Organic Modifiers Promote Furfuryl Alcohol Ring Hydrogenation via Surface Hydrogen-Bonding Interactions

被引:16
作者
Coan, Patrick D. [1 ]
Farberow, Carrie A. [2 ]
Griffin, Michael B. [2 ]
Medlin, J. Will [1 ]
机构
[1] Univ Colorado, Dept Chem & Biol Engn, Boulder, CO 80309 USA
[2] Catalyt Carbon Transformat & Scale Up Ctr, Golden, CO 80401 USA
来源
ACS CATALYSIS | 2021年 / 11卷 / 06期
关键词
heterogeneous catalysis; catalyst modification; self-assembled monolayers; phosphonic acids; thiols; ring hydrogenation; furfuryl alcohol;
D O I
10.1021/acscatal.0c04138
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Interactions between surface adsorbed species can affect catalyst reactivity, and thus, the ability to tune these interactions is of considerable importance. Deposition of organic modifiers provides one method of intentionally introducing controllable surface interactions onto catalyst surfaces. In this study, Pd/Al2O3 catalysts were modified with either thiol or phosphonic acid (PA) ligands and tested in the hydrogenation of furanic species. The thiol modifiers were found to inhibit ring hydrogenation (RH) activity, with the degree of inhibition trending with the thiol surface coverage. This suggests that thiols do not strongly interact with the reactants and simply serve to block active sites on the Pd surface. PAs, on the other hand, were found to enhance RH when furfuryl alcohol (FA) was used as the reactant. Density functional theory calculations suggested that this enhancement was due to hydrogen-bonding interactions between FA-derived surface intermediates and PA modifiers. Here, installation of hydrogen-bonding groups on the Pd surface served to preferentially stabilize RH product states. Furthermore, the promotional effect on the RH of FA was observed to be greater when a higher-coverage PA was used, providing a rate more than twice that of the unmodified Pd/Al2O3. The results of this work suggest that organic ligands can be designed to impart tunable surface interactions on heterogeneous catalysts, providing an additional method of controlling catalytic performance.
引用
收藏
页码:3730 / 3739
页数:10
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