Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

[Image: see text] The synthesis of renewable fuels from abundant water or the greenhouse gas CO(2) 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 CO(2) 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” H(2) evolution and CO(2) reduction to C(1) products, by summarizing cases for higher-value products from N(2) reduction, C(x>1) products from CO(2) utilization, and other reductive organic transformations.