promoted light absorption and photoelectron-hole (e-h ^(+) ) separation, corresponding to improved photocatalytic activity. On the other hand, PEI could significantly improve the ability of CN to generate H_(2)O_(2) through visible light photocatalysis. The maximum H_(2)O_(2) yield reached up to 102.6 μmol/L, which was 22 times higher than that of primitive CN. The cooperation of photocatalysis and the self-Fenton reaction has led to high-activity mineralizing organic pollutants with strong durability, indicating good potential for practical application in wastewater treatment.展开更多
A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state d...A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state depends on the thermal parameter,catalyzed photon number and squeezing parameter.We then analyze the nonclassical properties by examining the photon number distribution,photocount distribution and partial negativity of the Wigner function.Our findings indicate that nonclassicality can be achieved through the implementation of multiphoton catalysis operations and modulated by the thermal parameter,catalyzed photon number and squeezing parameter.展开更多
Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has...Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.展开更多
To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environment...To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environmental processing applications due to their exceptionally high surface areas,large pore sizes,and enough pore volumes.These properties might enhance the performance of materials concerning adsorption/catalysis capability,durability,and stability.In this review,we enumerate the ordered mesoporous materials as adsorbents/catalysts and their modifications in water pollution treatment from the past decade,including heavy metals(Hg^(2+),Pb^(2+),Cd^(2+),Cr^(6+),etc.),toxic anions(nitrate,phosphate,fluoride,etc.),and organic contaminants(organic dyes,antibiotics,etc.).These contributions demonstrate a deep understanding of the synergistic effect between the incorporated framework and homogeneous active centers.Besides,the challenges and perspectives of the future developments of ordered mesoporous materials in wastewater treatment are proposed.This work provides a theoretical basis and complete summary for the application of ordered mesoporous materials in the removal of contaminants from aqueous solutions.展开更多
Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are ...Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are becoming popular materials because of their low cost, high electron conductivity, and controllable surface property. At the stage of catalysts preparation, the rational design of active sites is necessary for the substantial improvement of activity of catalysts. To date, the reported design strategies are mainly about synthesis mechanism and synthetic method. The level of understanding of design strategies of carbon-based single atom catalysts is requiring deep to be paved. The design strategies about manufacturing defects and coordination modulation of catalysts are presented. The design strategies are easy to carry out in the process of drawing up preparation routes. The components of carbon-based SACs can be divided into two parts: active site and carbon skeleton. In this review, the manufacture of defects and coordination modulation of two parts are introduced, respectively. The structure features and design strategies from the active sites and carbon skeletons to the overall catalysts are deeply discussed.Then, the structural design of different nano-carbon SACs is introduced systematically. The characterization of active site and carbon skeleton and the detailed mechanism of reaction process are summarized and analyzed. Next, the applications in the field of electrocatalysis for oxygen conversion and hydrogen conversion are illustrated. The relationships between the superior performance and the structure of active sites or carbon skeletons are discussed. Finally, the conclusion of this review and prospects on the abundant space for further promotion in broader fields are depicted. This review highlights the design and preparation thoughts from the parts to the whole. The detailed and systematic discussion will provide useful guidance for design of SACs for readers.展开更多
Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with th...Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.展开更多
The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and deba...The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.展开更多
