N-doped hierarchical porous carbon nanosheets-supported copper catalysts (Cu/NCNS-x) were fabricated to solve the problem of deactivation caused by the leaching, agglomeration and oxidation of Cu nanoparticles (NPs) in the dimethyl carbonate (DMC) synthesis. The optimal Cu/NCNS-12 exhibited superb activity and stability without obvious deactivation after 10 cycles. The nanosheet structure produced new defects resulting in Cu reconstruction during the reaction process, while the strong interaction between Cu⁰ and N atoms greatly inhibited the oxidation of Cu⁰. The reconstruction of Cu was stimulated at above 100 °C, regardless of atmosphere, solvent types, pressure and rotation speed. The mechanism was elaborated that the initial Cu NPs (11 nm) migrated and then was trapped into newly created defects, finally formed into clusters (0.91 nm) as well as single-atom sites. This work provides profound potential in understanding metal reconstruction and developing a promising synthetic strategy of metal cluster catalysts.

为了解决碳酸二甲酯（DMC）合成中Cu纳米颗粒（NPs）的浸出、团聚和氧化导致的失活问题，制备了N掺杂分级多孔碳纳米片负载的铜催化剂（Cu/NCNS- x）。最佳的 Cu/NCNS-12 在 10 次循环后表现出极好的活性和稳定性，没有明显的失活。纳米片结构在反应过程中产生了新的缺陷导致Cu重构，而Cu ⁰和N原子之间的强相互作用极大地抑制了Cu ⁰的氧化. 无论气氛、溶剂类型、压力和旋转速度如何，在 100°C 以上都会刺激 Cu 的重建。详细阐述了最初的 Cu NPs (11 nm) 迁移然后被捕获到新产生的缺陷中，最终形成簇 (0.91 nm) 以及单原子位点的机制。这项工作为理解金属重建和开发有前途的金属簇催化剂合成策略提供了巨大的潜力。