Mao Qiqi, Mu Xu, Wang Wenxin, Deng Kai, Yu Hongjie, Wang Ziqiang, Xu You, Wang Liang, Wang Hongjing
State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.
Nat Commun. 2023 Sep 14;14(1):5679. doi: 10.1038/s41467-023-41423-2.
Organic electrocatalytic conversion is an essential pathway for the green conversion of low-cost organic compounds to high-value chemicals, which urgently demands the development of efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on Cu foam for cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In the coupled electrocatalytic system, the Cu-Rh metallene arrays on Cu foam requires only the low voltages of 1.18 V to reach current densities of 100 mA cm for generating aniline and formate, with up to ~100% of nitrobenzene conversion/ aniline selectivity and over ~90% of formate Faraday efficiency, achieving synthesis of high-value chemicals. Density functional theory calculations reveal the electron effect between Cu single-atom and Rh host and catalytic reaction mechanism. The synergistic catalytic effect and H*-spillover effect can improve catalytic reaction process and reduce energy barrier for reaction process, thus enhancing electrocatalytic reaction activity and target product selectivity.
有机电催化转化是将低成本有机化合物绿色转化为高价值化学品的重要途径，这迫切需要开发高效的电催化剂。在此，我们报道了一种用于阴极硝基苯电还原反应和阳极甲醇氧化反应的、铜单原子分散在泡沫铜上的铑金属烯阵列。在耦合电催化体系中，泡沫铜上的铜-铑金属烯阵列仅需1.18 V的低电压就能达到100 mA cm 的电流密度以生成苯胺和甲酸盐，硝基苯转化率/苯胺选择性高达约100%，甲酸盐法拉第效率超过约90%，实现了高价值化学品的合成。密度泛函理论计算揭示了铜单原子与铑主体之间的电子效应及催化反应机理。协同催化效应和H*溢流效应可改善催化反应过程并降低反应过程的能垒，从而提高电催化反应活性和目标产物选择性。