The main idea of this paper is what the resource of the serious error of the widely popular Chemical Reaction Mode catalysis Mechanism-CRMM is. The wrong definition of “catalysis, catalyst” by the catalytic academia...The main idea of this paper is what the resource of the serious error of the widely popular Chemical Reaction Mode catalysis Mechanism-CRMM is. The wrong definition of “catalysis, catalyst” by the catalytic academia boss leads to the wrong interpretation of “catalysis, catalyst” by linguists (Dictionary). The interpretation of “catalysis, catalyst” in a dictionary is misleading. The most fundamental reason for this error is that catalysis experts always believe that catalysts participate in chemical reactions. The result will appear as a series of impossible events. Such as catalysis cyclic reaction, opinions vary intermedium, catalysts repeated decomposition—formation, oxidation-reduction or life and death (enzyme), Sabatier’s principle and Boudart’s principle. The wrong theory leads the research and application of catalysts to the bottomless abyss, and industrial production suffers great losses. Electron Orbital Deformation-Recovere cyclic catalysis Mechanism-EODRM or Electron Cyclic Donate-Adopt catalysis Mechanism-ECDAM shows that the catalytic phenomenon is a physical phenomenon, not a chemical phenomenon, the catalyst does not participate in chemical reactions, only contact is the electron donate-adopt cycle, is the electron orbital deformation recovery cycle Chinese and foreign scholars should change the interpretation on the “catalysis, catalyst”, or add two new words: “contact and contactor”, it is to give up “catalysis, catalyst” altogether.展开更多
Non-aqueous phase enzymatic catalysis technology has been widely ap- plied in the area of food additives production. This paper reviewed the types of re- action medium of non-aqueous phase enzymatic catalysis reaction...Non-aqueous phase enzymatic catalysis technology has been widely ap- plied in the area of food additives production. This paper reviewed the types of re- action medium of non-aqueous phase enzymatic catalysis reaction, introduced the application of non-aqueous phase enzymatic catalysis technology in catalysis of L-ascorbic (isoascorbic) acid esters, short-chain acid esters, sugar esters, vitamin A esters, vi- tamin E esters, and other food additives, and finally predicted the prospects of non- aqueous phase enzymatic catalysis technology.展开更多
Hydrogenation and ammoniation of SrTiOa (STO), a normal ultraviolet photocatalyst, were performed by annealing STO(100) in Hz:N2=5%:95% and NH3, respectively, at various temperatures T. It was found that hydroge...Hydrogenation and ammoniation of SrTiOa (STO), a normal ultraviolet photocatalyst, were performed by annealing STO(100) in Hz:N2=5%:95% and NH3, respectively, at various temperatures T. It was found that hydrogenation at T≥900℃ remarkably enhanced the UV photocatalytic ability of STO, but the visible-light photocatalysis was still unavailable, while ammoniation at T≥800℃ introduced the N doping, resulting in visible-light photocat- alytie activity. Furthermore, when a hydrogenated STO was subjected to ammoniation, the visible-light photocatalytie ability was nearly the same as that of the ammoniated one; but the hydrogenation of an ammoniated one significantly enhanced visible-light photoeatalysis, indicating a synergetic effect of hydrogenation and ammoniation. Discussions and identifications have been made to analyze these results.展开更多
Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. ...Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.展开更多
We introduced bipyridine ligands into a series of two‐dimensional (2D) covalent organic frame‐works (COFs) using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde (2,2’‐BPyDCA) as a component in the mixed building bl...We introduced bipyridine ligands into a series of two‐dimensional (2D) covalent organic frame‐works (COFs) using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde (2,2’‐BPyDCA) as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium(II) acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd(II) ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd(II)‐loaded COFs exhibited good catalytic activity for the Heck reaction.展开更多
This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentratio...This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...展开更多
文摘Synergetic effects for p-nitrophenol degradation were observed in the combination of two-advanced oxidation processes, UV/Fe3+ and electrocatalysis. The enhancement of removal rate for p-nitrophenol and COD was around 123% and 278%, respectively. The possible contributions for the synergetic effects were the electrochemically regeneration of ferric ion and the role of the oxygen that formed on the anode.
