The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule-material hybrid systems are organized as "dark" cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. The final section extends the scope of this review to prospects and challenges in targeting catalysis beyond "classical" H2 evolution and CO2 reduction to C1 products, by summarizing cases for higher-value products from N2 reduction, C x>1 products from CO2 utilization, and other reductive organic transformations.

中文翻译：

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使用第一行过渡金属配合物进行电力和太阳能驱动的燃料合成。

利用丰富的水或温室气体二氧化碳合成可再生燃料是创造可持续和可扩展能源存储技术的重要一步。在过去的几十年中，人们的注意力集中在非贵金属催化剂的开发上，近年来，它们在固态支撑材料和在水中运行的设备中的集成。本综述调查了有关 3D 金属基分子催化剂的文献，重点关注其在水介质中电催化、光催化和光电催化合成燃料的非均相固态载体上的固定化。第一部分重点介绍使用质子和 CO2 还原 3d 过渡金属催化剂的基准均相系统以及常用的催化剂固定方法，包括对支撑材料和锚定基团的讨论。随后的部分详细阐述了分子催化剂与基于碳、量子点、金属氧化物表面和半导体的各种基材之间的有效关联。分子-材料混合系统被组织为“暗”阴极、胶体光催化剂和光电阴极，并讨论了它们的品质因数以及系统稳定性和催化剂完整性。最后一节通过总结 N2 还原产生的高价值产品、CO2 利用产生的 C x>1 产品的案例，将本次综述的范围扩展到“经典”H2 演化和 CO2 还原到 C1 产品之外的靶向催化的前景和挑战，和其他还原有机转化。