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
氨是重要的工业原料和潜在的无碳能源载体。电催化硝酸根还原合成氨(NO_(3)RR)是一种新兴制氨工艺,具有可再生适配性强及条件温和等优势。此外,硝酸根离子作为常见污染物广泛存在于工农业废水中,NO_(3)RR既能制取高价值氨产品,又可净化...氨是重要的工业原料和潜在的无碳能源载体。电催化硝酸根还原合成氨(NO_(3)RR)是一种新兴制氨工艺,具有可再生适配性强及条件温和等优势。此外,硝酸根离子作为常见污染物广泛存在于工农业废水中,NO_(3)RR既能制取高价值氨产品,又可净化污水,达到“一石二鸟”的效果。通过熔炼甩带和化学脱合金的方法制备了纳米多孔Cu材料,随后通过电沉积的方法在其表面负载了CoO纳米颗粒,制备了纳米多孔Cu/CoO异质结构电催化剂。由于其独特的双连续纳米多孔结构以及Cu与CoO之间的协同作用,Cu/CoO异质结构电催化剂在碱性条件下具有优异的NO_(3)RR催化活性,在-0.5 V vs. RHE电位下氨产率及法拉第效率分别达到1.64 mmol·h^(-1)·cm^(-2)及99.59%,并具有良好的催化稳定性。展开更多
丙烯水合法生成异丙醇过程中会产生水/异丙醇/正丙醇共沸体系,将其中有机产物及附加产品高效回收是分离领域的研究重点。通过量子化学计算筛选出二甲基亚砜为萃取剂。利用Aspen Plus V12软件搭建常规萃取精馏(ED)工艺并分离出符合工业...丙烯水合法生成异丙醇过程中会产生水/异丙醇/正丙醇共沸体系,将其中有机产物及附加产品高效回收是分离领域的研究重点。通过量子化学计算筛选出二甲基亚砜为萃取剂。利用Aspen Plus V12软件搭建常规萃取精馏(ED)工艺并分离出符合工业要求的产品。引入渗透汽化技术进行节能改进,进一步提出渗透汽化-萃取精馏耦合工艺(PV-ED)。通过计算年总成本(TAC)、气体排放量(M_(gas))和[火用]效率来对工艺进行经济性能、环境性能和热力学效率方面的评价和比较。计算结果显示,相较ED工艺,PV-ED工艺的TAC减少了21.31%;M_(gas)降低了38.83%;整体[火用]损失减少了541.46 kW,[火用]效率提高了7.01%。展开更多
以麻疯树油为原料,研究了生产生物柴油过程中的酯交换反应条件的影响及反应动力学。结果表明,酯交换反应的适宜操作条件为:油∶甲醇=1∶6(摩尔比),使用油重的1.3%的KOH为催化剂,在64℃下反应20 m in,甲酯收率达98%以上。在优化反应条件...以麻疯树油为原料,研究了生产生物柴油过程中的酯交换反应条件的影响及反应动力学。结果表明,酯交换反应的适宜操作条件为:油∶甲醇=1∶6(摩尔比),使用油重的1.3%的KOH为催化剂,在64℃下反应20 m in,甲酯收率达98%以上。在优化反应条件的基础上,研究了其动力学特征,32℃和51℃时的反应速率常数k分别为0.6627 L/(m in.mol)和0.9474 L/(m in.mol),反应的活化能约为Ea=15.46 kJ/mol。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.
文摘氨是重要的工业原料和潜在的无碳能源载体。电催化硝酸根还原合成氨(NO_(3)RR)是一种新兴制氨工艺,具有可再生适配性强及条件温和等优势。此外,硝酸根离子作为常见污染物广泛存在于工农业废水中,NO_(3)RR既能制取高价值氨产品,又可净化污水,达到“一石二鸟”的效果。通过熔炼甩带和化学脱合金的方法制备了纳米多孔Cu材料,随后通过电沉积的方法在其表面负载了CoO纳米颗粒,制备了纳米多孔Cu/CoO异质结构电催化剂。由于其独特的双连续纳米多孔结构以及Cu与CoO之间的协同作用,Cu/CoO异质结构电催化剂在碱性条件下具有优异的NO_(3)RR催化活性,在-0.5 V vs. RHE电位下氨产率及法拉第效率分别达到1.64 mmol·h^(-1)·cm^(-2)及99.59%,并具有良好的催化稳定性。
文摘丙烯水合法生成异丙醇过程中会产生水/异丙醇/正丙醇共沸体系,将其中有机产物及附加产品高效回收是分离领域的研究重点。通过量子化学计算筛选出二甲基亚砜为萃取剂。利用Aspen Plus V12软件搭建常规萃取精馏(ED)工艺并分离出符合工业要求的产品。引入渗透汽化技术进行节能改进,进一步提出渗透汽化-萃取精馏耦合工艺(PV-ED)。通过计算年总成本(TAC)、气体排放量(M_(gas))和[火用]效率来对工艺进行经济性能、环境性能和热力学效率方面的评价和比较。计算结果显示,相较ED工艺,PV-ED工艺的TAC减少了21.31%;M_(gas)降低了38.83%;整体[火用]损失减少了541.46 kW,[火用]效率提高了7.01%。
