Chemical functionalized noble metal nanocrystals for electrocatalysis

Electrocatalysis is an interface-dominated process, in which the activity of the catalyst highly relates to the adsorption/desorption behaviors of the reactants/intermediates/products on the active sites. From the perspective of catalyst design, the chemical functionalization design on noble metal surfaces will inevitably affect the reaction process, which is considered to be one of the effective strategies to tune the electrocatalytic performance of noble metal nanocrystals. Polyamines (PAM) with high stability and good coordination ability have been widely studied as important functional molecules. In this account, we first introduce the PAM-assisted synthesis mechanism of noble metal nanocrystals, which provides a theoretical basis and guidance for their design and optimization with controllable morphology. Then, the effects of adsorbed PAM on the electronic structure, geometric structure, electrode/electrolyte interface structure and catalytic reaction pathway of noble metal-based catalysts are specifically described. The internal mechanism of noble metal-PAM interfacial effect increasing catalyst activity and selectivity is stated, and the latest research progress of PAM functionalized catalysts applied in important reactions is listed, such as hydrogen evolution reaction, oxygen reduction reaction, formic acid oxidation reaction, and nitrate reduction reaction, and so on. These findings open a new avenue for constructing advanced electrocatalysts based on inorganic/organic polymer-mediated interface engineering in various energy-related catalysis/electrocatalysis fields. Finally, the current challenges and future prospects of PAM molecule functionalized noble metal electrocatalysts are proposed.