The dramatic increase in anthropogenic carbon dioxide emissions in recent decades has forced us to look for alternative carbon-neutral processes for the production of energy vectors and commodity chemicals. Photo- and electrochemical reduction of CO₂ are appealing strategies for the storage of sustainable and intermittent energies in the form of chemical bonds of synthetic fuels and value-added molecules. In these approaches, carbon dioxide is converted to products such as CO, HCOOH and MeOH through proton-coupled electron transfer reactions. The use of earth-abundant elements as components of the catalytic materials is crucial for the large-scale applicability of this technology. This review summarizes the most recent advances related to this issue, with particular focus on studies where molecular metal complexes are used as catalysts. In addition, with the aim of aiding in the design of more robust and efficient non-noble metal-based catalysts, we discuss the lessons learned from the corresponding mechanistic studies.

近几十年来，人为造成的二氧化碳排放量急剧增加，迫使我们寻找替代的碳中和工艺来生产能源载体和商品化学品。光和电化学还原CO ₂以合成燃料和增值分子的化学键形式存储可持续和间歇性能量的有吸引力的策略。在这些方法中，二氧化碳通过质子偶联的电子转移反应转化为产物，例如CO，HCOOH和MeOH。大量使用稀土元素作为催化材料的组成部分对于该技术的大规模应用至关重要。这篇综述总结了与该问题有关的最新进展，特别侧重于使用分子金属络合物作为催化剂的研究。另外，为了帮助设计更耐用和高效的非贵金属基催化剂，我们讨论了从相应的机理研究中汲取的经验教训。