以苯甲醛和甘油为原料,环己烷为带水剂,苄基三乙基氯化铵相转移催化剂催化,制备了苯甲醛甘油缩醛香料。考察了催化剂用量、反应时间、反应物配比及带水剂用量对产品收率的影响,优化反应条件为:催化剂用量3%、环己烷8 m L、醇醛物质的量...以苯甲醛和甘油为原料,环己烷为带水剂,苄基三乙基氯化铵相转移催化剂催化,制备了苯甲醛甘油缩醛香料。考察了催化剂用量、反应时间、反应物配比及带水剂用量对产品收率的影响,优化反应条件为:催化剂用量3%、环己烷8 m L、醇醛物质的量之比1.3∶1,反应时间为3 h。优化条件下产物的收率达90.3%。。展开更多
Mesoporous metals have shown considerable promise in the field of electrocatalysis due to their intrinsic properties[1,2].On one hand,high porosity offers a larger surface area than solid nanoparticles,significantly e...Mesoporous metals have shown considerable promise in the field of electrocatalysis due to their intrinsic properties[1,2].On one hand,high porosity offers a larger surface area than solid nanoparticles,significantly enhancing the utilization efficiency of precious metals[3-5].On the other hand,the continuous crystalline framework facilitates rapid electron and mass transfer while inhibiting Ostwald ripening,thereby significantly enhancing electrocatalytic activity and stability[2].More importantly,nanopores create a confined,enzyme-like microenvironment that modulates local electronic states and reaction conditions,steering catalytic selectivity[6].Despite their great potential,the application of mesoporous metals,especially through precise modulation of electronic structure to achieve single-product selectivity in complex electrocatalytic reactions,remains limited.展开更多
Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanoshe...Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanosheets(PtBi DONS)with an optimal Pt_(1)Bi_(1) ratio of 1:1 were successfully synthesized using a galvanic replacement method.Pt,Bi,DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation,achieving an excellent catalytic activity(current of 0.82 A mg_(Pt)^(-1) at 0.67 V vs.reversible hydrogen electrode(RHE))and an exceptional selectivity of 96.6%for C_(3) products,particularly glyceric acid.The superior performance stems from two key factors:(1)electron transfer from Bi_(2)O_(3) to Pt creates electron-rich Pt sites that suppress C-C bond cleavage and(2)Bi_(2)O_(3) facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions.Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi_(2)O_(3) promotes rapid charge transfer and stable intermediate formation.Moreover,PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.展开更多
文摘以苯甲醛和甘油为原料,环己烷为带水剂,苄基三乙基氯化铵相转移催化剂催化,制备了苯甲醛甘油缩醛香料。考察了催化剂用量、反应时间、反应物配比及带水剂用量对产品收率的影响,优化反应条件为:催化剂用量3%、环己烷8 m L、醇醛物质的量之比1.3∶1,反应时间为3 h。优化条件下产物的收率达90.3%。。
文摘Mesoporous metals have shown considerable promise in the field of electrocatalysis due to their intrinsic properties[1,2].On one hand,high porosity offers a larger surface area than solid nanoparticles,significantly enhancing the utilization efficiency of precious metals[3-5].On the other hand,the continuous crystalline framework facilitates rapid electron and mass transfer while inhibiting Ostwald ripening,thereby significantly enhancing electrocatalytic activity and stability[2].More importantly,nanopores create a confined,enzyme-like microenvironment that modulates local electronic states and reaction conditions,steering catalytic selectivity[6].Despite their great potential,the application of mesoporous metals,especially through precise modulation of electronic structure to achieve single-product selectivity in complex electrocatalytic reactions,remains limited.
基金supported by the National Natural Science Foundation of China(22272103)Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27 and 2022TD-35)+1 种基金the Technology Innovation Leading Program of Shaanxi in China,Sanqin Scholars Innovation Teams in Shaanxi Province in China,the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2023YSIP-MSESNNU008)Shaanxi Province Postdoctoral Science Foundation(2024BSHSDZZ080).
文摘Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanosheets(PtBi DONS)with an optimal Pt_(1)Bi_(1) ratio of 1:1 were successfully synthesized using a galvanic replacement method.Pt,Bi,DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation,achieving an excellent catalytic activity(current of 0.82 A mg_(Pt)^(-1) at 0.67 V vs.reversible hydrogen electrode(RHE))and an exceptional selectivity of 96.6%for C_(3) products,particularly glyceric acid.The superior performance stems from two key factors:(1)electron transfer from Bi_(2)O_(3) to Pt creates electron-rich Pt sites that suppress C-C bond cleavage and(2)Bi_(2)O_(3) facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions.Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi_(2)O_(3) promotes rapid charge transfer and stable intermediate formation.Moreover,PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.
