The increasing emission of carbon dioxide （CO2） caused by the unrestrained consumption of fossil fuels in recent hundreds of years, has caused global environmental and social problems. Meanwhile, CO2 is a cheap, abu...The increasing emission of carbon dioxide （CO2） caused by the unrestrained consumption of fossil fuels in recent hundreds of years, has caused global environmental and social problems. Meanwhile, CO2 is a cheap, abundant and renewable Cl-feedstock, which can be converted into alco- hols, ethers, acids and other value-added chemicals. Compared with the thermal reactions, electrochemical reduction of CO2 is more attractive because of its advantages by using the seasonal, geographical and intermittent energy （tide, wind and solar） under mild conditions. In recent years, taking ionic liquids （ILs） as electrolytes in the CO2 electrochemical reduction reaction has been paid much more attention due to the advantages of lowering the overpotential of CO2 electroreduction and improving the Faradaic efficiency. In this paper, we summarized the recent progresses of electrochemical re- duction of CO2 in ILs electrolytes, and analyzed the reaction mechanism of CO2 reaction in the electrode-electrolyte interface region by experimental and simulation methods. Finally, the research which needs to be highlighted in this area was proposed.展开更多
Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of u...Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of unstable nitrate species causes desorption to release NO_(2).In this study,SnO_(2) quantum dots and oxygen vacancies co-modified Zn_(2)SnO_(4)(ZSO-SnO_(2)-OVs)were prepared by a one-step hydrothermal procedure,the NO photo-oxidation was investigated by a combination of solid experimental and theoretical support.Impressively,spectroscopic measurements indicate that fast carrier dynamics can be achieved due to the electron transfer efficiency of ZSO-SnO_(2)-OVs reaching 99.99%,far outperforming the counterpart and previously reported photocatalysts.During NO oxidation,molecular NO/O_(2) and H2O are efficiently adsorbed/activated around OVs and SnO_(2) QDs,respectively.In-situ infrared measurements and calculated electron localized function disclose two main findings:(1)richly electrons enable NO promptly form NOinstead of toxic NO_(2) or NO^(+);(2)the generation of stable and undecomposed bidentate NO_(3)rather than bridging or monodentate one benefits the deep oxidation of NO via shifting reaction sites from O terminals for original ZSO to Sn ones for ZSO-SnO_(2)-OVs.The synergistic action of SnO_(2) QDs and OVs positively contributes to the NO oxidation performance enhancement(60.6%,0.1 g of sample)and high selectivity of NO to NO_(3)(99.2%).Results from this study advance the mechanistic understanding of NO photooxidation and its selectivity to NO_(3)over photocatalysts.展开更多
Achieving efficient degradation of organic pollutants via activation of sulfite is meaningful but challenging.Herein,we have constructed a heterogeneous catalyst system involving Co_(3)O_(4) and TiO_(2) nanoparticles ...Achieving efficient degradation of organic pollutants via activation of sulfite is meaningful but challenging.Herein,we have constructed a heterogeneous catalyst system involving Co_(3)O_(4) and TiO_(2) nanoparticles to form the p-n heterojunction(Co_(3)O_(4)/TiO_(2)) to degrade acetaminophen(ACE) through photocatalytic activation of sulfite.Specifically,X-ray photoelectron spectroscopy analysis and theoretical calculations provide compelling evidence of electron transfer from Co_(3)O_(4) to TiO_(2) at the heterointerface.The interfacial electron redistribution of Co_(3)O_(4)/TiO_(2) tunes the adsorption energy of HSO_(3)^(-)/SO_(3)^(2-) in sulfite activation process for enhanced the catalytic activity.Owing to its unique heterointerface,the degradation efficiency of ACE reached 96.78%within 10 min.The predominant active radicals were identified as ·OH,h^(+),and SO_(x)^(·-) through radical quenching experiments and electron spin resonance capture.Besides,the possible degradation pathway was deduced by monitoring the generated intermediate products.Thereafter,the enhanced roles of well-engineered compositing interface in photocatalytic activation of sulfite for complete degradation of ACE were unveiled that it can improve light absorption ability,facilitate the generation of active species,and optimize reactive pathways.Considering that sulfite is a waste from flue gas desulfurization process,the photocatalytic activation of sulfite system will open up new avenues of beneficial use of air pollutants for the removal of pharmaceutical wastewater.展开更多
