澳大利亚莫纳什大学Jie Zhang课报道了CuPd双金属催化剂在醋酸水溶液中提高2-甲基呋喃选择性的糠醛加氢反应。相关研究成果于2022年1月18日发表在国际顶尖学术期刊《德国应用化学》。

该文中，研究人员报道了一系列用于糠醛在0.1M醋酸（pH 2.9）水溶液中电化学加氢（ECH）生成2-甲基呋喃（MF或FurCH 3，其中Fur=糠基）的CuPd催化剂。MF的最高法拉第效率（FE）在-0.58vs可逆氢电极时达到75%，平均分电流密度为4.5 mA cm^-2。原位表面增强拉曼光谱和动力学同位素实验表明，电生吸附氢（H ads）参与了反应，钯的加入提高了H ads的表面覆盖率，优化了糠醛的吸附模式，从而使MF的铁含量更高。

密度泛函理论计算表明，钯的加入降低了FurCH 2*到FurCH 3*加氢反应的能垒。研究表明，催化剂的表面结构/组成在决定ECH的选择性方面起着至关重要的作用，并为设计生物衍生氧化物的ECH高级催化剂提供了新的策略。

附：英文原文

Title: Electrochemical hydrogenation of furfural in aqueous acetic acid media with enhanced 2-methylfuran selectivity using CuPd bimetallic catalysts

Author: Peng Zhou, Linbo Li, Venkata Sai Sriram Mosali, Yu Chen, Peng Luan, Qinfen Gu, David R Turner, Liang Huang, Jie Zhang

Issue&Volume: 2022-01-18

Abstract: Herein, we report a series of CuPd catalysts for electrochemical hydrogenation (ECH) of furfural to 2-methylfuran (MF or FurCH  3  where Fur = furyl) in aqueous 0.1 M acetic acid (pH 2.9). The highest faradaic efficiency (FE) for MF reached 75 % at -0.58 V  vs  . reversible hydrogen electrode with an average partial current density of 4.5 mA cm  -2  .  In situ  surface-enhanced Raman spectroscopic and kinetic isotopic experiments suggested that electrogenerated adsorbed hydrogen (H  ads  ) was involved in the reaction and incorporation of Pd enhanced the surface coverage of H  ads  and optimized the adsorption pattern of furfural, leading to a higher FE for MF. Density functional theory calculations revealed that Pd incorporation reduced the energy barrier for the hydrogenation of FurCH  2  *  to FurCH  3  *  . Our study demonstrates that catalyst surface structure/composition plays a crucial role in determining the selectivity in ECH and provides a new strategy for designing advanced catalysts for ECH of bio-derived oxygenates.

DOI: 10.1002/anie.202117809

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202117809