文献类型：期刊文献

中文题名：Pt-Bi界面结构调控及其催化甘油选择性氧化反应性能

英文题名：Regulation of Pt-Bi interfaces for selective catalytic oxidation of glycerol

作者：于志奕[1];方俊彦[1];陈文尧[1];钱刚[1];段学志[1]

机构：[1]华东理工大学化工学院,化学工程联合国家重点实验室,上海200237

年份：2024

卷号：75

期号：10

起止页码：3568

中文期刊名：化工学报

外文期刊名：CIESC Journal

收录：CSTPCD;;EI(收录号：20251218059630);北大核心:【北大核心2023】；CSCD:【CSCD2023_2024】；

基金：国家自然科学基金项目(22178101)。

语种：中文

中文关键词：甘油;氧化;Pt基催化剂;界面;分子模拟

外文关键词：glycerol;oxidation;Pt-based catalyst;interface;molecular simulation

摘要：通过原子层沉积(ALD)技术和浸渍-还原法,分别制备了两种具有不同Pt-Bi界面结构的Pt基催化剂:Pt/Bi_(2)O_(3)-CNTs和PtBi/CNTs,结合实验和密度泛函理论(DFT)计算比较研究了两种催化剂上甘油选择性氧化反应行为。表征结果显示,Pt/Bi_(2)O_(3)-CNTs催化剂中存在相对均一的Pt-Bi_(2)O_(3)界面结构,而PtBi/CNTs催化剂则形成了Pt1Bi1金属间化合物。活性评价实验发现,两种催化剂均促进了甘油仲羟基的优先氧化;相对而言,Pt/Bi_(2)O_(3)-CNTs催化剂由于具有较小的粒径和较高的Pt04f结合能从而表现出较好的甘油氧化反应活性,PtBi/CNTs催化剂会导致产物1,3-二羟基丙酮(DHA)的深度氧化。进一步的DFT计算结果表明,两种催化剂上甘油仲羟基氧化生成DHA过程的决速步骤均为仲碳上C—H键断裂反应,Pt/Bi_(2)O_(3)-CNTs催化剂上该步骤的能垒相对较低,因而表现出更高的反应活性;PtBi/CNTs催化剂表面,DHA较容易吸附,因此更易被深度氧化。
The interfacial sites between Pt and promoters are highly conducive to the selective oxidation of glycerol to 1,3-dihydroxyacetone(DHA).In this study,two Pt-based catalysts with different Pt-Bi interfacial structures,Pt/Bi_(2)O_(3)-CNTs and PtBi/CNTs,were prepared by using atomic layer deposition and impregnation-reduction method,respectively.The selective oxidation of glycerol on the two catalysts was investigated through a combination of experiments and density functional theory(DFT)calculations.Characterization results show that there is a relatively uniform Pt-Bi_(2)O_(3)interface structure in the Pt/Bi_(2)O_(3)-CNTs catalyst,while the PtBi/CNTs catalyst forms a Pt1Bi1 intermetallic compound.Both catalysts promote the preferential oxidation of the secondary hydroxyl group in glycerol.Comparatively,the Pt/Bi_(2)O_(3)-CNTs catalyst demonstrates superior glycerol oxidation activity due to its smaller particle size and higher Pt04f binding energy,whereas the PtBi/CNTs catalyst facilitates the deep oxidation of DHA.Furthermore,DFT calculations reveal that the rate-determining step for the oxidation of the secondary hydroxyl group of glycerol to DHA on both catalysts is C—H bond cleavage,with a relatively lower energy barrier glycerol[J].CIESC Journal,2024,75(10):3568-3578 observed on the Pt/Bi_(2)O_(3)-CNTs catalyst,resulting in higher reaction activity.On the surface of the PtBi/CNTs catalyst,DHA exhibits greater adsorption affinity,rendering it more susceptible to deep oxidation.The insights provided here could serve as a guide for the design and optimization of Pt-based catalysts for the selective oxidation of glycerol to DHA.