将温室气体二氧化碳（CO 2 ）减少为碳基燃料为可持续和可扩展的能源存储挑战提供了潜在的解决方案。为了解决活性、选择性和稳定性问题，卟啉催化剂受到了广泛关注，最近，将卟啉集成在非均相条件下运行的导电载体上。本文综述了卟啉催化剂应用于电化学CO 2还原的主要原理和策略，从均相催化和非均相催化到结构修饰和固定化技术。第一部分讨论卟啉催化剂的机理研究，包括涉及 CO 2的催化步骤还原，卟啉配体对催化活性的影响。第二部分深入介绍了卟啉催化剂的动力学研究。第三部分介绍了均相催化中卟啉的例子，特别关注铁卟啉以及路易斯酸和布朗斯台德酸带来的促进作用。下一节总结了导电载体上卟啉催化剂异质化的主要技术，包括非共价、共价和周期性固定，而周期性固定包括结构中的卟啉支架或框架。最后一部分介绍了流通池中使用的卟啉的最新情况。本文综述了卟啉在CO 2中的最新进展和基本原理研究结果有助于设计高效、选择性的 CO 2还原催化剂。
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A review of the development of porphyrin-based catalysts for electrochemical CO2 reduction
The reduction of greenhouse gas carbon dioxide (CO2) to carbon-based fuels provides a potential solution to the sustainable and scalable energy storage challenges. To solve the issues with activity, selectivity and stability, much attention has been put on porphyrin catalysts, and more recently, the integration of porphyrins on conductive supports that operate in heterogeneous conditions. This review summarizes the main principles and strategies explored for the application of porphyrin catalysts to electrochemical CO2 reduction, ranging from homogeneous catalysis and heterogeneous catalysis to structure modification and immobilization techniques. The first section discusses mechanistic study of porphyrin catalysts including the catalytic steps involved in CO2 reduction, the effects of porphyrin ligands on catalytic activities. The second section provides insight into the kinetic study of porphyrin catalysts. The third section presents examples of porphyrins in homogeneous catalysis with particular focus on iron porphyrins and the boosting effects brought by Lewis acid and Brønsted acid. The next section summarizes the main techniques for the heterogenization of porphyrin catalysts on conductive supports, including non-covalent, covalent and periodic immobilization, whereas periodic immobilization comprises porphyrin scaffolds or frameworks in the structure. The last section gives an update of porphyrins employed in a flow cell. This review surveys the recent advances and basic principles of porphyrins in CO2 reduction, and the findings can be instrumental for designing efficient and selective catalysts for CO2 reduction.