The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts hav...The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.展开更多
It is of great interest to develop the novel transition metal-based electrocatalysts with high selectivity and activity for two electron oxygen reduction reaction(2e^(-) ORR).Herein,the nickel ditelluride(NiTe_(2)) wi...It is of great interest to develop the novel transition metal-based electrocatalysts with high selectivity and activity for two electron oxygen reduction reaction(2e^(-) ORR).Herein,the nickel ditelluride(NiTe_(2)) with layered structure was explored as the 2e^(-) ORR electrocatalyst,which not only showed the highest 2e^(-) selectivity more than 97%,but also delivered a slight activity decay after 5000 cycles in alkaline media.Moreover,when NiTe_(2) was assembled as the electrocatalyst in H-type electrolyzer,the on-site yield of H_(2)O_(2) could reach up to 672 mmol h^(-1)g^(-1) under 0.45 V vs.RHE.Further in situ Raman spectra,theoretical calculation and post microstructural analysis synergistically unveiled that such a good 2e^(-) ORR performance could be credited to the intrinsic layered crystal structure,the high compositional stability,as well as the electron modulation on the active site Ni atoms by neighboring Te atoms,leading to the exposure of active sites as well as the optimized adsorption free energy of Ni to –OOH.More inspiringly,such telluride electrocatalyst has also been demonstrated to exhibit high activity and selectivity towards 2e^(-) ORR in neutral media.展开更多
As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and...As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and heavy carbon footprint.Alternatively,photoelectrocatalytic(PEC)production of H2O2 has shown great promises to make H2O2 a renewable fuel to store solar energy.Transition‐metal‐oxide(TMO)semiconductor based photoelectrocatalysts are among the most promising candidates for PEC H2O2 production.In this work,the fundamentals of H2O2 synthesis through PEC process are briefly introduced,followed by the state‐of‐the‐art of TMO semiconductor based photoelectrocatalysts for PEC production H2O2.Then,the progress on H2O2 fuel cells from on‐site PEC production is presented.Furthermore,the challenges and future perspectives of PEC H2O2 production are discussed.This review aims to provide inspiration for the PEC production of H2O2 as a renewable solar fuel.展开更多
Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show...Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show that the valence oftransition metal ion is also responsible for thedecomposition of hydrogen peroxide.Iron ions are present in two oxidation states, Fe2+ andFe3+. They are both catalytically active to hydrogenperoxide decomposition. Because Fe3+ is brown, itcan affect the brightness of pulp directly, it can alsocombine with phenol, forming complexes which notonly are stable structures and are difficult to beremoved from pulp, but also significantly affect thebrightness of pulp because of their color.Sodium silicate and magnesium sulfate, when usedtogether, can greatly decrease hydrogen peroxidedecomposition. The optimum dosage of sodiumsilicate is about 0.1% (on solution) for Fe2~ and0.25% (on solution) for Fe3~. Adding chelants such asDTPA or EDTA with stabilizers simultaneously canobviously improve pulp brightness. For iron ions, thechelate effect of DTPA is better than that of EDTA.Under acidic conditions, sodium hyposulfite andcellulose can reduce Fe3+ to Fez+ effectively, and pulpbrightness is improved greatly. Adding sodiumthiosulfate simultaneously with magnesium sulfate,sodium silicate, and DTPA to alkaline peroxidesolution can result in higher brightness of pulp.pH is a key parameter during hydrogen peroxidebleaching, the optimum pH value should be 10.5-12.展开更多
