CO2 electroreduction (CO2ER) into high value-added chemicals or fuels is of great significance to solve the current energy shortage and realize the carbon cycle. Although there are reports that Cu-based CO2ER catalysts can achieve multicarbon products, the influence of the microenvironment of Cu-based catalysts on their valence states, interface and CO2ER performance still deserve further investigation. Herein, a CoII-porphyrin derivative (m-CoTPyP) is used to decorate on Cu2O/Cu nanoparticles with Cu+/Cu0 mixed valence states and Cu2O/Cu interface for constructing a novel CoTPyP-Cu2O/Cu composite, where m-CoTPyP as ultrathin layer on Cu2O/Cu nanoparticles can not only efficiently promote the adsorption/activation of CO2 and the formation of *CO on the active sites by regulating the microenvironment via H-bonding, but also improve the stability of Cu valence states. Moreover, the Cu+/Cu0 mixed valence states and abundant Cu2O/Cu interfaces of the Cu2O/Cu nanoparticles significantly enhance the electron transfer rate and CC coupling kinetics. Specifically, the CoTPyP-Cu2O/Cu(1:15) delivers an ethylene (C2H4) Faraday efficiency up to 71 % and excellent stability (>50 h). This work provides a new perspective on the structural design of CO2ER catalyst with synergistic active sites, high Faraday efficiency and selectivity of C2H4 by regulating the microenvironment.

中文翻译：

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通过 CoII-卟啉调节的 Cu2O/Cu 纳米复合材料促进 CO2 电还原乙烯


将 CO2 电还原 （CO2ER） 转化为高附加值的化学品或燃料，对于解决当前能源短缺和实现碳循环具有重要意义。尽管有报道称 Cu 基 CO2ER 催化剂可以获得多碳产物，但 Cu 基催化剂的微环境对其价态、界面和 CO2ER 性能的影响仍值得进一步研究。本文采用 CoII-卟啉衍生物 （m-CoTPyP） 在具有 Cu+/Cu0 混合价态和 Cu2O/Cu 界面的 Cu2O/Cu 纳米颗粒上装饰，构建了一种新型的 CoTPyP-Cu2O/Cu 复合材料，其中 m-CoTPyP 作为 Cu2O/Cu 纳米颗粒上的超薄层，不仅可以通过 H 键调节微环境，有效地促进 CO2 的吸附/活化和活性位点上 *CO 的形成， 而且还提高了 Cu 价态的稳定性。此外，Cu2O/Cu 纳米颗粒的 Cu+/Cu0 混合价态和丰富的 Cu2O/Cu 界面显著提高了电子传递速率和 CC 耦合动力学。具体来说，CoTPyP-Cu2O/Cu（1：15） 可提供高达 71% 的乙烯 （C2H4） 法拉第效率和出色的稳定性 （>50 h）。这项工作通过调节微环境，为具有协同活性位点、高法拉第效率和 C2H4 选择性的 CO2ER 催化剂的结构设计提供了新的视角。