Low Overpotential in Vacancy-Rich Ultrathin CoSe₂ Nanosheets for Water Oxidation

Abstract

According to Yang Shao-Horn’s principle, CoSe₂ is a promising candidate as an efficient, affordable, and sustainable alternative electrocatalyst for the oxygen evolution reaction, owing to its well-suited electronic configuration of Co ions. However, the catalytic efficiency of pure CoSe₂ is still far below what is expected, because of its poor active site exposure yield. Herein, we successfully overcome the disadvantage of insufficient active sites in bulk CoSe₂ by reducing its thickness into the atomic scale rather than any additional modification (such as doping or hybridizing with graphene or noble metals). The positron annihilation spectrometry and XAFS spectra provide clear evidence that a large number of V_Co″ vacancies formed in the ultrathin nanosheets. The first-principles calculations reveal that these V_Co″ vacancies can serve as active sites to efficiently catalyze the oxygen evolution reaction, manifesting an OER overpotential as low as 0.32 V at 10 mA cm^–2 in pH 13 medium, which is superior to the values for its bulk counterparts as well as those for the most reported Co-based electrocatalysts. Considering the outstanding performance of the simple, unmodified ultrathin CoSe₂ nanosheets as the only catalyst, further improvement of the catalytic activity is expected when various strategies of doping or hybridizing are used. These results not only demonstrate the potential of a notable, affordable, and earth-abundant water oxidation electrocatalyst based on ultrathin CoSe₂ nanosheets but also open up a promising avenue into the exploration of excellent active and durable catalysts toward replacing noble metals for oxygen electrocatalysis