LAUSR

Analogously to enzymatic catalysis, where the active metal sites and their environment are controlled by protein residues, the catalytic properties of metal nanoparticles (NPs) can be tuned by carefully selecting their surface‐coordinated species. In artificial photosynthesis, surface‐functionalization emerged in the last decade, grounded on the development of reliable methods for tailored synthesis, advanced characterization and theoretical modeling of metal NPs, altogether with the aim of transferring to the nanoscale the mechanistic knowledge acquired from molecular complexes. Metal NPs surface‐functionalization modulates the energetics of key catalytic intermediates, introduces second coordination sphere effects, influences the catalyst‐electrolyte interface, and determines the metal NPs surface coverage and, accordingly, the number of accessible active sites. In photoactivated systems, metal NPs surface‐functionalization may play a key role in modulating the charge transfers and recombination processes between the light absorber and the active sites and in the light absorber itself. Thus, after a presentation of the most relevant synthetic methods to produce well‐defined surface‐functionalized metal NPs, a critical analysis of why the above effects are the cornerstone in enhancing their catalytic performance in the key processes of artificial photosynthesis, namely the oxygen evolution reaction, the hydrogen evolution reaction, and the CO2 reduction reaction, is given.