Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropo...Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropogenic carbon cycle.Among various electrocatalysts for electrochemical CO_(2)reduction,multifunctional metal–organic frameworks(MOFs)have been employed as highly efficient and selective heterogeneous electrocatalysts due to their ultrahigh porosity and topologically diverse structures.Up to now,great progress has been achieved in the design and synthesis of highly active and selective MOF-related catalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR),and their corresponding reaction mechanisms have been thoroughly studied.In this review,we summarize the recent progress of applying MOFs and their derivatives in CO_(2)RR,with a focus on the design strategies for electrocatalysts and electrolyzers.We first discussed the reaction mechanisms for different CO_(2)RR products and introduced the commonly applied electrolyzer configurations in the current CO_(2)RR system.Then,an overview of several categories of products(CO,HCOOH,CH_(4),CH_(3)OH,and multi-carbon chemicals)generated from MOFs or their derivatives via CO_(2)RR was discussed.Finally,we offer some insights and perspectives for the future development of MOFs and their derivatives in electrochemical CO_(2)reduction.We aim to provide new insights into this field and further guide future research for large-scale applications.展开更多
Electroreduction of carbon dioxide(CO_(2)) into value-added chemicals offers an entrancing approach to main-taining the global carbon cycle and eliminating environmental threats.A key obstacle to achieving long-term a...Electroreduction of carbon dioxide(CO_(2)) into value-added chemicals offers an entrancing approach to main-taining the global carbon cycle and eliminating environmental threats.A key obstacle to achieving long-term and large-scale implementation of electrochemical CO_(2) reduction technology is the lack of active and selective cat-alysts.Copper(Cu)is one of the few candidates that can facilitate C–C coupling to obtain high-energy oxygenates and hydrocarbons beyond carbon monoxide(CO),but it suffers from poor selectivity for products of interest and high overpotentials.Alloying is an effective way to break the linear scaling relations and uniquely manipulate the reactivity and selectivity,which is hard to achieve by using monometallic compositions alone.By alloying Cu with other metals,one could change the catalytic properties of the catalyst by tuning the local electronic structure and modulating the adsorption strength of the reaction intermediates,thus improving the catalytic activity and selectivity.In this review,we focus on the recently developed Cu-based alloy catalysts(including conventional alloys,high-entropy alloys and single-atom alloys)that have been applied in electrocatalytic CO_(2) reduction(ECR).Theoretical calculations and experimental advances in understanding the key rate-limiting and selectivity-determining steps in those alloys are summarized,with a particular focus on identifying binding energy de-scriptors and the dynamic product formation mechanisms.In addition,we outline the opportunities and chal-lenges in the fundamental understanding of ECR by recommending advanced in-situ characterization techniques and standardized electrochemical methods and offer atomic-level design principles for steering the reaction pathways to the desired products.展开更多
基金the National Key Research and Development Program of China(2022YFB4102000)NSFC(22102018 and 52171201)+5 种基金the Natural Science Foundation of Sichuan Province(2022NSFSC0194)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)the Hefei National Research Center for Physical Sciences at the Microscale(KF2021005)the University of Electronic Science and Technology of China for startup funding(A1098531023601264)Q.J.acknowledges the China Postdoctoral Science Foundation funded project(2022M710601)the University of Electronic Science and Technology of China for startup funding(Y030212059003039).
文摘Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropogenic carbon cycle.Among various electrocatalysts for electrochemical CO_(2)reduction,multifunctional metal–organic frameworks(MOFs)have been employed as highly efficient and selective heterogeneous electrocatalysts due to their ultrahigh porosity and topologically diverse structures.Up to now,great progress has been achieved in the design and synthesis of highly active and selective MOF-related catalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR),and their corresponding reaction mechanisms have been thoroughly studied.In this review,we summarize the recent progress of applying MOFs and their derivatives in CO_(2)RR,with a focus on the design strategies for electrocatalysts and electrolyzers.We first discussed the reaction mechanisms for different CO_(2)RR products and introduced the commonly applied electrolyzer configurations in the current CO_(2)RR system.Then,an overview of several categories of products(CO,HCOOH,CH_(4),CH_(3)OH,and multi-carbon chemicals)generated from MOFs or their derivatives via CO_(2)RR was discussed.Finally,we offer some insights and perspectives for the future development of MOFs and their derivatives in electrochemical CO_(2)reduction.We aim to provide new insights into this field and further guide future research for large-scale applications.
基金the National Natural Science Foundation of China(NSFC 22102018 and 52171201)the Natural Science Foundation of Sichuan Province(2022NSFSC0194)+6 种基金the Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province(2021ZYD0043)the University of Electronic Science and Technology of China for Startup Funding(A1098531023601264)the Hefei National Research Center for Physical Sciences at the Micro-scale(KF2021005)the China Postdoctoral Science Foundation funded project(2022M710601)the University of Elec-tronic Science and Technology of China for Startup Funding(Y030212059003039)the NSFC(22005291 and 22278067)University of Electronic Science and Technology of China for Startup Funding(A1098531023601356).
文摘Electroreduction of carbon dioxide(CO_(2)) into value-added chemicals offers an entrancing approach to main-taining the global carbon cycle and eliminating environmental threats.A key obstacle to achieving long-term and large-scale implementation of electrochemical CO_(2) reduction technology is the lack of active and selective cat-alysts.Copper(Cu)is one of the few candidates that can facilitate C–C coupling to obtain high-energy oxygenates and hydrocarbons beyond carbon monoxide(CO),but it suffers from poor selectivity for products of interest and high overpotentials.Alloying is an effective way to break the linear scaling relations and uniquely manipulate the reactivity and selectivity,which is hard to achieve by using monometallic compositions alone.By alloying Cu with other metals,one could change the catalytic properties of the catalyst by tuning the local electronic structure and modulating the adsorption strength of the reaction intermediates,thus improving the catalytic activity and selectivity.In this review,we focus on the recently developed Cu-based alloy catalysts(including conventional alloys,high-entropy alloys and single-atom alloys)that have been applied in electrocatalytic CO_(2) reduction(ECR).Theoretical calculations and experimental advances in understanding the key rate-limiting and selectivity-determining steps in those alloys are summarized,with a particular focus on identifying binding energy de-scriptors and the dynamic product formation mechanisms.In addition,we outline the opportunities and chal-lenges in the fundamental understanding of ECR by recommending advanced in-situ characterization techniques and standardized electrochemical methods and offer atomic-level design principles for steering the reaction pathways to the desired products.