In this investigation, the catalytic activities of Mn(II),Mn(III) and Mn(IV) towards decomposing hydrogenperoxide were compared. Among Mn (II), Mn (III)and Mn (IV), Mn (II) is not catalytically active indecomposing hy...In this investigation, the catalytic activities of Mn(II),Mn(III) and Mn(IV) towards decomposing hydrogenperoxide were compared. Among Mn (II), Mn (III)and Mn (IV), Mn (II) is not catalytically active indecomposing hydrogen peroxide. However, both Mn(113) and Mn (IV) are, and Mn (III) has a strongereffect than Mn(IV).In addition, we also studied the practical methods todecrease the Mn-induced decomposition of hydrogenperoxide. The results showed that sodium silicate andmagnesium sulfite in combination can effectivelydecrease the decomposition of hydrogen peroxide.The optimum dosage of sodium silicate was about0.5% (on solution). Adding chelants such as DTPAor EDTA simultaneously with stabilizers candecrease hydrogen peroxide decomposition. For Mn(IV), the EDTA is more effective than DTPA.Adding sodium thiosulfate simultaneously withmagnesium sulfate, sodium silicate and DTPA toalkaline peroxide solution can result in more residualhydrogen peroxide, and a higher pulp brightness.展开更多
Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In...Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In this work,we demonstrate a general synthesis of Pt-early transition metal oxide(Pt-MO_(x),M=Ti,Zr,V,and Y)catalysts with rich interfacial sites,which is based on the air-induced surface segregation and oxidation of M in the supported Pt-M alloy catalysts.Systematic characterizations verify the dynamic structural response of Pt-M alloy catalysts to air and the formation of Pt-MO_(x) catalysts with abundant interfacial sites.The prepared Pt-TiO_(x) interfacial catalysts exhibit improved performance in hydrogenation reactions of benzaldehyde,nitrobenzene,styrene,and furfural,as a result of the heterolytic dissociation of H_(2) at Pt-metal oxide interfacial sites.展开更多
Herein,a layer of molybdenum oxide(MoO_(x)),a transition metal oxide(TMO),which has outstanding catalytic properties in combination with a carbonbased thin film,is modified to improve the hydrogen production performan...Herein,a layer of molybdenum oxide(MoO_(x)),a transition metal oxide(TMO),which has outstanding catalytic properties in combination with a carbonbased thin film,is modified to improve the hydrogen production performance and protect the MoO_(x)in acidic media.A thin film of graphene is transferred onto the MoO_(x)layer,after which the graphene structure is doped with N and S atoms at room temperature using a plasma doping method to modify the electronic structure and intrinsic properties of the material.The oxygen functional groups in graphene increase the interfacial interactions and electrical contacts between graphene and MoO_(x).The appearance of surface defects such as oxygen vacancies can result in vacancies in MoO_(x).This improves the electrical conductivity and electrochemically accessible surface area.Increasing the number of defects in graphene by adding dopants can significantly affect the chemical reaction at the interfaces and improve the electrochemical performance.These defects in graphene play a crucial role in the adsorption of H^(+)ions on the graphene surface and their transport to the MoO_(x)layer underneath.This enables MoO_(x)to participate in the reaction with the doped graphene.N^(‐)and S^(‐)doped graphene(NSGr)on MoO_(x)is active in acidic media and performs well in terms of hydrogen production.The initial overpotential value of 359 mV for the current density of−10 mA/cm^(2)is lowered to 228 mV after activation.展开更多
Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually sig...Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually significance in enabling a rebuilt ecological system for unconventional fuels. This concept is appealing when the process is considered as a solution for the storage of renewable energy, which may also find a variety of potential end uses for the outer space exploration. However, a big challenge to this issue is the rational design of high temperature endurable RWGS catalysts with desirable CO product selectivity. In this work, we present a comprehensive overview of recent publications on this research topic,mainly focusing on the catalytic performance of RWGS reaction over three major kinds of heterogeneous catalysts, including supported metal catalysts, mixed oxide catalysts and transition metal carbides. The reaction thermodynamic analysis, kinetics and mechanisms are also described in detail. The present review attempts to provide a general guideline about the construction of well-performed heterogeneous catalysts for the RWGS reaction, as well as discussing the challenges and further prospects of this process.展开更多
文摘The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.
