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_single-atom-Rh metallene arrays on Cu foam requires only the low voltages of 1.18 V to reach current densities of 100 mA cm⁻² 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，迫切需要开发高效的电催化剂。在这里，我们报道了一种在泡沫铜上分散的铜单原子铑金属烯阵列，用于阴极硝基苯电还原反应和阳极甲醇氧化反应。在耦合电催化系统中，泡沫铜上的铜_单原子-Rh金属烯阵列仅需要1.18 V的低电压即可达到100 mA cm ^-2的电流密度，生成苯胺和甲酸盐，硝基苯含量高达~100%转化率/苯胺选择性和超过~90%的甲酸法拉第效率，实现高价值化学品的合成。密度泛函理论计算揭示了Cu单原子与Rh主体之间的电子效应及催化反应机理。协同催化效应和H*-溢出效应可以改善催化反应过程，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。