Surface Modification of a Nanoporous Carbon Photoanode upon Irradiation.

The photocorrosion of a nanoporous carbon photoanode, with low surface functionalization and high performance towards the photoelectrochemical oxidation of water using simulated solar light, was investigated. Two different light configurations were used to isolate the effect of the irradiation wavelength (UV and visible light) on the textural and chemical features of the carbon photoanode, and its long-term photocatalytic performance for the oxygen evolution reaction. A complete characterization of the carbon showed that the photocorrosion of carbon anodes of low functionalization follows a different pathway than highly functionalized carbons. The carbon matrix gets slightly oxidized, with the formation of carboxylic and carbonyl-like moieties in the surface of the carbon anode after light exposure. The oxidation of the carbon occurred due to the photogeneration of oxygen reactive species upon the decomposition of water during the irradiation of the photoanodes. Furthermore, the photoinduced surface reactions depend on the nature of the carbon anode and its ability to photogenerate reactive species in solution, rather than on the wavelength of the irradiation source. This surface modification is responsible for the decreased efficiency of the carbon photoanode throughout long illumination periods, due to the effect of the oxidation of the carbon matrix on the charge transfer. In this work, we have corroborated that, in the case of a low functionalization carbon material, the photocorrosion also occurs although it proceeds through a different pathway. The carbon anode gets gradually slightly oxidized due to the photogeneration of O-reactive species, being the incorporation of the O-groups responsible for the decreased performance of the anode upon long-term irradiation due to the effect of the oxidation of the carbon matrix on the electron transfer.