Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
使用Anton Paar DMA 4500U型振动管密度计,测量碳酸二甲酯+碳酸二乙酯和碳酸二甲酯+碳酸甲乙酯两个混合体系在293.15~313.15K温度区间和常压下,全浓度范围的密度;基于所测得的密度数据,计算这两个混合体系的超额摩尔体积。用Redlich-Kis...使用Anton Paar DMA 4500U型振动管密度计,测量碳酸二甲酯+碳酸二乙酯和碳酸二甲酯+碳酸甲乙酯两个混合体系在293.15~313.15K温度区间和常压下,全浓度范围的密度;基于所测得的密度数据,计算这两个混合体系的超额摩尔体积。用Redlich-Kister方程对超额体积和摩尔分数关系进行关联检验。结果表明,不同温度下超额摩尔体积随组分摩尔分率升高,碳酸二甲酯+碳酸二乙酯体系超额摩尔体积均为正偏差,碳酸二甲酯+碳酸甲乙酯呈先正偏差后负偏差的趋势。这些现象是由这两个混合体系中偶极-偶极相互作用、分子间作用力、以及溶剂化效应等多种因素的综合作用导致的。通过Prigogine-Flory-Patterson预测理论对混合物的超额摩尔体积数据进行分析。展开更多
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
文摘使用Anton Paar DMA 4500U型振动管密度计,测量碳酸二甲酯+碳酸二乙酯和碳酸二甲酯+碳酸甲乙酯两个混合体系在293.15~313.15K温度区间和常压下,全浓度范围的密度;基于所测得的密度数据,计算这两个混合体系的超额摩尔体积。用Redlich-Kister方程对超额体积和摩尔分数关系进行关联检验。结果表明,不同温度下超额摩尔体积随组分摩尔分率升高,碳酸二甲酯+碳酸二乙酯体系超额摩尔体积均为正偏差,碳酸二甲酯+碳酸甲乙酯呈先正偏差后负偏差的趋势。这些现象是由这两个混合体系中偶极-偶极相互作用、分子间作用力、以及溶剂化效应等多种因素的综合作用导致的。通过Prigogine-Flory-Patterson预测理论对混合物的超额摩尔体积数据进行分析。
