The incorporation of vacancies in a system is considered a proficient method of defect engineering in general catalytic modulation. Among two-dimensional materials, the deficiency of surface active sites and a high band gap restrict the catalytic activity of hexagonal boron nitride (hBN) material towards the oxygen reduction reaction (ORR), which hinders its applicability in fuel cells. A bane to boon strategy has been introduced here by coupling two sluggish ORR materials (hBN & MoS2) by a probe-sonication method to form a heterostructure (termed HBPS) which fosters four electron pathways to assist the reduction of oxygen. Theoretical and experimental studies suggest the kinetically and thermodynamically favorable formation of boron vacancies (B-vacancies) in the presence of MoS2, which act as active sites for oxygen adsorption in HBPS. B-vacancy induced uneven charge distribution together with band gap depression promote rapid electron transfer from the valance band to the conduction band which prevails over the kinetic limitation of pure hBN nanosheets towards ORR kinetics. The formed B-vacancy induced HBPS further exhibits a low Tafel slope (66 mV dec-1), and a high onset potential (0.80 V vs. RHE) with an unaltered electrochemically active surface area (ESCA) after long-term cycling. Thus, vacancy engineering in hBN has proved to be an efficient approach to unlock the potential of catalytic performance enhancement.
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