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在温和条件下使用储量丰富的过渡金属纳米颗粒对含氧化合物进行电催化氢化反应。

Electrocatalytic Hydrogenation of Oxygenates using Earth-Abundant Transition-Metal Nanoparticles under Mild Conditions.

作者信息

Carroll Kyler J, Burger Thomas, Langenegger Lukas, Chavez Steven, Hunt Sean T, Román-Leshkov Yuriy, Brushett Fikile R

机构信息

Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, MA, 02139, USA.

Department of Chemistry, Technical University of Munich, Lichtenbergstraße 4, 85748, Garching, Germany.

出版信息

ChemSusChem. 2016 Aug 9;9(15):1904-10. doi: 10.1002/cssc.201600290. Epub 2016 Jun 23.

Abstract

Electrocatalytic hydrogenation (ECH) is a sustainable pathway for the synthesis of value-added organic compounds, provided affordable catalysts with high activity, selectivity and durability are developed. Here, we synthesize Cu/C, Ni/C, and CuNi/C nanoparticles and compare their performance to Pt/C, Ru/C, PtRu/C for the ECH of hydroxyacetone, a bio-derived feedstock surrogate containing a carbonyl and a hydroxyl functional group. The non-precious metal electrocatalysts show promising conversion-time behavior, product selectivities, and Faradaic efficiencies. Ni/C forms propylene glycol with a selectivity of 89 % (at 80 % conversion), while Cu/C catalyzes ECH (52 % selectivity) and hydrodeoxygenation (HDO, 48 % selectivity, accounting for evaporation). CuNi/C shows increased turnover frequencies but reduced ECH selectivity (80 % at 80 % conversion) as compared to the Ni/C catalyst. Importantly, stability studies show that the non-precious metal catalysts do not leach at operating conditions.

摘要

电催化氢化(ECH)是合成高附加值有机化合物的一条可持续途径,前提是要开发出具有高活性、选择性和耐久性且价格合理的催化剂。在此,我们合成了铜/碳(Cu/C)、镍/碳(Ni/C)和铜镍/碳(CuNi/C)纳米颗粒,并将它们在对羟基丙酮(一种含有羰基和羟基官能团的生物衍生原料替代物)进行电催化氢化反应中的性能与铂/碳(Pt/C)、钌/碳(Ru/C)、铂钌/碳(PtRu/C)进行了比较。这些非贵金属电催化剂表现出了令人期待的转化率-时间行为、产物选择性和法拉第效率。镍/碳形成丙二醇的选择性为89%(转化率为80%时),而铜/碳催化电催化氢化反应(选择性为52%)和加氢脱氧反应(HDO,选择性为48%,包括蒸发所致)。与镍/碳催化剂相比,铜镍/碳的周转频率有所提高,但电催化氢化反应的选择性降低(转化率为80%时为80%)。重要的是,稳定性研究表明,这些非贵金属催化剂在操作条件下不会浸出。

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