Heteratom doping is a possible way to tune the hydrogen evolution reaction (HER) catalytic capability of electrocatalysts. In this work, we report the development of Mn-doped CoP (Mn–Co–P) nanosheets array on Ti mesh (Mn–Co–P/Ti) as an efficient 3D HER electrocatalyst with good stability at all pH values. Electrochemical tests demonstrate that Mn doping leads to enhanced catalytic activity of CoP. In 0.5 M H2SO4, this Mn–Co–P/Ti catalyst drives 10 mA cm–2 at an overpotential of 49 mV, which is 32 mV less than that for CoP/Ti. To achieve the same current density, it demands overpotentials of 76 and 86 mV in 1.0 M KOH and phosphate-buffered saline, respectively. The enhanced HER activity for Mn–Co–P can be attributed to its more thermo-neutral hydrogen adsorption free energy than CoP, which is supported by density functional theory calculations.

Ni2P nanoflake arrays on carbon cloth act as an efficient and durable catalyst electrode for the urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Its two-electrode alkaline electrolyzer needs 1.35 V for 50 mA cm−2, which is 0.58 V less than that required for pure water splitting.

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