氢铵
化学
催化作用
无机化学
水溶液
吸附
苯酚
氢
光化学
电子转移
双水相体系
作者
Guoju Yang,Vineet Maliekkal,Xi Chen,Sebastian Eckstein,Hui Shi,Donald M. Camaioni,Eszter Baráth,Gary L. Haller,Yue Liu,Matthew Neurock,Johannes A. Lercher
标识
DOI:10.1016/j.jcat.2021.11.003
摘要
• Rate of phenol hydrogenation on Pt/HMFI increases with the acid concentrations of support. • The presence of hydronium ions weakens the adsorption of hydrogen and phenol on the catalyst. • Hydrogenation proceeds via the addition of surface H atom to phenol under low concentrations of hydronium ions. • Hydrogenation proceeds via a proton coupled electron transfer to phenol under high concentrations of hydronium ions. • The pathway of proton coupled electron transfer has a low activation energy than the H addition pathway. Metal-containing zeolites exhibit remarkable catalytic activity for hydrogenation owing to the synergistic interactions between acid and metal sites. In the aqueous phase, the presence of water and, in particular, hydronium ions, complicate the adsorption of H 2 and organic substrates. It is shown how hydrated hydronium ions formed from zeolite Brønsted acid sites promote the rate of hydrogenation of phenol on Pt by modifying reaction pathways in the aqueous phase. Hydrogen is preferentially added to the ortho -C of phenol at low concentrations of hydronium ions, while at high concentrations of hydronium ions hydrogen adds to both ortho- and para -C of phenol with equal probability. A proton coupled electron transfer (PCET) pathway is hypothesized to occur at metal surfaces associated with large concentrations of hydrated hydronium ions and adsorbed H, establishing a (quasi-) equilibrium open circuit potential. In the presence of lower concentrations of hydrated hydronium ions, the reaction follows a Langmuir-Hinshelwood mechanism in which adsorbed H atoms add to co-adsorbed phenol. DFT calculations show a lower activation energy barrier for the PCET pathway in the presence of hydronium ions compared to the pathway following a Langmuir-Hinshelwood type mechanism.
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