Reasonable construction of atomically accurate photocatalysts is the key to building efficient photocatalytic systems. Herein, we propose a collective effects strategy that enables the consolidation of both cobalt single atoms (Co_SAs) and nickel nanoparticles (Ni_NPs) in hierarchical porous MOFs for the foundational features for the preparation of high-performance photocatalysts. Among them, the optimal sample Co_SAs/Al-bpydc/Ni_NPs achieved a CO generation rate of 12.8 mmol·g^–1·h^–1 and selectivity of 91% in 4 h. According to the experiment characterizations and theoretical simulations, we found that Co_SAs facilitate CO₂ adsorption and activation, while Ni_NPs promote hydrogen spillover and transfer of hydrogen protons to Co_SAs, highlighting the collective effect of the catalytic system with multiple active sites. Most importantly, as a proof of concept, this performance enhancement strategy can also be applied to other hierarchically porous MOF photocatalysts, such as Al-bpdc, DUT-4, and UiO-67. This work provides new insight into the development of performance optimization of CO₂ conversion photocatalysts through the ingenious design of collective catalytic sites.

中文翻译：

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结合单个原子和纳米颗粒的多级多孔 MOF 中的集体效应，用于增强 CO2 光还原为 CO


合理构建原子精确的光催化剂是构建高效光催化系统的关键。在此，我们提出了一种集体效应策略，能够将钴单原子 （Co_SAs） 和镍纳米颗粒 （Ni_NPs） 整合到多级多孔 MOF 中，以获得制备高性能光催化剂的基础特征。其中，最佳样品 Co_SAs/Al-bpydc/Ni_NPs 在 4 h 内实现了 12.8 mmol·g^–1·h–1 的 CO 生成速率和 91% 的选择性。根据实验表征和理论模拟，我们发现 Co_SAs 促进 CO₂ 的吸附和活化，而 Ni_NPs 促进氢溢出和氢质子向 Co_SAs 的转移，突出了具有多个活性位点的催化体系的集体效应。最重要的是，作为概念验证，这种性能增强策略也可以应用于其他分层多孔 MOF 光催化剂，例如 Al-bpdc、DUT-4 和 UiO-67。这项工作通过巧妙地设计集体催化位点，为 CO₂ 转化光催化剂的性能优化开发提供了新的见解。