Architecting the interfacial microenvironment is highly desirable for achieving enhanced electrochemical CO₂ reduction reaction (CO₂RR), but it is still a challenge. Herein, a π-conjugated matrix of graphitic carbon nitride/graphene (C₃N₄/G) is built to tailor cobalt phthalocyanine (CoPc) into an efficient CO₂ electrocatalyst. The enhanced mechanism of microenvironment-mediated CO₂RR on CoPc/C₃N₄/G is fully distinguished by integrating the experimental and theoretical results. C₃N₄/G is energetic for CO₂ enrichment and H₂O dissociation to produce activated H* species, which enables a ceaseless yet fast power injection into the kinetic process of the CO₂RR. Meanwhile, the electron structure of Co active sites modulated by C₃N₄/G also thermodynamically favors the conversion of CO₂ and intermediates. Consequently, in a flow cell, CoPc/C₃N₄/G delivers a high turnover frequency value (50.5 s^–1), gratifying CO selectivity (∼100%) as well as current density (67.8 mA cm^–2) at −1.1 V vs RHE, and maintains a Faradaic efficiency for CO above 98% in an ultrawide potential window of over 500 mV, ranking among the state-of-the-art macrocyclic complex-based catalysts currently reported for CO₂ reduction to CO. This work underlines the significance of well-tailored microenvironment design in the electrocatalytic system.

中文翻译：

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通过靶向多功能 π 共轭调节剂重新编程酞菁钴的微环境，实现协同 CO2 电还原


构建界面微环境对于实现增强的电化学 CO ₂ 还原反应 (CO ₂ RR) 非常理想，但这仍然是一个挑战。在此，构建了石墨碳氮化物/石墨烯 (C ₃ N ₄ /G) 的 π 共轭基质，将钴酞菁 (CoPc) 定制为高效的 CO ₂ RR对CoPc/C ₃ N ₄ /G的增强机制。 C ₃ N ₄ /G 为 CO ₂ 富集和 H ₂ O 解离提供能量，以产生活化的 H* 物种，这使得不断而快速地将动力注入到 CO ₂ RR 的动力学过程中。同时，C ₃ N ₄ /G 调节的 Co 活性位点的电子结构在热力学上也有利于 CO ₂ 和中间体的转化。因此，在流通池中，CoPc/C ₃ N ₄ /G 提供高周转频率值 (50.5 s ^–1 )，令人满意的 CO 选择性 (∼ 100%）以及-1.1 V vs RHE 下的电流密度（67.8 mA cm ^–2 ），并在超过 500 mV 的超宽电位窗口中保持 CO 的法拉第效率高于 98%，位居同类产品之列。目前报道的最先进的大环复合物催化剂可将 CO ₂ 还原为 CO。这项工作强调了电催化系统中精心设计的微环境设计的重要性。