Development of high-efficiency electrode materials for the electrochemical CO_(2)reduction reaction(CO_(2)RR)with high current density and selectivity compatible with industry is an important but significant challenge...Development of high-efficiency electrode materials for the electrochemical CO_(2)reduction reaction(CO_(2)RR)with high current density and selectivity compatible with industry is an important but significant challenge.Herein,we describe a facile strategy to enhance the selectivity and current density by regulating the local electron density of the cobalt site in a series of stable,conjugated,bimetallic Co/Zn polyphthalocyanine frameworks Co_(x)Zn_(y)PPc with an AB stacking model under alkaline aqueous conditions.When adjusting the ratio of Co and Zn to 3:1,the optimal Co3Zn1PPc exhibits an industry-compatible CO partial current density of 212 mA cm^(−2)at−0.9 V versus reversible hydrogen electrode in a flow cell,which is 1.7 and 9.1 times that of the single metal polyphthalocyanine CoPPc and ZnPPc,respectively.Co_(3)Zn_(1)PPc shows a high CO Faraday efficiency of more than 90%in a wide operating potential window of−0.3 to−0.9 V.In-depth experimental and theoretical analysis revealed that introduction of electron-rich Zn atoms modified the electron density of the active Co center,placing Co in the electronrich region and weakening the bonding strength with the reaction intermediate,thereby improving the CO_(2)RR performance.These results clarify the interaction mechanism of dual metal sites at the atomic level and provide a new avenue for the design of electrocatalysts with potential in industrial applications.展开更多
Tandem catalytic reactions have attracted extensive interest because of their ability to reduce reaction steps,energy consumption,and waste.However,the construction of highly efficient tandem catalytic systems is stil...Tandem catalytic reactions have attracted extensive interest because of their ability to reduce reaction steps,energy consumption,and waste.However,the construction of highly efficient tandem catalytic systems is still a significant challenge due to the problematic integration of multiple active sites in one reaction system and the incompatibility of different reaction conditions.Although metal nanoparticles(MNPs)supported on porous framework materials have shown excellent catalytic performances in various reactions,their cooperative catalysis for tandem reactions is rarely reported.展开更多
基金support from the National Key Research and Development Program of China(nos.2018YFA0208600,2018YFA0704502)NSFC(nos.21871263,22071245,and 22033008)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(no.2021ZZ103).
文摘Development of high-efficiency electrode materials for the electrochemical CO_(2)reduction reaction(CO_(2)RR)with high current density and selectivity compatible with industry is an important but significant challenge.Herein,we describe a facile strategy to enhance the selectivity and current density by regulating the local electron density of the cobalt site in a series of stable,conjugated,bimetallic Co/Zn polyphthalocyanine frameworks Co_(x)Zn_(y)PPc with an AB stacking model under alkaline aqueous conditions.When adjusting the ratio of Co and Zn to 3:1,the optimal Co3Zn1PPc exhibits an industry-compatible CO partial current density of 212 mA cm^(−2)at−0.9 V versus reversible hydrogen electrode in a flow cell,which is 1.7 and 9.1 times that of the single metal polyphthalocyanine CoPPc and ZnPPc,respectively.Co_(3)Zn_(1)PPc shows a high CO Faraday efficiency of more than 90%in a wide operating potential window of−0.3 to−0.9 V.In-depth experimental and theoretical analysis revealed that introduction of electron-rich Zn atoms modified the electron density of the active Co center,placing Co in the electronrich region and weakening the bonding strength with the reaction intermediate,thereby improving the CO_(2)RR performance.These results clarify the interaction mechanism of dual metal sites at the atomic level and provide a new avenue for the design of electrocatalysts with potential in industrial applications.
基金support from the National Key Research and Development Program of China(nos.2018YFA0208600 and 2018YFA0704502)NSFC(nos.22071245,21671188,21871263,and 21520102001)+2 种基金Key Research Program of Frontier Science,CAS(no.QYZDJ-SSW-SLH045)Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000)and Youth Innovation Promotion Association,CAS(no.Y201850).
文摘Tandem catalytic reactions have attracted extensive interest because of their ability to reduce reaction steps,energy consumption,and waste.However,the construction of highly efficient tandem catalytic systems is still a significant challenge due to the problematic integration of multiple active sites in one reaction system and the incompatibility of different reaction conditions.Although metal nanoparticles(MNPs)supported on porous framework materials have shown excellent catalytic performances in various reactions,their cooperative catalysis for tandem reactions is rarely reported.
