Chen Di, Chu Bingxian, Li Fayan, Zheng Yu-Tao, Lu Yu, Shao Bing, Li Lei, Huang Ning-Yu, Xu Qiang
Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials (SKLPM), Southern University of Science and Technology, Shenzhen 518055, China.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
J Am Chem Soc. 2025 Jul 2;147(26):22705-22713. doi: 10.1021/jacs.5c04364. Epub 2025 Jun 17.
Photocatalytic CO reduction to C hydrocarbons is considered more valuable and yet highly challenging due to the multielectron process and sluggish kinetics of C-C coupling, which requires multiple active sites to work synergistically. In this work, through a photodeposition method, Cu single-atom sites and atomically Cu-doped Au nanoparticles were simultaneously anchored on a photoactive metal-organic framework (MOF) with mesoporous channels, closely integrating distinct sites within a confined environment. Thanks to the electron accumulation of plasmonic metal nanoparticles and the synergy among different active sites, this MOF composite can achieve efficient photocatalytic reduction of CO to CH with a production rate as high as 69.9 μmol g h and a selectivity as high as 71.1%. Photocatalytic experiments with control samples unveiled the critical roles of different active sites at each step, which was further confirmed by in situ characterizations and theoretical calculations. This finding highlights the potential of MOFs as an ideal platform for the integration of various active sites for synergistically catalytic applications.
光催化将CO还原为碳氢化合物被认为更具价值，但由于多电子过程和C-C偶联的缓慢动力学，这一过程极具挑战性，需要多个活性位点协同工作。在这项工作中，通过光沉积方法，将Cu单原子位点和原子级Cu掺杂的Au纳米颗粒同时锚定在具有介孔通道的光活性金属有机框架（MOF）上，在受限环境中紧密整合不同的位点。由于等离子体金属纳米颗粒的电子积累以及不同活性位点之间的协同作用，这种MOF复合材料能够实现高效的光催化将CO还原为CH，产率高达69.9 μmol g h，选择性高达71.1%。对照样品的光催化实验揭示了不同活性位点在每个步骤中的关键作用，原位表征和理论计算进一步证实了这一点。这一发现突出了MOF作为整合各种活性位点以进行协同催化应用的理想平台的潜力。
