(Invited) Tuning the Activity of Iron Phosphide Electrocatalysts for Sustainable Energy Conversion

Abstract

Electrocatalysis is a promising approach for the sustainable conversion of renewable energy sources, such as solar and wind power, into chemical energy that can be stored and used on demand. By harnessing renewable electricity to drive electrochemical reactions, we can produce fuels and chemicals in a way that is both clean and cost-effective. As we continue to develop new electrocatalytic materials and improve the efficiency of existing processes, the potential for electrocatalysis to transform our energy system will only continue to grow.We report the use of iron phosphide (Fe2P, FeP) in several electrocatalytic applications, such as reduction of nitrate ions (NO3), hydrogen and oxygen evolution studies. The electrochemical reduction of the nitrate ion (NO3), a widespread water pollutant, to valuable ammonia (NH3) is a promising approach to achieving green energy conservation. Particularly, FeP and Fe2P phases were successfully demonstrated as efficient catalysts for NH3 generation. Detection of the in-situ formed product using a bi-potentiostat was achieved by electrooxidation of NH3 to nitrogen (N2) on a Pt electrode. The Fe2P catalyst exhibits the highest Faradaic efficiency (96%) for NH3 generation with a yield (0.25 mmol h−1 cm-−2 or 2.10 mg h−1 cm−2) at −0.55 V vs. reversible hydrogen electrode (RHE). To get relevant information about the reaction mechanisms and the fundamental origins behind the better performance of Fe2P, density functional theory (DFT) calculations were performed.In addition to NH3 synthesis, the iron phosphide catalyst was used in electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) studies. To enhance the catalytic activities of the obtained iron phosphide particles, heat-treatments were carried out at elevated temperatures. Heat-treatment at 500°C under a reductive atmosphere induced structural changes in the samples: (i) Fe2P yielded a pure Fe3P phase (Fe3P−500°C) and (ii) FeP transformed into a mixture of iron phosphide phases (Fe2P/FeP−500°C). The electrocatalytic activities of heat-treated Fe3P−500°C, and Fe2P/FeP−500°C catalysts were studied for hydrogen evolution reaction (HER) in 0.5 M H2SO4. The lowest HER electrode potential of 110 mV vs. a reversible hydrogen electrode (RHE) at 10 mA cm−2 was achieved with a Fe2P/FeP−500°C catalyst. The intrinsic activity of FeP catalysts was also tuned and studied for OER.