Abstract
The hydrogen evolution reaction (HER) is one of the most promising methods of obtaining high-purity hydrogen. However, the high cost and limited resources of materials with low cathodic hydrogen evolution overvoltage values, such as platinum group metals, are the main obstacles to the use HER for obtaining hydrogen on an industrial scale. Therefore, it is necessary to develop new alternative materials and methods of their production. One of the promising materials are catalysts based on refractory metals, in particular tungsten carbides. Metal tungsten can also be used for these purposes. In our opinion, high-temperature electrochemical synthesis (HTES) in molten salts can be a promising method of obtaining materials with properties that meet the requirements for effective catalysts, namely: ultra-dispersity, high specific surface area, mesoporosity and defective structure, high chemical and electrochemical stability. Therefore, the purpose of this work is to evaluate the electrocatalytic activity of a group of materials for HER, which are obtained by HTES in melts. Four samples of electrolytic materials were chosen for the study: tungsten, carbon, tungsten mono- and semi-carbides (WC and W2С). All samples were characterized in detail using X-ray diffraction (phase composition), SEM (morphology), Raman spectroscopy (structure of carbon phases), DTG (free carbon content).
Based on the analysis of the obtained data, it was established that all samples can be used as catalysts: crystallites have a nanometer size and a large number of structural defects; morphology provides increased surface area; tungsten carbide particles are covered with a layer of free carbon, which prevents oxidation of carbide to WO3, which has a lower catalytic activity; carbon particles are nanosized (20–30 nm) and contain a large number of structural defects; tungsten carbide-based samples contain free carbon, which increases the specific surface area, but does not cause clogging of pores.
Polarization measurements were carried out at room temperature at a polarization rate of 5 mV/s in a standard three-electrode cell with an Ag|AgCl reference electrode. 1N H2SO4 was used as a base solution, which was bubbled with high-purity argon. Onset potentials for all samples are -0.05 – -0.25 V (in order WC/C – W2C/WC/C – C – W). The overvoltage and Tafel slope were calculated and WC/C composite was shown to have the lowest values of -0.2 V and -75 mV, respectively.
Electrolytic composite of tungsten carbide/carbon have demonstrated the best characteristics, so we plan to continue the development of synthesis method of carbide compounds, which will allow us to reveal even greater potential of carbide catalysts and pave the way for their wide application in catalytic processes.
References
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