基金financially supported by the National Natural Science Foundation of China(21706224,21671075)the China Postdoctoral Science Foundation(2020M672810)+3 种基金the Science and Technology Innovation Commission of Shenzhen Municipality(JCYJ20180307123906004 and JCYJ20190808181003717)the Research Grants Council of Hong Kong(CityU 21301817,11215518)the Strategic Research Grants from City University of Hong Kong(Ref:CityU 11306419 and 11308420)the Applied Research Grant from City University of Hong Kong(Ref:CityU 9667217)。
文摘Porous photocatalysts are promising materials capable of simultaneously adsorbing and oxidizing/reducing target species,showing great potentials in environmental remediation and energy generation.This review offered a comprehensive overview of the recent progress in design,fabrication,and applications of porous photocatalysts,including carbon-based semiconductors,metal oxides/sulfides,metal–organic frameworks,and adsorbent–photocatalyst hybrids.The fundamental understanding of the structure–performance relationships of porous materials together with the in-depth insights into the synergetic effects between adsorption and photocatalysis was presented.The strategies to further improve the photocatalytic activity of porous photocatalysts were proposed.This review would provide references and outlooks of constructing efficient porous materials for adsorptive and photocatalytic removal of pollutants and energy production.
基金the National Science Foundation of China(21822103,21820102003,21772052,21772053,21572074,21472057)the Program of Introducing Talents of Discipline to Universities of China(111 Program,B17019)+1 种基金the Natural Science Foundation of Hubei Province(2017AHB047)the International Joint Research Center for Intelligent Biosensing Technology and Health for support of this research~~
文摘An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis.This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and nickel complexes as transition metal catalysts provided a variety of organophosphorus compounds from readily available aryl and vinyl halides,as well as aryl triflates,with generally a good-to-excellent reaction efficiency(31 examples,46%-98%yields).The current protocol features mild reaction conditions,a broad substrate scope,recyclability of photocatalysts,and inexpensive catalysts,thus defining the practical and economic proprieties of the present catalyst system.
基金supported by the Science and Technology Project of SGCC(kj2022-075).
文摘The integration of distributed generation brings in new challenges for the operation of distribution networks,including out-of-limit voltage and power flow control.Soft open points(SOP)are new power electronic devices that can flexibly control active and reactive power flows.With the exception of active power output,photovoltaic(PV)devices can provide reactive power compensation through an inverter.Thus,a synergetic optimization operation method for SOP and PV in a distribution network is proposed.A synergetic optimization model was developed.The voltage deviation,network loss,and ratio of photovoltaic abandonment were selected as the objective functions.The PV model was improved by considering the three reactive power output modes of the PV inverter.Both the load fluctuation and loss of the SOP were considered.Three multi-objective optimization algorithms were used,and a compromise optimal solution was calculated.Case studies were conducted using an IEEE 33-node system.The simulation results indicated that the SOP and PVs complemented each other in terms of active power transmission and reactive power compensation.Synergetic optimization improves power control capability and flexibility,providing better power quality and PV consumption rate.
基金supported by the National Key R&D Program of China (2018YFA0901700)National Natural Science Foundation of China (22278241)+1 种基金a grant from the Institute Guo Qiang, Tsinghua University (2021GQG1016)Department of Chemical Engineering-iBHE Joint Cooperation Fund。
文摘The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.
基金the National Key Research and Development Program of China (No. 2020YFA0211004)Key Grant of Nation Science Funding of China (No. 22236005)+5 种基金Nation Science Funding of China (No. 22376141)Ministry of Education of China (No. PCSIRT_IRT_16R49)“111” Innovation and Talent Recruitment Base (D18020)Shanghai Government (No. 20ZR1440700)Shanghai Engineering Research Center of Green Energy Chemical Engineering (No. 18DZ2254200)Scientific and Technological Innovation Team for Green Catalysis and Energy Materialien Yunnan Institutions of Higher Learning, and Surface project of Yunnan Province science and technology Department (No. 20210 A070001-050).
