Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive...Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.展开更多
Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of...Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of the crystal-facet effect of crystalline coordination compounds on the performance of electrocatalytic CO_(2)reduction has not yet been reported.Herein,a stable hexanuclear copper cluster(Cu6)catalyst model system is designed and synthesized.By effectively regulating the growth size(micro-nano size)and morphology of the Cu6 single crystal,Cu6(P)with the main(100)facet,Cu6(H)with the main(100)and(001)facets,and Cu6(S)with the main(001)facet are obtained.From Cu6(P)via Cu6(H)to Cu6(S),there is a shift from the predominantly exposed(100)facet(involving two non-adjacent active Cu sites)to the(001)facet(involving three adjacent active Cu sites),which directly affects the adsorption direction of the key*CO intermediate and the potential of C-C coupling,thus enabling effective regulation of the selectivity of C1(CO and CH4)and C2(C2H4)reduction products.This work provides an essential molecular model system and a novel design perspective for the systematic study of the crystalfacet effect of coordination compounds on the species and selectivity of CO_(2)reduction reaction products.展开更多
Electrochemical CO_(2) reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for f...Electrochemical CO_(2) reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for further application of this process.Here,we regulate CO adsorption by forming a Nafion layer on the copper(Cu)electrode that is repulsive to OH^(-),contributing to enhanced selectivity of CO_(2) reduction to C_(2) products with the suppression of C 1 products.The operando Raman spectroscopy indicates that the local OH^(-)would adsorb on part of active sites and decrease the adsorption of CO.Therefore,the electrode with repulsive to OH^(-)can adjust the concentration of OH^(-),leading to the increased adsorption of CO and enhanced C–C coupling.This work shows that electrode design could be an effective strategy for improving the selectivity of CO_(2) reduction to multi-carbon products.展开更多
文摘Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.
基金financially supported by the NSFC(grant nos.92061101,21871141,and 22225109)the Excellent Youth Foundation of Jiangsu Natural Science Foundation(grant no.BK20211593)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1546)Priority Academic Program Development of Jiangsu Higher Education Institutions,and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of the crystal-facet effect of crystalline coordination compounds on the performance of electrocatalytic CO_(2)reduction has not yet been reported.Herein,a stable hexanuclear copper cluster(Cu6)catalyst model system is designed and synthesized.By effectively regulating the growth size(micro-nano size)and morphology of the Cu6 single crystal,Cu6(P)with the main(100)facet,Cu6(H)with the main(100)and(001)facets,and Cu6(S)with the main(001)facet are obtained.From Cu6(P)via Cu6(H)to Cu6(S),there is a shift from the predominantly exposed(100)facet(involving two non-adjacent active Cu sites)to the(001)facet(involving three adjacent active Cu sites),which directly affects the adsorption direction of the key*CO intermediate and the potential of C-C coupling,thus enabling effective regulation of the selectivity of C1(CO and CH4)and C2(C2H4)reduction products.This work provides an essential molecular model system and a novel design perspective for the systematic study of the crystalfacet effect of coordination compounds on the species and selectivity of CO_(2)reduction reaction products.
基金This work was supported by the following projects:INTERNATIONAL COOPERATION Projects of the Ministry of Science and Technology(2014DFE60170)the Strategic Japanese-Swiss Science and Technology Program from the Swiss National Science Foundation(project No.IZJSZ2_180176)+4 种基金the Sino-Swiss Science and Technology Cooperation(SSSTC)2016 project from the Swiss National Science Foundation(project No.IZLCZ2_170294)the National Natural Science Foundation of China(Grant No.61674084)the Overseas Expertise Introduction Project for DisciplineInnovation of Higher Education of China(Grant No.B16027)Tianjin Science and Technology Project(Grant No.18ZXJMTG00220)the Fundamental Research Fund for the Central Universities of China.
文摘Electrochemical CO_(2) reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for further application of this process.Here,we regulate CO adsorption by forming a Nafion layer on the copper(Cu)electrode that is repulsive to OH^(-),contributing to enhanced selectivity of CO_(2) reduction to C_(2) products with the suppression of C 1 products.The operando Raman spectroscopy indicates that the local OH^(-)would adsorb on part of active sites and decrease the adsorption of CO.Therefore,the electrode with repulsive to OH^(-)can adjust the concentration of OH^(-),leading to the increased adsorption of CO and enhanced C–C coupling.This work shows that electrode design could be an effective strategy for improving the selectivity of CO_(2) reduction to multi-carbon products.