Water and solar energy are inexhaustible on Earth,and thus hydrogen evolution through photocatalytic water splitting taking sunlight as the input energy is an ideal green energy generation technology.As a typical visi...Water and solar energy are inexhaustible on Earth,and thus hydrogen evolution through photocatalytic water splitting taking sunlight as the input energy is an ideal green energy generation technology.As a typical visible-light-responsive photocatalyst,ZnIn_(2)S_(4)attracted worldwide research attention because of its many advantages for photocatalytic hydrogen evolution(PHE),such as layered structure,simple syn-theses,structural stability,environmental friendliness,and suitable electronic band structure.In recent years,constructing ZnIn_(2)S_(4)-based heterostructured photocatalysts has become a research focus for their significantly improved spatial charge carrier separation efficiency and PHE performances.According to the charge carrier transfer/separation mechanisms,heterostructured ZnIn_(2)S_(4)-based photocatalysts are divided into five categories,conventional heterojunctions(type-I and type-II),p-n heterojunction,Z-scheme het-erojunction,S-scheme(or Step-scheme)heterojunction,and co-catalyst deposition based heterojunction systems.This article reviews the recent advances in ZnIn_(2)S_(4)-based heterostructured photocatalysts for PHE.Firstly,the central part of this review introduced various ZnIn_(2)S_(4)-based heterojunctions and their PHE application.Secondly,apart from common half-reaction of water-splitting,we expressly introduced overall water splitting,dual-functional and photothermal effect-assisted PHE systems.Then,we briefly presented some identification methods for confirming heterojunction types.Finally,the current states,challenges and perspectives of ZnIn_(2)S_(4)-based heterostructured photocatalysts for PHE are also discussed.This review aims to explore the advantages of diverse ZnIn_(2)S_(4)-based heterostructures,and can provide an insight into designing high-efficiency heterostructured photocatalysts for PHE application.展开更多
Galvanic replacement, one of the popular strategies for producing hollow metallic nanostructures, has enjoyed great success in the past. However, it is rarely used with Au nanopartides as the self-sacrificed templates...Galvanic replacement, one of the popular strategies for producing hollow metallic nanostructures, has enjoyed great success in the past. However, it is rarely used with Au nanopartides as the self-sacrificed templates, even though these nanoparticles can be produced with well-controlled size, shape, and structure. Here, both Ag and Au from the core-sheU Au@Ag nanorods are demonstrated to be involved in the galvanic replacement for producing hollow nanostructures. The enhanced oxidation of metallic Au could be attributed to the close contact between Au and Ag and the unique charge compensation from Au to Ag, both of which are indispensable for the etching of Au via galvanic replacement. As a result of this reaction, these bimetallic nanorods experience a structural evolution from nanorattles, to tip-empty nanorods, and eventually to porous nanotubes. The nanotubes exhibit high catalytic activities in the electrooxidation of formic acid. These results not only disclose the underlying mechanism by which metallic Au could be replaced under mild conditions, but also expand the selection of self-sacrificed templates for galvanic replacement, which is an important reaction in many applications.展开更多
基金This work was supported by Fundamental Research and the National Key Projects for Development of China （2018YFB0605802）, the National Natural Science Foundation of China （21425625 ＆ 21506219）, Beijing Natural Science Founda- tion （2182072）, the Research Council of Norway {267615）, and Beijing Hundreds of Leading Talents Training Project of Science and Technology （Z171100001117154）.