文摘Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catalyst (Fe-PEI-CN) by codoping graphitic carbon nitride (CN) with polyethyleneimine ethoxylated (PEI) and Fe species, which demonstrated high activity during p-chlorophenol (p-ClPhOH) degradation via H_(2)O_(2) from the photocatalytic process. The relationship between the catalytic efficiency and the structure was explored using diff erent characterization methods. The Fe modification of CN was achieved through Fe-N coordination, which ensured high dispersion of Fe species and strong stability against leaching during liquid- phase reactions. The Fe modification initiated the Fenton reaction by activating H_(2)O_(2) into ·OH radicals for deep degradation of p-ClPhOH. In addition, it eff ectively promoted light absorption and photoelectron-hole (e-h ^(+) ) separation, corresponding to improved photocatalytic activity. On the other hand, PEI could significantly improve the ability of CN to generate H_(2)O_(2) through visible light photocatalysis. The maximum H_(2)O_(2) yield reached up to 102.6 μmol/L, which was 22 times higher than that of primitive CN. The cooperation of photocatalysis and the self-Fenton reaction has led to high-activity mineralizing organic pollutants with strong durability, indicating good potential for practical application in wastewater treatment.
基金supported by the National Natural Science Foundation of China (Grant No.11347026)the Natural Science Foundation of Shandong Province,China (Grant Nos.ZR2020MA085 and ZR2020MF113)。
文摘A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state depends on the thermal parameter,catalyzed photon number and squeezing parameter.We then analyze the nonclassical properties by examining the photon number distribution,photocount distribution and partial negativity of the Wigner function.Our findings indicate that nonclassicality can be achieved through the implementation of multiphoton catalysis operations and modulated by the thermal parameter,catalyzed photon number and squeezing parameter.
文摘Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.
基金supported by the National Natural Science Foundation of China(52370041)National Natural Science Foundation of China(21976134 and 21707104)State Key Laboratory of Pollution treatment and Resource Reuse Foundation(NO.PCRRK21001).
文摘To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environmental processing applications due to their exceptionally high surface areas,large pore sizes,and enough pore volumes.These properties might enhance the performance of materials concerning adsorption/catalysis capability,durability,and stability.In this review,we enumerate the ordered mesoporous materials as adsorbents/catalysts and their modifications in water pollution treatment from the past decade,including heavy metals(Hg^(2+),Pb^(2+),Cd^(2+),Cr^(6+),etc.),toxic anions(nitrate,phosphate,fluoride,etc.),and organic contaminants(organic dyes,antibiotics,etc.).These contributions demonstrate a deep understanding of the synergistic effect between the incorporated framework and homogeneous active centers.Besides,the challenges and perspectives of the future developments of ordered mesoporous materials in wastewater treatment are proposed.This work provides a theoretical basis and complete summary for the application of ordered mesoporous materials in the removal of contaminants from aqueous solutions.
基金funded by the National Natural Science Foundation of China (Nos. 22279118, 31901272, 21401168, U1204203)National Science Fund for Distinguished Young of China (No. 22225202)+1 种基金Young Top Talent Program of Zhongyuan-YingcaiJihua (No. 30602674)Top-Notch Talent Program of Henan Agricultural University (No. 30501034)。
文摘Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are becoming popular materials because of their low cost, high electron conductivity, and controllable surface property. At the stage of catalysts preparation, the rational design of active sites is necessary for the substantial improvement of activity of catalysts. To date, the reported design strategies are mainly about synthesis mechanism and synthetic method. The level of understanding of design strategies of carbon-based single atom catalysts is requiring deep to be paved. The design strategies about manufacturing defects and coordination modulation of catalysts are presented. The design strategies are easy to carry out in the process of drawing up preparation routes. The components of carbon-based SACs can be divided into two parts: active site and carbon skeleton. In this review, the manufacture of defects and coordination modulation of two parts are introduced, respectively. The structure features and design strategies from the active sites and carbon skeletons to the overall catalysts are deeply discussed.Then, the structural design of different nano-carbon SACs is introduced systematically. The characterization of active site and carbon skeleton and the detailed mechanism of reaction process are summarized and analyzed. Next, the applications in the field of electrocatalysis for oxygen conversion and hydrogen conversion are illustrated. The relationships between the superior performance and the structure of active sites or carbon skeletons are discussed. Finally, the conclusion of this review and prospects on the abundant space for further promotion in broader fields are depicted. This review highlights the design and preparation thoughts from the parts to the whole. The detailed and systematic discussion will provide useful guidance for design of SACs for readers.