基金supported by the National MCF Energy R&D Program of China (2018YFE0306105)the National Key R&D Program of China (2020YFA0406104, 2020YFA0406101)+8 种基金the Innovative Research Group Project of the National Natural Science Foundation of China (51821002)the National Natural Science Foundation of China (52201269, 52302296, 51972216)the Natural Science Foundation of Jiangsu Province (BK20220028, BK20210735)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (21KJB430043)the Collaborative Innovation Center of Suzhou Nano Science & Technology, the 111 Projectthe Suzhou Key Laboratory of Functional Nano & Soft Materials, the Jiangsu Key Laboratory for Advanced Negative Carbon Technologiesthe Science and Technology Development Fund, Macao SAR (0009/2022/ITP)the funding from Gusu leading talent plan for scientific and technological innovation and entrepreneurship (ZXL2022487)China Scholarship Council (CSC) for the Ph.D. fellowship。
文摘It is of great interest to develop the novel transition metal-based electrocatalysts with high selectivity and activity for two electron oxygen reduction reaction(2e^(-) ORR).Herein,the nickel ditelluride(NiTe_(2)) with layered structure was explored as the 2e^(-) ORR electrocatalyst,which not only showed the highest 2e^(-) selectivity more than 97%,but also delivered a slight activity decay after 5000 cycles in alkaline media.Moreover,when NiTe_(2) was assembled as the electrocatalyst in H-type electrolyzer,the on-site yield of H_(2)O_(2) could reach up to 672 mmol h^(-1)g^(-1) under 0.45 V vs.RHE.Further in situ Raman spectra,theoretical calculation and post microstructural analysis synergistically unveiled that such a good 2e^(-) ORR performance could be credited to the intrinsic layered crystal structure,the high compositional stability,as well as the electron modulation on the active site Ni atoms by neighboring Te atoms,leading to the exposure of active sites as well as the optimized adsorption free energy of Ni to –OOH.More inspiringly,such telluride electrocatalyst has also been demonstrated to exhibit high activity and selectivity towards 2e^(-) ORR in neutral media.
基金support from the Australian Research Council through its DECRA(DE210100930)Discovery Project (DP200101900)+2 种基金Lau-reate Fellowship (FL190100139) schemesfinancial support from Research Donation Generic(2020003431) from the Faculty of EngineeringArchitecture and Information Technology,The University of Queensland
文摘As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and heavy carbon footprint.Alternatively,photoelectrocatalytic(PEC)production of H2O2 has shown great promises to make H2O2 a renewable fuel to store solar energy.Transition‐metal‐oxide(TMO)semiconductor based photoelectrocatalysts are among the most promising candidates for PEC H2O2 production.In this work,the fundamentals of H2O2 synthesis through PEC process are briefly introduced,followed by the state‐of‐the‐art of TMO semiconductor based photoelectrocatalysts for PEC production H2O2.Then,the progress on H2O2 fuel cells from on‐site PEC production is presented.Furthermore,the challenges and future perspectives of PEC H2O2 production are discussed.This review aims to provide inspiration for the PEC production of H2O2 as a renewable solar fuel.
文摘Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show that the valence oftransition metal ion is also responsible for thedecomposition of hydrogen peroxide.Iron ions are present in two oxidation states, Fe2+ andFe3+. They are both catalytically active to hydrogenperoxide decomposition. Because Fe3+ is brown, itcan affect the brightness of pulp directly, it can alsocombine with phenol, forming complexes which notonly are stable structures and are difficult to beremoved from pulp, but also significantly affect thebrightness of pulp because of their color.Sodium silicate and magnesium sulfate, when usedtogether, can greatly decrease hydrogen peroxidedecomposition. The optimum dosage of sodiumsilicate is about 0.1% (on solution) for Fe2~ and0.25% (on solution) for Fe3~. Adding chelants such asDTPA or EDTA with stabilizers simultaneously canobviously improve pulp brightness. For iron ions, thechelate effect of DTPA is better than that of EDTA.Under acidic conditions, sodium hyposulfite andcellulose can reduce Fe3+ to Fez+ effectively, and pulpbrightness is improved greatly. Adding sodiumthiosulfate simultaneously with magnesium sulfate,sodium silicate, and DTPA to alkaline peroxidesolution can result in higher brightness of pulp.pH is a key parameter during hydrogen peroxidebleaching, the optimum pH value should be 10.5-12.
