The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_(2)products remains challenge.Cu-based catalyst with the specific Cu^(0)and Cu^(+)sites is important to generate C_(2)products.This work used nitrogen(N)to tune amounts of Cu^(0)and Cu^(+)sites in Cu_(2)O catalysts and improve C_(2)-product conversion.The controllable Cu^(0)/Cu^(+)ratio of Cu_(2)O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment.The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu^(0)/Cu^(+)ratio.The optimal Cu^(0)/Cu^(+)ratio was determined as 0.43 for selective electroreduction CO_(2)to ethylene.X-ray spectroscopy and density functional theory(DFT)calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of N–Cu bond and stabilize Cu^(+),resulting in a 92.3%reduction in the potential energy change for^(∗)CO-^(∗)CO dimerization.This study is inspiring in designing high performance electrocatalysts for CO_(2)conversion.展开更多
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
Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collap...Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.展开更多
基金supported by“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Nos.2022C03146 and 2023C03017)the National Natural Science Foundation of China(Nos.U23A20677 and 22022610)+1 种基金Zhejiang Provincial Natural Science Foundation of China(No.LDT23E06015B06)the National Funded Postdoctoral Researcher Program of China(No.GZC20232363).
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_(2)products remains challenge.Cu-based catalyst with the specific Cu^(0)and Cu^(+)sites is important to generate C_(2)products.This work used nitrogen(N)to tune amounts of Cu^(0)and Cu^(+)sites in Cu_(2)O catalysts and improve C_(2)-product conversion.The controllable Cu^(0)/Cu^(+)ratio of Cu_(2)O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment.The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu^(0)/Cu^(+)ratio.The optimal Cu^(0)/Cu^(+)ratio was determined as 0.43 for selective electroreduction CO_(2)to ethylene.X-ray spectroscopy and density functional theory(DFT)calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of N–Cu bond and stabilize Cu^(+),resulting in a 92.3%reduction in the potential energy change for^(∗)CO-^(∗)CO dimerization.This study is inspiring in designing high performance electrocatalysts for CO_(2)conversion.
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financially supported by the National Natural Science Foundation of China(52102233)Science and Technology Project of Hebei Education Department(QN2023019)。
文摘Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.
