Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of −69 mV and −118 mV with a small Tafel slope of 51 mV dec−1 to obtain current densities of 10 mA cm−2 and 50 mA cm−2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.