Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)acc...Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.展开更多
The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and...The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.展开更多
The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficien...The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficiency and limited reversibility due to the sluggish kinetics of the CO_(2) reduction and evolution reactions.Herein,a multiscale nanoporous interpenetrating phase nanohybrid of RuAl intermetallic and Cu_(2)O(MP-Cu_(2)O/RuAl) was carved by driving synchronous phase and microstructure evolutions through dealloying of one RuCuAl master alloy.The built-in RuAl intermetallic and Cu_(2)O closely stack to form abundant nano-interfaces with revolutionized electronic structure,The theoretical simulations reveal that the Cu_(2)O/RuAl interface can distinctly reduce the energy barrier of the Li_(2)CO_(3) decomposition reaction,The interconnected pore channels with large surface area can enhance catalytic site accessibility,mass transfer,and uniform deposition of the discharge products.In situ differential electrochemical mass spectrometry discloses that the CO_(2)-to-electron ratio during charging coincides with the theoretical value of 3/4,demonstrating the high efficacy of MP-Cu_(2)O/RuAl in achieving the recycling of CO_(2).The dealloying protocol provides an affordable platform to empower transition metal oxides into high-efficiency electrocatalysts by hybridizing with metallic nano-sponge for advancing the application of Li-CO_(2)batteries.展开更多
This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of ...This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.展开更多
Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O ...Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).展开更多
为制备具有光热和光催化性能的双功能织物用于净化水,通过分子组装制备出兼具可见光与近红外响应的金氧化亚铜异质结纳米颗粒(Au@Cu_(2)O),使用轧-烘-焙将纳米材料整理到棉织物上,得到可用于界面蒸发生产清洁水的光热-光催化双功能棉织...为制备具有光热和光催化性能的双功能织物用于净化水,通过分子组装制备出兼具可见光与近红外响应的金氧化亚铜异质结纳米颗粒(Au@Cu_(2)O),使用轧-烘-焙将纳米材料整理到棉织物上,得到可用于界面蒸发生产清洁水的光热-光催化双功能棉织物。利用SEM、TEM、UV-VIS-NIR、XRD、FTIR等对Au@Cu_(2)O及Au@Cu_(2)O改性棉织物进行形貌、结构的表征,并对改性棉织物在模拟太阳光下对水的净化处理性能进行研究。结果表明:Au@Cu_(2)O改性棉织物具有良好的光热、光催化性能,在功率密度0.1 W cm^(2)的模拟太阳光源照射下,Au@Cu_(2)O改性棉织物的蒸发速率为1.25 kg(m^(2)·h),太阳光-蒸汽转换效率为77.4%,可见光辐照180 min后对甲基橙的降解率达到89.2%。制备的Au@Cu_(2)O改性棉织物在净化水领域展示出良好的应用潜力。展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22479097)the Shanghai Science and Technology Committee(Grant No.23ZR1433000)the National High-Level Talent Program for Young Scholars,the Start-up Fund(F.S.)from Shanghai Jiao Tong University.
文摘Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010042,2021R1A6C103A427)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1I1A1A01060380,2021R1C1C2010726,2019H1D3A1A01071209)。
文摘The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.
基金financially National Natural Science Foundation of China (52201254)Natural Science Foundation of Shandong Province (ZR2023ME155, ZR2023ME085)+4 种基金project of “20 Items of University” of Jinan (202228046)Taishan Scholar Project of Shandong Province (tsqn202306226)Scientific Research Foundation for New Talents in University of Jinan (16010089104)Introducing Major Universities and Research Institutions to Jointly Build Innovative Carrier Project of Jining City (2023DYDS022)support provided by the Shandong Province Laboratory of Technology and Equipment for Molecular Diagnosis。
文摘The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficiency and limited reversibility due to the sluggish kinetics of the CO_(2) reduction and evolution reactions.Herein,a multiscale nanoporous interpenetrating phase nanohybrid of RuAl intermetallic and Cu_(2)O(MP-Cu_(2)O/RuAl) was carved by driving synchronous phase and microstructure evolutions through dealloying of one RuCuAl master alloy.The built-in RuAl intermetallic and Cu_(2)O closely stack to form abundant nano-interfaces with revolutionized electronic structure,The theoretical simulations reveal that the Cu_(2)O/RuAl interface can distinctly reduce the energy barrier of the Li_(2)CO_(3) decomposition reaction,The interconnected pore channels with large surface area can enhance catalytic site accessibility,mass transfer,and uniform deposition of the discharge products.In situ differential electrochemical mass spectrometry discloses that the CO_(2)-to-electron ratio during charging coincides with the theoretical value of 3/4,demonstrating the high efficacy of MP-Cu_(2)O/RuAl in achieving the recycling of CO_(2).The dealloying protocol provides an affordable platform to empower transition metal oxides into high-efficiency electrocatalysts by hybridizing with metallic nano-sponge for advancing the application of Li-CO_(2)batteries.
基金FAPESP,Brazil(#2023/10027-5,#2014/50945-4,#2020/15230-5,and#2021/000675-4)CNPq,Brazil(#465571/2014-0,#303269/2021-9,and#307837/2014-9)+6 种基金Instituto Serrapilheira(grant number Serra-2211-41925)FAPEMIG,Brazil(#PPM-00831-15)for support of this workCNPq,Brazil(#105944/2022-0)and PROPEUNESP(13/2022)FAPESP(#2019/00463-7,#2018/22845-6,and#2021/08007-0,respectively)for scholarshipsthe National Institute for Alternative Technologies of Detection,Toxicological Evaluation and Removal of Micropollutants and Radioactives(INCT-DATREM)the support of the Research Centre for Greenhouse Gas Innovation(RCGI),hosted by the University of Sao Paulo(USP)and sponsored by FAPESP and Shell Brasilthe strategic support given by ANP,Brazil(Brazilian National Oil,Natural Gas,and Biofuels Agency)through the R&D levy regulation。
文摘This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.
文摘Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).
文摘为制备具有光热和光催化性能的双功能织物用于净化水,通过分子组装制备出兼具可见光与近红外响应的金氧化亚铜异质结纳米颗粒(Au@Cu_(2)O),使用轧-烘-焙将纳米材料整理到棉织物上,得到可用于界面蒸发生产清洁水的光热-光催化双功能棉织物。利用SEM、TEM、UV-VIS-NIR、XRD、FTIR等对Au@Cu_(2)O及Au@Cu_(2)O改性棉织物进行形貌、结构的表征,并对改性棉织物在模拟太阳光下对水的净化处理性能进行研究。结果表明:Au@Cu_(2)O改性棉织物具有良好的光热、光催化性能,在功率密度0.1 W cm^(2)的模拟太阳光源照射下,Au@Cu_(2)O改性棉织物的蒸发速率为1.25 kg(m^(2)·h),太阳光-蒸汽转换效率为77.4%,可见光辐照180 min后对甲基橙的降解率达到89.2%。制备的Au@Cu_(2)O改性棉织物在净化水领域展示出良好的应用潜力。
