The Cu^(+)/Cu^(0)sites of copper-based catalysts are crucial for enhancing the production of multicarbon(C_(2+))products from electrochemical CO_(2)reduction reaction(eCO_(2)RR).However,the unstable Cu^(+)and insuffic...The Cu^(+)/Cu^(0)sites of copper-based catalysts are crucial for enhancing the production of multicarbon(C_(2+))products from electrochemical CO_(2)reduction reaction(eCO_(2)RR).However,the unstable Cu^(+)and insufficient Cu^(+)/Cu^(0)active sites lead to their limited selectivity and stability for C_(2+)production.Herein,we embedded copper oxide(CuO_(x))particles into porous nitrogen-doped carbon nanofibers(CuO_(x)@PCNF)by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu_(2)O particles.The porous nitrogendoped carbon nanofibers protected and dispersed Cu^(+)species,and its micro porous structure enhanced the interaction between CuO_(x)and reactants during eCO_(2)RR.The obtained CuO_(x)@PCNF created more effective and stable Cu^(+)/Cu^(0)active sites.It showed a high Faradaic efficiency of 62.5%for C_(2+)products in Hcell,which was 2 times higher than that of bare CuO_(x)(~31.1%).Furthermore,it achieved a maximum Faradaic efficiency of 80.7%for C_(2+)products in flow cell.In situ characterization and density functional theory(DFT)calculation confirmed that the N-doped carbon layer protected Cu^(+)from electrochemical reduction and lowered the energy barrier for the dimerization of^(*)CO.Stable and exposed Cu^(+)/Cu^(0)active sites enhanced the enrichment of^(*)CO and promoted the C-C coupling reaction on the catalyst surface,which facilitated the formation of C_(2+)products.展开更多
By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we rep...By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.展开更多
基金supported by the National Natural Science Foundation of China(22222601 and 22076019)the Fundamental Research Funds for the Central Universities(DUT23LAB611).
文摘The Cu^(+)/Cu^(0)sites of copper-based catalysts are crucial for enhancing the production of multicarbon(C_(2+))products from electrochemical CO_(2)reduction reaction(eCO_(2)RR).However,the unstable Cu^(+)and insufficient Cu^(+)/Cu^(0)active sites lead to their limited selectivity and stability for C_(2+)production.Herein,we embedded copper oxide(CuO_(x))particles into porous nitrogen-doped carbon nanofibers(CuO_(x)@PCNF)by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu_(2)O particles.The porous nitrogendoped carbon nanofibers protected and dispersed Cu^(+)species,and its micro porous structure enhanced the interaction between CuO_(x)and reactants during eCO_(2)RR.The obtained CuO_(x)@PCNF created more effective and stable Cu^(+)/Cu^(0)active sites.It showed a high Faradaic efficiency of 62.5%for C_(2+)products in Hcell,which was 2 times higher than that of bare CuO_(x)(~31.1%).Furthermore,it achieved a maximum Faradaic efficiency of 80.7%for C_(2+)products in flow cell.In situ characterization and density functional theory(DFT)calculation confirmed that the N-doped carbon layer protected Cu^(+)from electrochemical reduction and lowered the energy barrier for the dimerization of^(*)CO.Stable and exposed Cu^(+)/Cu^(0)active sites enhanced the enrichment of^(*)CO and promoted the C-C coupling reaction on the catalyst surface,which facilitated the formation of C_(2+)products.
基金supported by the Fundamental Research Funds for the Central Universities(22120230104).
文摘By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.
