Spontaneous Catalytic Reaction of a Surfactant in the Interfacial Microenvironment of Colloidal Gold Nanoparticles

The performance of nanomaterials is significantly determined by the interfacial microenvironment, in which a surfactant plays an essential role as the adsorbent, but its involvement in the interfacial reaction is often overlooked. Here, it was discovered that citrate and ascorbic acid, the two primarily used surfactants for colloidal gold nanoparticles (Au NPs), can spontaneously undergo catalytic reaction with trace-level nitrogenous residue under ambient environment to form oxime, which is subsequently cleaved to generate CN^- or a compound containing the -CN group. Such a catalytic reaction shows wide universality in both reactants, including various carbonaceous and nitrogenous sources, and metal catalysts, including Au, Ag, Fe, Cu, Ni, Pt, and Pd NPs. Furthermore, with the removal of this reaction, adsorbed CO with diverse adsorption configurations was observed via surface-enhanced Raman spectroscopy under ambient conditions without an applied potential. Our work highlights the non-negligible significance of surfactants in interfacial microenvironments and provides crucial insights into the fundamental understanding of interfacial chemical reactions.