以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴...以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴极材料电镀时间、溶剂、支持电解质、电流密度、通电量和温度等因素对烯丙基氯电羧化反应的影响。在25℃反应温度、90 min Cu-In复合材料电镀时间、MeCN溶剂、四乙基碘化铵(TEAI)支持盐、3.0 F/mol电解电量、8 mA·cm^(2)电流密度的优化条件下,3-丁烯酸的产率可达56%。此外,在优化条件下还考察了烯丙基溴、肉桂基氯、肉桂基溴、3-氯-2-甲基丙烯等烯丙基卤代物的电羧化反应,结果表明均可得到相应的羧酸,意味着Cu-In双金属电极对催化烯丙基卤代物电羧化反应具一定的普适性。展开更多
The combination of a powerful CO_(2)-enriching carrier and robust active component provides a new idea for the construction of efficient catalysts for electrocatalytic CO_(2)reduction.Herein,novel perforated nitrogen-...The combination of a powerful CO_(2)-enriching carrier and robust active component provides a new idea for the construction of efficient catalysts for electrocatalytic CO_(2)reduction.Herein,novel perforated nitrogen-rich graphene-like carbon nanolayers(PNGC)are prepared from biomass derivatives,which promotes the oriented deposition of In-doped Cu_(2)(OH)_(3)(NO_(3))nanosheet patches.A robust Cu-In/PNGC composite catalyst is then obtained via simple in-situ electrochemical reduction.Unsurprisingly,CuIn/PNGC exhibits a CO Faradaic efficiency(FECO)of 91.3%and a remarkable CO partial current density(jCO)of 136.4 m A cm^(-2)at a moderate overpotential of 0.59 V for electrocatalytic CO_(2)reduction reaction(CO_(2)RR).DFT calculations and experimental studies indicate that the strong carrier effect of PNGC makes PNGC carried Cu-In nanosheets improved the adsorption capacity of CO_(2)gas,reconfigured electronic structure,and reduced free energy of key intermediate formation,thereby the CO_(2)activation and conversion are promoted.展开更多
Four compositions of alloys were designed. They were Cu 2% In, Cu 7% In, Cu 11% In and Cu 23% In(mass fraction). These alloy specimens were prepared by metal mold. By means of microstructure observation, macrostructur...Four compositions of alloys were designed. They were Cu 2% In, Cu 7% In, Cu 11% In and Cu 23% In(mass fraction). These alloy specimens were prepared by metal mold. By means of microstructure observation, macrostructure observation and electron probe analyzing, microstructures and macrostructures of the specimens were analyzed by comparison method. Microstructure component and relationship between structure and composition of alloys were investigated. The results show that with increasing indium content, the grain changes from columnar one to equiaxed one, the equiaxed grain increases, the columnar grain zone decreases and the grain size becomes small. With increasing indium content, the growth way changes from planar one to dendritic one. Peritectic reaction plays inhibiting role on the growth of dendrite and affects the orientation of dendrite. Indium content has influence on lattice constant of Cu solid展开更多
Local segregation in Cu-In precursors and its effects on the element distribution and microstructures of selenized CuInSe2 thin films were investigated. Cu-In precursors with an ideal total mole ratio of Cu to In of 0...Local segregation in Cu-In precursors and its effects on the element distribution and microstructures of selenized CuInSe2 thin films were investigated. Cu-In precursors with an ideal total mole ratio of Cu to In of 0.92 were prepared by middle frequency alternating current magnetron sputtering with Cu-In alloy target, then CuInSe2 absorbers for solar cells were formed by selenization process in selenium atmosphere. Scanning electron microscope and energy dispersive X-ray spectroscope were used respectively to observe the surface morphologies and determine the compositions of both Cu-In precursors and CuInSe2 thin films. Their microstructures were characterized by X-ray diffractometry and Raman spectroscope. The results show that Cu-In precursors are mainly composed of (Cu11In9) phase with In-rich solid solution. Stoichiometric CuInSe2 thin films with a homogeneous element distribution and single chalcopyrite phase can be synthesized from a segregated Cu-In precursor film with an ideal total mole ratio of Cu to In of 0.92. CuInSe2 thin film shows P-type conductivity and its resistivity reaches 1.2×103Ω·cm.展开更多
Bimetallic Cu-In hybrid electrocatalysts are promising noble metal-free catalysts for selective electrochemical CO_(2) reduction reaction(ECO_(2) RR).Most reports show Cu-In catalysts are selective towards CO evolutio...Bimetallic Cu-In hybrid electrocatalysts are promising noble metal-free catalysts for selective electrochemical CO_(2) reduction reaction(ECO_(2) RR).Most reports show Cu-In catalysts are selective towards CO evolutio n.However,few show similarly high selectivity towards formate.Herein we fabricated composition tunable Cu-In hydroxides(Cu_xIn_y-OH) by the hydrothermal method and studied their composition effect on electrochemical CO_(2) reduction in detail. We found that the selectivity of CO_(2) reduction products shifted from CO to formate when the content of In increased in the Cu_xIn_y-OH electrocatalysts.The Cu rich electrocatalyst mostly produced CO,which could achieve a Faradaic efficiency(FE) to 75.8% at-0.59 V vs.RHE(Cu_(76)In_(24)based electrocatalysts).In comparison,the In rich electrocatalysts selectively produced formate,which possessed the FE of formate up to 85% at-1.01 V vs.RHE.Our work systematically illustrates the composition effect on hybrid catalysts,and provides insights into the design of highly selective catalysts for ECO_(2) RR.展开更多