文摘The increasing emission of carbon dioxide （CO2） caused by the unrestrained consumption of fossil fuels in recent hundreds of years, has caused global environmental and social problems. Meanwhile, CO2 is a cheap, abundant and renewable Cl-feedstock, which can be converted into alco- hols, ethers, acids and other value-added chemicals. Compared with the thermal reactions, electrochemical reduction of CO2 is more attractive because of its advantages by using the seasonal, geographical and intermittent energy （tide, wind and solar） under mild conditions. In recent years, taking ionic liquids （ILs） as electrolytes in the CO2 electrochemical reduction reaction has been paid much more attention due to the advantages of lowering the overpotential of CO2 electroreduction and improving the Faradaic efficiency. In this paper, we summarized the recent progresses of electrochemical re- duction of CO2 in ILs electrolytes, and analyzed the reaction mechanism of CO2 reaction in the electrode-electrolyte interface region by experimental and simulation methods. Finally, the research which needs to be highlighted in this area was proposed.
基金the National Natural Science Foundation of China(Grant No.51808080)China Postdoctoral Science Foundation(No.2022M710830)+4 种基金Venture and Innovation Support Program for Chongqing Overseas Returnees(No.cx2022005)the Natural Science Foundation Project of CQ CSTC(No.CSTB2022NSCQ-MSX1267)Research Project of Chongqing Education Commission Foundation(No.KJQN201800826)Science and Technology Research Program of Chongqing Municipal Education Commission of China(No.KJZD-K202100801)Post-doctoral Program Funded by Chongqing,and Chongqing University Innovation Research Group project(No.CXQT21023).
文摘Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of unstable nitrate species causes desorption to release NO_(2).In this study,SnO_(2) quantum dots and oxygen vacancies co-modified Zn_(2)SnO_(4)(ZSO-SnO_(2)-OVs)were prepared by a one-step hydrothermal procedure,the NO photo-oxidation was investigated by a combination of solid experimental and theoretical support.Impressively,spectroscopic measurements indicate that fast carrier dynamics can be achieved due to the electron transfer efficiency of ZSO-SnO_(2)-OVs reaching 99.99%,far outperforming the counterpart and previously reported photocatalysts.During NO oxidation,molecular NO/O_(2) and H2O are efficiently adsorbed/activated around OVs and SnO_(2) QDs,respectively.In-situ infrared measurements and calculated electron localized function disclose two main findings:(1)richly electrons enable NO promptly form NOinstead of toxic NO_(2) or NO^(+);(2)the generation of stable and undecomposed bidentate NO_(3)rather than bridging or monodentate one benefits the deep oxidation of NO via shifting reaction sites from O terminals for original ZSO to Sn ones for ZSO-SnO_(2)-OVs.The synergistic action of SnO_(2) QDs and OVs positively contributes to the NO oxidation performance enhancement(60.6%,0.1 g of sample)and high selectivity of NO to NO_(3)(99.2%).Results from this study advance the mechanistic understanding of NO photooxidation and its selectivity to NO_(3)over photocatalysts.
基金financially supported by the National Natural Science Foundation of China(No.51878273)the Natural Science Foundation of Hebei Province(No.E2019502199)。
文摘Achieving efficient degradation of organic pollutants via activation of sulfite is meaningful but challenging.Herein,we have constructed a heterogeneous catalyst system involving Co_(3)O_(4) and TiO_(2) nanoparticles to form the p-n heterojunction(Co_(3)O_(4)/TiO_(2)) to degrade acetaminophen(ACE) through photocatalytic activation of sulfite.Specifically,X-ray photoelectron spectroscopy analysis and theoretical calculations provide compelling evidence of electron transfer from Co_(3)O_(4) to TiO_(2) at the heterointerface.The interfacial electron redistribution of Co_(3)O_(4)/TiO_(2) tunes the adsorption energy of HSO_(3)^(-)/SO_(3)^(2-) in sulfite activation process for enhanced the catalytic activity.Owing to its unique heterointerface,the degradation efficiency of ACE reached 96.78%within 10 min.The predominant active radicals were identified as ·OH,h^(+),and SO_(x)^(·-) through radical quenching experiments and electron spin resonance capture.Besides,the possible degradation pathway was deduced by monitoring the generated intermediate products.Thereafter,the enhanced roles of well-engineered compositing interface in photocatalytic activation of sulfite for complete degradation of ACE were unveiled that it can improve light absorption ability,facilitate the generation of active species,and optimize reactive pathways.Considering that sulfite is a waste from flue gas desulfurization process,the photocatalytic activation of sulfite system will open up new avenues of beneficial use of air pollutants for the removal of pharmaceutical wastewater.
