Synergistic effect of Mn doping and hollow structure boosting Mn-CoP/Co₂P nanotubes as efficient bifunctional electrocatalyst for overall water splitting

The sluggish kinetic of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) severely hampers the commercial application of electrochemical water splitting, promoting the urgent exploration of high-efficient bifunctional electrocatalysts. Heteroatom doping and structure engineering have been identified as the most effective strategies to boost the catalytic activity of electrocatalysts. Herein, Mn doping and hollow structure were integrated in the design of Co-based transition metal phosphide catalyst to prepare Mn-CoP/Co₂P nanotubes (denoted as Mn-CP NTs) by a facile template-free method. Confirmed by characterization analysis, the introduced Mn species were in high dispersion in the regular CoP/Co₂P hollow tubular framework. Such a favorable design in composition and structure effectively boosted the catalytic activity of Mn-CP NTs toward electrochemical water splitting. The Mn-CP NTs showed superior HER and OER activity demonstrated by the low overpotentials of 82 mV (vs HER) and 309 mV (vs OER) at the current density of 10 mA cm^-2, as well as the satisfactory durability. When used as both cathode and anode in electrolyzer for overall water splitting, only a low cell voltage of 1.67 V was required for the Mn-CP NTs to drive 10 mA cm^-2, accompanied with excellent stability confirmed by over 50 h test.