Man Yang,Xiaochen Zhao,Yujing Ren,Jia Wang,Nian Lei,Aiqin Wang,Tao Zhang
Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PD) is an important yet challenging method for the transformation of biomass into value-added chemicals due to steric hindrance and unfavorable thermodynamics. In previous studies, chemoselective performances were found demanding and sensitive to H 2 pressure. In this regard, we manipulate the chemical/physical characteristics of the catalyst supports via doping Nb into WO x and prepared 1D needle-, 2D flake-, and 3D sphere-stack mesoporous structured Nb-WO x with increased surface acid sites. Moreover, Nb doping can successfully inhibit the over-reduction of active W species during glycerol hydrogenolysis and substantially broaden the optimal H 2 pressure from 1 to 5 MPa. When Nb doping is 2%, supported Pt catalysts showed promising performance for the selective hydrogenolysis of glycerol to 1,3-PD over an unprecedentedly wide H 2 pressure range, which will guarantee better catalyst stability in the long run, as well as expand their applications to other hydrogen-related reactions.
Graphical Surface hydroxyl groups of the support play a crucial role for WO x -support interaction. A strong interaction between WO x species and support can improve the dispersion of WO x species and generate more WO x -support interface Brønsted acid sites, which are beneficial for 1,3-propanediol synthesis in glycerol hydrogenolysis. For Pt-WO x -based catalysts, researchers pay much attention to study the influence of Pt-WO x interaction on glycerol hydrogenolysis, ignoring the interaction between WO x and support. Herein, four Pt/W/SiZr-T catalysts with different surface hydroxyl groups on support are prepared and characterized. The results show that bibridged (OH II ) and tribridged hydroxyl groups (OH III ) on SiZr-T supports could react with WO x species through forming Zr−O−W bands and retard the agglomeration of WO x species. The highly dispersed WO x species and Zr−O−W bands are the origination of inherent and in-situ generated Brønsted acid, which are beneficial for 1,3-propanediol synthesis. As a result, Pt/W/SiZr-70 exhibits outstanding performance due to abundant OH II and OH III on SiZr-70. The initial space time yield of 1,3-propanediol on Pt/W/SiZr-70 reaches 2.280 g 1,3-PDO ⋅ g cat −1 ⋅ h −1 , the highest among reported results. This r esearch reveals the role of WO x -support interaction on glycerol hydrogenolysis and provides a new direction to design Pt-WO x -based catalysts for selective hydrogenation reactions.
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