基金This work was financially supported by the National Natural Science Foundation of China(No.51902282)the Qinglan Project of Jiangsu of China,the Natural Science Foundation of Jiangsu Province(Nos.BK20211361 and BX2021054)+1 种基金the College Natural Science Research Project of Jiangsu Province(No.20KJA430004)the Open Fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province.
文摘Water and solar energy are inexhaustible on Earth,and thus hydrogen evolution through photocatalytic water splitting taking sunlight as the input energy is an ideal green energy generation technology.As a typical visible-light-responsive photocatalyst,ZnIn_(2)S_(4)attracted worldwide research attention because of its many advantages for photocatalytic hydrogen evolution(PHE),such as layered structure,simple syn-theses,structural stability,environmental friendliness,and suitable electronic band structure.In recent years,constructing ZnIn_(2)S_(4)-based heterostructured photocatalysts has become a research focus for their significantly improved spatial charge carrier separation efficiency and PHE performances.According to the charge carrier transfer/separation mechanisms,heterostructured ZnIn_(2)S_(4)-based photocatalysts are divided into five categories,conventional heterojunctions(type-I and type-II),p-n heterojunction,Z-scheme het-erojunction,S-scheme(or Step-scheme)heterojunction,and co-catalyst deposition based heterojunction systems.This article reviews the recent advances in ZnIn_(2)S_(4)-based heterostructured photocatalysts for PHE.Firstly,the central part of this review introduced various ZnIn_(2)S_(4)-based heterojunctions and their PHE application.Secondly,apart from common half-reaction of water-splitting,we expressly introduced overall water splitting,dual-functional and photothermal effect-assisted PHE systems.Then,we briefly presented some identification methods for confirming heterojunction types.Finally,the current states,challenges and perspectives of ZnIn_(2)S_(4)-based heterostructured photocatalysts for PHE are also discussed.This review aims to explore the advantages of diverse ZnIn_(2)S_(4)-based heterostructures,and can provide an insight into designing high-efficiency heterostructured photocatalysts for PHE application.
基金We would like to acknowledge the financial support from the National Natural Science Foundation of China （Nos. 21071055 and 21172076）, Shandong Provincial Natural Science Foundation for Distinguished Young Scholar （No. JQ201205）, Taishan Scholar Program of Shandong Province （No. ts201511004）, and Independent Innovation Foundation of Shandong University.
文摘Galvanic replacement, one of the popular strategies for producing hollow metallic nanostructures, has enjoyed great success in the past. However, it is rarely used with Au nanopartides as the self-sacrificed templates, even though these nanoparticles can be produced with well-controlled size, shape, and structure. Here, both Ag and Au from the core-sheU Au@Ag nanorods are demonstrated to be involved in the galvanic replacement for producing hollow nanostructures. The enhanced oxidation of metallic Au could be attributed to the close contact between Au and Ag and the unique charge compensation from Au to Ag, both of which are indispensable for the etching of Au via galvanic replacement. As a result of this reaction, these bimetallic nanorods experience a structural evolution from nanorattles, to tip-empty nanorods, and eventually to porous nanotubes. The nanotubes exhibit high catalytic activities in the electrooxidation of formic acid. These results not only disclose the underlying mechanism by which metallic Au could be replaced under mild conditions, but also expand the selection of self-sacrificed templates for galvanic replacement, which is an important reaction in many applications.
