Energetic catalyst for electrochemical CO₂ conversion into high value-added chemicals is critical. Herein, an ethynyl-linked cobalt(II) porphyrin conjugated polymer (PCP) is decorated on the carbon nanotubes (CNTs) to fabricate bi-metallic central electrocatalyst (CoCoPCP/CNTs) for electrochemical CO₂ reduction (CO₂ RR). By regulating the porphyrins’ central sites of the PCP, the resultant CoCoPCP/CNTs performs a high CO faradic efficiency of 94 % with a TOF of 2.4 s⁻¹ at an extremely low overpotential of 0.44 V, which are much better than that of its CNTs-containing analogues. The effects of central site on the electrocatalytic performance and its mechanism are discussed based on the experimental study and theoretical calculation, and it is found that both of the Co centers in the four- and two-linked porphyrin units of the CoCoPCP are critical for CO₂ RR. The present work should be of significance for the exploration of porphyrin-based conjugated polymers as energetic electrocatalyst in CO₂ reduction.

将电化学CO ₂转化为高附加值化学品的高能催化剂至关重要。这里，乙炔联钴（II）卟啉的共轭聚合物（PCP）装饰的碳纳米管（CNT），以制造用于电化学CO双金属中心电极催化剂（CoCoPCP / CNT）的₂还原（CO ₂ RR）。通过调节PCP的卟啉中心部位，所得CoCoPCP / CNT具有94％的高CO法拉第效率，TOF为2.4 s ^-1在0.44 V的极低超电势下，比其含CNTs的类似物要好得多。在实验研究和理论计算的基础上，讨论了中心位点对电催化性能的影响及其机理，发现CoCoPCP的四链和双链卟啉单元中的两个Co中心对CO都是至关重要的。₂ RR。目前的工作对于探索基于卟啉的共轭聚合物作为CO ₂还原的高能电催化剂具有重要意义。