Cobalt Phosphotungstate-Based Composites as Bifunctional Electrocatalysts for Oxygen Reactions

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key reactions in energy-converting systems, such as fuel cells (FCs) and water-splitting (WS) devices. However, the current use of expensive Pt-based electrocatalysts for ORR and IrO2 and RuO2 for OER is still a major drawback for the economic viability of these clean energy technologies. Thus, there is an incessant search for low-cost and efficient electrocatalysts (ECs). Hence, herein, we report the preparation, characterization (Raman, XPS, and SEM), and application of four composites based on doped-carbon materials (CM) and cobalt phosphotungstate (MWCNT_N8_Co4, GF_N8_Co4, GF_ND8_Co4, and GF_NS8_Co4) as ORR and OER electrocatalysts in alkaline medium (pH = 13). Structural characterization confirmed the successful carbon materials doping with N and/or N, S, and the incorporation of the cobalt phosphotungstate. Overall, all composites showed good ORR performance with onset potentials ranging from 0.83 to 0.85 V vs. RHE, excellent tolerance to methanol crossover with current retentions between 88 and 90%, and good stability after 20,000 s at E = 0.55 V vs. RHE (73% to 82% of initial current). In addition, the number of electrons transferred per O-2 molecule was close to four, suggesting selectivity to the direct process. Moreover, these composites also presented excellent OER performance with GF_N8_Co4 showing an overpotential of 0.34 V vs. RHE (for j = 10 mA cm(-2)) and j(max) close to 70 mA cm(-2). More importantly, this electrocatalyst outperformed state-of-the-art IrO2 electrocatalyst. Thus, this work represents a step forward toward bifunctional electrocatalysts using less expensive materials.

Automated summary

This study reports the preparation, characterization, and application of composites based on doped-carbon materials and cobalt phosphotungstate as electrocatalysts for the oxygen reduction reaction and oxygen evolution reaction. The composites showed good catalytic performance and stability in alkaline medium.