Electrocatalytic CO_(2)-to-CO conversion is crucial for advancing sustainable processes,and providing essential feedstocks for the chemical industry.Cobalt phthalocyanine(CoPc)is a well-established molecular catalyst ...Electrocatalytic CO_(2)-to-CO conversion is crucial for advancing sustainable processes,and providing essential feedstocks for the chemical industry.Cobalt phthalocyanine(CoPc)is a well-established molecular catalyst for this conversion;however,maintaining high selectivity at industrially relevant current densities remains a significant challenge.Herein,we present a Co–N_(5)local structure anchored on nitrogen-doped carbon nanotubes through axial nitrogen coordination engineering to CoPc(CoPc/N-CNTs).The catalyst demonstrates near-unity CO selectivity and a high CO turnover frequency,peaking at 19.2 s^(−1)across a wide range of overpotentials.In flow cell tests,CoPc/N-CNTs achieve a CO Faradaic efficiency exceeding 95%at a current density of−800 mA cm^(−2).When integrated into a membrane electrode assembly,it maintained over 90%CO Faradaic efficiency at an industrial-scale current of−5 A for up to 20 h.Mechanistic studies revealed that Co–N_(5)active sites accelerate*COOH formation and inhibit deeper*CO reduction to CH_(3)OH while reducing HER activity by lowering H_(2)O surface coverage.These findings offer a delicate catalyst design that enables the efficient and sustained conversion of CO_(2)to CO.展开更多
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
基金the National Key Research and Development Program of China(2022YFA1505700)the Fundamental Research Funds for the Central Universities(ZYGX2022J012)+2 种基金the NSFC(52171201,22278067,22322201,22201272)the Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province(2024ZYD0152)the Natural Science Foundation of Sichuan Province(2025NSFJQ0017,2024NSFSC1107,2024NSFSC1104,2023NSFSC0094)。
文摘Electrocatalytic CO_(2)-to-CO conversion is crucial for advancing sustainable processes,and providing essential feedstocks for the chemical industry.Cobalt phthalocyanine(CoPc)is a well-established molecular catalyst for this conversion;however,maintaining high selectivity at industrially relevant current densities remains a significant challenge.Herein,we present a Co–N_(5)local structure anchored on nitrogen-doped carbon nanotubes through axial nitrogen coordination engineering to CoPc(CoPc/N-CNTs).The catalyst demonstrates near-unity CO selectivity and a high CO turnover frequency,peaking at 19.2 s^(−1)across a wide range of overpotentials.In flow cell tests,CoPc/N-CNTs achieve a CO Faradaic efficiency exceeding 95%at a current density of−800 mA cm^(−2).When integrated into a membrane electrode assembly,it maintained over 90%CO Faradaic efficiency at an industrial-scale current of−5 A for up to 20 h.Mechanistic studies revealed that Co–N_(5)active sites accelerate*COOH formation and inhibit deeper*CO reduction to CH_(3)OH while reducing HER activity by lowering H_(2)O surface coverage.These findings offer a delicate catalyst design that enables the efficient and sustained conversion of CO_(2)to CO.
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.
