Insights into DFT-guided synthesis of atomic clusters for electrocatalysis

Abstract It is non-trivial to perform density functional theory (DFT) screening for experimental validation that can accelerate qualitative materials discovery to give priority to the top candidates. Cluster catalysts, owing to their adequate active sites, quantum effect, high ratio of volume/surface, excellent activity and selectivity, have garnered widespread attention in various complicated multi-step catalytic reactions. However, the design concept, structure formation principle, electrocatalysis process and potential reaction mechanism are rarely unveiled. This perspective will summarize the DFT calculation-assisted screening concept with emphasis on theoretical calculation descriptor, geometric structures, electronic properties, adsorption behaviors, and reaction mechanism to monitor the cluster catalysis. Thereafter, experimental design of advanced clusters will be presented, including synthetic strategies and various characterization techniques for intrinsic active sites identification. Subsequently, an overview of the structure-property correlation to drive diverse electrochemical reactions will be exemplified and discussed, encompassing cathode reaction of oxygen reduction reaction (ORR), anode oxidation of H2, alcohols and acids, water splitting, nitrogen reduction reaction (NRR), carbon dioxide reduction reaction (CO2RR). Finally, a fundamental insight into the existing challenges and perspectives were proposed for rational screening and structural regulation of the advanced clusters for the electrochemical reactions in clean energy conversion devices.