Abstract
Research for the development of noble metal-free electrodes for hydrogen evolution has blossomed in recent years. Transition metal carbides compounds, such as W(2)C, have been considered as a promising alternative to replace Pt-family metals as electrocatalysts towards hydrogen evolution reaction (HER). Moreover, hybridization of TMCs with graphene nanostructures has emerged as a reliable strategy for the preparation of compounds with high surface to volume ratio and abundant active sites. The present study focuses in the preparation of tungsten carbide/oxide compounds deposited in a three-dimensional vertical graphene nanowalls (VGNW) substrate via chemical vapor deposition, magnetron sputtering and thermal annealing processes. Structural and chemical characterization reveals the partial carburization and oxidation of the W film sputtered on the VGNWs, due to C and O migration from VGNWs towards W during the high temperature annealing process. Electrochemical characterization shows the enhanced performance of the nanostructured hybrid W(2)C/WO(x) on VGNW compound towards HER, when compared with planar W(2)C/WO(x) films. The W(2)C/WO(x) nanoparticles on VGNWs require an overpotential of -252 mV for the generation of 10 mA cm(-2). Chronoamperometry tests in high overpotentials reveal the compounds stability while sustaining high currents, in the order of hundreds of mA. Post-chronoamperometry test XPS characterization unveils the formation of a W hydroxide layer which favours hydrogen evolution in acidic electrolytes. We aspire that the presented insights can be valuable for those working on the preparation of hybrid electrodes for electrochemical processes.