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Aqueous-phase effects on ethanol decomposition over Ru-based catalysts
Catalysis Science & Technology ( IF 5 ) Pub Date : 2021-09-07 , DOI: 10.1039/d1cy01057c
Mehdi Zare 1 , Mohammad Saleheen 1 , Osman Mamun 1 , Andreas Heyden 1
Affiliation  

The effects of an aqueous phase on ethanol decomposition for hydrogen production over a Ru(0001) catalyst surface model have been investigated from first principles. Solvent effects on the reaction mechanism and kinetic parameters have been quantified with the help of a microkinetic reactor model, density functional theory, and an implicit solvation scheme (iSMS). Our calculations indicate that in both vapor- and aqueous-phase reaction environments, the ethanol decomposition starts with acetaldehyde formation on the surface, some of which further dehydrogenates to ketenyl species (CHCO), where the C–C bond cleaves to form methylidyne (CH) and CO. In the vapor phase, adsorbed CH gets hydrogenated to methane, and CO desorbs or undergoes methanation reducing the amount of hydrogen produced. In contrast, under aqueous phase reaction conditions, the methanation is inhibited, and the water–gas shift (WGS) reaction is accelerated, leading to complete conversion of CO to CO2 and H2. Calculations indicate that the observed reaction behavior under aqueous phase reforming conditions originates primarily from the higher water chemical potential, and implicit solvent models predict only a small solvation effect.

中文翻译:

水相对 Ru 基催化剂乙醇分解的影响

已经从第一性原理研究了水相对在 Ru(0001) 催化剂表面模型上的乙醇分解制氢的影响。溶剂对反应机理和动力学参数的影响已在微动力学反应器模型、密度泛函理论和隐式溶剂化方案 (iSMS) 的帮助下量化。我们的计算表明,在气相和水相反应环境中,乙醇分解开始于表面形成乙醛,其中一些进一步脱氢为烯基物质 (CHCO),其中 C-C 键裂解形成甲基炔 (CH ) 和 CO。在气相中,吸附的 CH 被氢化成甲烷,CO 解吸或发生甲烷化,从而减少了产生的氢气量。相比之下,在水相反应条件下,2和 H 2。计算表明,在水相重整条件下观察到的反应行为主要源于较高的水化学势,而隐式溶剂模型仅预测很小的溶剂化效应。
更新日期:2021-09-15
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