![]() The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO 2 reduction. In contrast, an electrode prepared by precipitation of CoPc onto glassy carbon produced. Finally, design approaches for metal nanoparticles (NPs) based on size, shape, and support tuning are summarized and compared to novel strategies based on the interaction with surface-bonded organic molecules. No formate was detected as a CO2 reduction product in this early paper. The superior performances of single-atom catalysts (SACs) and the structural similarity with their molecular analogs, suggest that transition metal catalysts containing well-defined sites may be intrinsically more active and selective towards CO 2 conversion than the bulk heterogeneous materials. A simple, effective, and environment-friendly recycling process has been designed to recover cobalt as a nanoporous carbon/cobalt (NPCCo) composite from the electrode black powder of spent lithium cobalt oxide-type (LiCoO2 cathode-based) lithium-ion batteries (LIBs). ![]() The main strategies to minimize catalyst cost are also presented, leading to atomically dispersed molecular-like M–N x moieties embedded on 2D conducting materials. Transition metal complexes containing heme and non-heme ligands have been selected to discuss the recent advances in the understanding of the structure–function relationship in molecular homogeneous catalysis as well as to summarize the main approaches proposed for the heterogenization or confinement of molecular catalysts on conductive surfaces. In an effort to bridge the gap between the fields of homogeneous and heterogeneous catalysis, this review aims to survey the main strategies explored for the rational design of a wide variety of different metal catalysts, ranging from molecular systems to single-atom and nanostructured catalysts. In order to tackle the challenges related to selectivity, activity, overpotential and durability, transition metal-based catalysts have been widely investigated in the last decades. The electrochemical reduction of carbon dioxide (CO 2) powered by renewable energy is an attractive sustainable approach to mitigate CO 2 emissions and to produce fuels or value-added chemicals.
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