文摘以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴极材料电镀时间、溶剂、支持电解质、电流密度、通电量和温度等因素对烯丙基氯电羧化反应的影响。在25℃反应温度、90 min Cu-In复合材料电镀时间、MeCN溶剂、四乙基碘化铵(TEAI)支持盐、3.0 F/mol电解电量、8 mA·cm^(2)电流密度的优化条件下,3-丁烯酸的产率可达56%。此外,在优化条件下还考察了烯丙基溴、肉桂基氯、肉桂基溴、3-氯-2-甲基丙烯等烯丙基卤代物的电羧化反应,结果表明均可得到相应的羧酸,意味着Cu-In双金属电极对催化烯丙基卤代物电羧化反应具一定的普适性。
基金supported by the National Natural Science Foundation of China(U21B2099)。
文摘The combination of a powerful CO_(2)-enriching carrier and robust active component provides a new idea for the construction of efficient catalysts for electrocatalytic CO_(2)reduction.Herein,novel perforated nitrogen-rich graphene-like carbon nanolayers(PNGC)are prepared from biomass derivatives,which promotes the oriented deposition of In-doped Cu_(2)(OH)_(3)(NO_(3))nanosheet patches.A robust Cu-In/PNGC composite catalyst is then obtained via simple in-situ electrochemical reduction.Unsurprisingly,CuIn/PNGC exhibits a CO Faradaic efficiency(FECO)of 91.3%and a remarkable CO partial current density(jCO)of 136.4 m A cm^(-2)at a moderate overpotential of 0.59 V for electrocatalytic CO_(2)reduction reaction(CO_(2)RR).DFT calculations and experimental studies indicate that the strong carrier effect of PNGC makes PNGC carried Cu-In nanosheets improved the adsorption capacity of CO_(2)gas,reconfigured electronic structure,and reduced free energy of key intermediate formation,thereby the CO_(2)activation and conversion are promoted.
文摘Four compositions of alloys were designed. They were Cu 2% In, Cu 7% In, Cu 11% In and Cu 23% In(mass fraction). These alloy specimens were prepared by metal mold. By means of microstructure observation, macrostructure observation and electron probe analyzing, microstructures and macrostructures of the specimens were analyzed by comparison method. Microstructure component and relationship between structure and composition of alloys were investigated. The results show that with increasing indium content, the grain changes from columnar one to equiaxed one, the equiaxed grain increases, the columnar grain zone decreases and the grain size becomes small. With increasing indium content, the growth way changes from planar one to dendritic one. Peritectic reaction plays inhibiting role on the growth of dendrite and affects the orientation of dendrite. Indium content has influence on lattice constant of Cu solid
基金Project(2004AA513023) supported by the National High Technology Research and Development Program of China
文摘Local segregation in Cu-In precursors and its effects on the element distribution and microstructures of selenized CuInSe2 thin films were investigated. Cu-In precursors with an ideal total mole ratio of Cu to In of 0.92 were prepared by middle frequency alternating current magnetron sputtering with Cu-In alloy target, then CuInSe2 absorbers for solar cells were formed by selenization process in selenium atmosphere. Scanning electron microscope and energy dispersive X-ray spectroscope were used respectively to observe the surface morphologies and determine the compositions of both Cu-In precursors and CuInSe2 thin films. Their microstructures were characterized by X-ray diffractometry and Raman spectroscope. The results show that Cu-In precursors are mainly composed of (Cu11In9) phase with In-rich solid solution. Stoichiometric CuInSe2 thin films with a homogeneous element distribution and single chalcopyrite phase can be synthesized from a segregated Cu-In precursor film with an ideal total mole ratio of Cu to In of 0.92. CuInSe2 thin film shows P-type conductivity and its resistivity reaches 1.2×103Ω·cm.
基金funding support from the National Key Research and Development Program of China (2019YFE0123400)the Tianjin Distinguished YoungScholars Fund (20JCJQJC00260)+3 种基金the "111" Project (B16027)funding support from the Villum Foundation V-SUSTAIN Grant 9455funding from the European Union's Horizon 2020 research and innovation program through a Marie Sklodowska-Curie postdoctoral fellowship under grant agreement 844288 (STRATCAT-CO_(2))scholarship from the China Scholarship Council。
文摘Bimetallic Cu-In hybrid electrocatalysts are promising noble metal-free catalysts for selective electrochemical CO_(2) reduction reaction(ECO_(2) RR).Most reports show Cu-In catalysts are selective towards CO evolutio n.However,few show similarly high selectivity towards formate.Herein we fabricated composition tunable Cu-In hydroxides(Cu_xIn_y-OH) by the hydrothermal method and studied their composition effect on electrochemical CO_(2) reduction in detail. We found that the selectivity of CO_(2) reduction products shifted from CO to formate when the content of In increased in the Cu_xIn_y-OH electrocatalysts.The Cu rich electrocatalyst mostly produced CO,which could achieve a Faradaic efficiency(FE) to 75.8% at-0.59 V vs.RHE(Cu_(76)In_(24)based electrocatalysts).In comparison,the In rich electrocatalysts selectively produced formate,which possessed the FE of formate up to 85% at-1.01 V vs.RHE.Our work systematically illustrates the composition effect on hybrid catalysts,and provides insights into the design of highly selective catalysts for ECO_(2) RR.