文摘In this investigation, the catalytic activities of Mn(II),Mn(III) and Mn(IV) towards decomposing hydrogenperoxide were compared. Among Mn (II), Mn (III)and Mn (IV), Mn (II) is not catalytically active indecomposing hydrogen peroxide. However, both Mn(113) and Mn (IV) are, and Mn (III) has a strongereffect than Mn(IV).In addition, we also studied the practical methods todecrease the Mn-induced decomposition of hydrogenperoxide. The results showed that sodium silicate andmagnesium sulfite in combination can effectivelydecrease the decomposition of hydrogen peroxide.The optimum dosage of sodium silicate was about0.5% (on solution). Adding chelants such as DTPAor EDTA simultaneously with stabilizers candecrease hydrogen peroxide decomposition. For Mn(IV), the EDTA is more effective than DTPA.Adding sodium thiosulfate simultaneously withmagnesium sulfate, sodium silicate and DTPA toalkaline peroxide solution can result in more residualhydrogen peroxide, and a higher pulp brightness.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.
基金support from the National Natural Science Foundation of China(Nos.22221003 and 22071225)the Plan for Anhui Major Provincial Science&Technology Project(Nos.202203a0520013 and 2021d05050006)the fellowship of China Postdoctoral Science Foundation(No.2022M712179).
文摘Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In this work,we demonstrate a general synthesis of Pt-early transition metal oxide(Pt-MO_(x),M=Ti,Zr,V,and Y)catalysts with rich interfacial sites,which is based on the air-induced surface segregation and oxidation of M in the supported Pt-M alloy catalysts.Systematic characterizations verify the dynamic structural response of Pt-M alloy catalysts to air and the formation of Pt-MO_(x) catalysts with abundant interfacial sites.The prepared Pt-TiO_(x) interfacial catalysts exhibit improved performance in hydrogenation reactions of benzaldehyde,nitrobenzene,styrene,and furfural,as a result of the heterolytic dissociation of H_(2) at Pt-metal oxide interfacial sites.
基金Korea Institute of Industrial Technology,Grant/Award Number:KITECH EO‐22‐0005National Research Foundation of Korea,Grant/Award Numbers:2022R1A3B1078163,2022R1A4A1031182,2022R1A2C2005701。
文摘Herein,a layer of molybdenum oxide(MoO_(x)),a transition metal oxide(TMO),which has outstanding catalytic properties in combination with a carbonbased thin film,is modified to improve the hydrogen production performance and protect the MoO_(x)in acidic media.A thin film of graphene is transferred onto the MoO_(x)layer,after which the graphene structure is doped with N and S atoms at room temperature using a plasma doping method to modify the electronic structure and intrinsic properties of the material.The oxygen functional groups in graphene increase the interfacial interactions and electrical contacts between graphene and MoO_(x).The appearance of surface defects such as oxygen vacancies can result in vacancies in MoO_(x).This improves the electrical conductivity and electrochemically accessible surface area.Increasing the number of defects in graphene by adding dopants can significantly affect the chemical reaction at the interfaces and improve the electrochemical performance.These defects in graphene play a crucial role in the adsorption of H^(+)ions on the graphene surface and their transport to the MoO_(x)layer underneath.This enables MoO_(x)to participate in the reaction with the doped graphene.N^(‐)and S^(‐)doped graphene(NSGr)on MoO_(x)is active in acidic media and performs well in terms of hydrogen production.The initial overpotential value of 359 mV for the current density of−10 mA/cm^(2)is lowered to 228 mV after activation.
基金supported by the National Natural Science Foundation of China(Nos.21506204 and 21476226)China Ministry of Science and Technology under contact of 2016YFB0600902+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)State Grid Cooperation of China(SGRI-DL-71-16-015)Dalian Science Foundation for Distinguished Young Scholars(2016RJ04)the Youth Innovation Promotion Association of CAS
文摘Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually significance in enabling a rebuilt ecological system for unconventional fuels. This concept is appealing when the process is considered as a solution for the storage of renewable energy, which may also find a variety of potential end uses for the outer space exploration. However, a big challenge to this issue is the rational design of high temperature endurable RWGS catalysts with desirable CO product selectivity. In this work, we present a comprehensive overview of recent publications on this research topic,mainly focusing on the catalytic performance of RWGS reaction over three major kinds of heterogeneous catalysts, including supported metal catalysts, mixed oxide catalysts and transition metal carbides. The reaction thermodynamic analysis, kinetics and mechanisms are also described in detail. The present review attempts to provide a general guideline about the construction of well-performed heterogeneous catalysts for the RWGS reaction, as well as discussing the challenges and further prospects of this process.
