Over the past decade, electrocatalytic reduction of CO₂ has gained substantial attention. However, hardly any of the previous reviews have focused on the systematic discussion of polymer-molecular catalyst composites as an emerging system for the electrochemical transformation of CO₂ to value-added products. In this review, we first give a brief overview of the general features of solid-state and molecular catalysts, and then advance the discussion to polymer-catalyst composite systems, with particular emphasis on polymer-encapsulated molecular catalysts, where the coordination environment surrounding molecular catalysts can be modified via polymer encapsulation to promote the overall performance of CO₂ electrocatalysis. The elucidation of the possible reaction mechanisms of this emerging electrocatalytic system along with proposed optimization strategies is also summarized and discussed based on recently published reports, followed by the challenges and prospects of their industrial applications at the end of this review. From this review, we hope the audience can gain a comprehensive understanding of the electrocatalytic mechanism of the coordinating polymers and valuable insights into engineering the microenvironment surrounding the metal complexes for potential future research directions.

在过去的十年中，CO ₂的电催化还原引起了广泛的关注。_{然而，之前的评论几乎没有集中于对聚合物-分子催化剂复合材料作为将CO 2}电化学转化为增值产品的新兴系统的系统讨论。在这篇综述中，我们首先简要概述了固态和分子催化剂的一般特征，然后将讨论深入到聚合物-催化剂复合体系，特别是聚合物封装的分子催化剂，其中分子周围的配位环境催化剂可以通过聚合物封装进行改性，以提高CO ₂的整体性能电催化。还根据最近发表的报告总结和讨论了这种新兴电催化系统可能的反应机制以及提出的优化策略，并在本综述的最后总结了其工业应用的挑战和前景。通过这篇综述，我们希望观众能够全面了解配位聚合物的电催化机理，并为设计金属配合物周围的微环境提供有价值的见解，为未来潜在的研究方向提供宝贵的见解。