文摘Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.
基金supported by the National Natural Science Foundation of China(U2032151,22272059)。
文摘The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.
文摘The main idea of this paper is what the resource of the serious error of the widely popular Chemical Reaction Mode catalysis Mechanism-CRMM is. The wrong definition of “catalysis, catalyst” by the catalytic academia boss leads to the wrong interpretation of “catalysis, catalyst” by linguists (Dictionary). The interpretation of “catalysis, catalyst” in a dictionary is misleading. The most fundamental reason for this error is that catalysis experts always believe that catalysts participate in chemical reactions. The result will appear as a series of impossible events. Such as catalysis cyclic reaction, opinions vary intermedium, catalysts repeated decomposition—formation, oxidation-reduction or life and death (enzyme), Sabatier’s principle and Boudart’s principle. The wrong theory leads the research and application of catalysts to the bottomless abyss, and industrial production suffers great losses. Electron Orbital Deformation-Recovere cyclic catalysis Mechanism-EODRM or Electron Cyclic Donate-Adopt catalysis Mechanism-ECDAM shows that the catalytic phenomenon is a physical phenomenon, not a chemical phenomenon, the catalyst does not participate in chemical reactions, only contact is the electron donate-adopt cycle, is the electron orbital deformation recovery cycle Chinese and foreign scholars should change the interpretation on the “catalysis, catalyst”, or add two new words: “contact and contactor”, it is to give up “catalysis, catalyst” altogether.
基金Supported by Jiangxi Provincial Engineering & Technology Research Center for Food Additives Bio-ProductionScience & Technology Platform Construction Program of Jiangxi Province (2010DTZ01900)+1 种基金Priority Academic Program Development of Jiangsu Higher Education InstitutionsResearch Foundation for Advanced Talents of Jiangsu University (08JDG029)~~
文摘Non-aqueous phase enzymatic catalysis technology has been widely ap- plied in the area of food additives production. This paper reviewed the types of re- action medium of non-aqueous phase enzymatic catalysis reaction, introduced the application of non-aqueous phase enzymatic catalysis technology in catalysis of L-ascorbic (isoascorbic) acid esters, short-chain acid esters, sugar esters, vitamin A esters, vi- tamin E esters, and other food additives, and finally predicted the prospects of non- aqueous phase enzymatic catalysis technology.
文摘Hydrogenation and ammoniation of SrTiOa (STO), a normal ultraviolet photocatalyst, were performed by annealing STO(100) in Hz:N2=5%:95% and NH3, respectively, at various temperatures T. It was found that hydrogenation at T≥900℃ remarkably enhanced the UV photocatalytic ability of STO, but the visible-light photocatalysis was still unavailable, while ammoniation at T≥800℃ introduced the N doping, resulting in visible-light photocat- alytie activity. Furthermore, when a hydrogenated STO was subjected to ammoniation, the visible-light photocatalytie ability was nearly the same as that of the ammoniated one; but the hydrogenation of an ammoniated one significantly enhanced visible-light photoeatalysis, indicating a synergetic effect of hydrogenation and ammoniation. Discussions and identifications have been made to analyze these results.
基金Project (B2011203074) supported by the Natural Science Foundation of Hebei Province, ChinaProject (201101A129) supported by the Technology Research and Development Program of Qinhuangdao, Hebei Province, China
文摘Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.
基金supported by the National Natural Science Foundation of China(21473196,21403214)the 100‐Talents Program of Chinese Academy of SciencesState Key Laboratory of Fine Chemicals,Dalian University of Technology(KF1415)~~
文摘We introduced bipyridine ligands into a series of two‐dimensional (2D) covalent organic frame‐works (COFs) using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde (2,2’‐BPyDCA) as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium(II) acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd(II) ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd(II)‐loaded COFs exhibited good catalytic activity for the Heck reaction.
基金the Science and Technology Department of Zhejiang Province (No.2006C13120).
文摘This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...