物理化学学报2022，Vol.38Issue(10)：73-80,8.DOI:10.3866/PKU.WHXB202207014
负载Pt-WOx催化剂上甘油选择氢解合成1,3-丙二醇
Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts
摘要
Abstract
Glycerol is a versatile platform compound that is formed in considerable amounts as a by-product of biodiesel production.The catalytic selective hydrogenolysis of glycerol to 1,3-propanediol(1,3-PDO)provides a sustainable route for the synthesis of this important diol.In this study,a series of platinum-tungsten oxide(Pt-WOx)catalysts with different WOx surface densities dispersed on titanium(IV)oxide,zirconium(IV)oxide,and aluminum oxide supports were prepared and evaluated for the glycerol hydrogenolysis to 1,3-PDO.The highest reaction activity and 1,3-PDO selectivity were achieved at a WOx density of approximately 1.5-2.0 W·nm-2,with all three support materials.Such a strong dependence on the surface density of WOx revealed the critical role of the dispersed WOx domains in the hydrogenolysis of glycerol to 1,3-PDO.The infrared spectra for carbon monoxide adsorption confirmed the electron transfer and strong interaction between the Pt particles and WOx domains.These phenomena were hypothesized to contribute to the superior selectivity to 1,3-PDO over 1,2-PDO of the supported Pt-WOx catalysts when compared with the corresponding supported Pt catalysts.The realized superior 1,3-PDO selectivity was consistent with its higher stability on the Pt-WOx catalysts,as reflected by the lower reaction rate constant of 1,3-PDO than those of 1,2-PDO and glycerol obtained in their hydrogenolysis reactions.There existed a volcano-type dependence of the glycerol reaction activity on the hydrogen partial pressure.Such a dependence,together with the measured ratio(1:2)of the secondary to the primary C—H bonds in 1,3-PDO in the presence of deuterium and deuterium oxide(replacing hydrogen and water,respectively),indicated that the glycerol hydrogenolysis proceeds by the kinetically relevant dehydrogenation of glycerol to the glyceraldehyde intermediate,followed by the dehydration and hydrogenation of glyceraldehyde to 1,3-PDO over the Pt-WOx catalysts.关键词
甘油/1,3-丙二醇/氢解反应/Pt催化剂/WO3/强相互作用Key words
Glycerol/1,3-propandiol/Hydrogenolysis/Platinum/Tungsten oxide/Strong interaction分类
化学化工引用本文复制引用
李宇明,刘海超..负载Pt-WOx催化剂上甘油选择氢解合成1,3-丙二醇[J].物理化学学报,2022,38(10):73-80,8.基金项目
This work was supported by the National Key Research and Development Program of China(2021YFA1501104),Natural Science Foundation of China(22032001,21832001,21821004),Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201905).国家重点研发计划项目(2021YFA1501104),国家自然科学基金项目(22032001,21832001,21821004),北京分子科学国家研究中心项目(BNLMS-CXXM-201905)资助 （2021YFA1501104）
