Metal Doping Effect of the M–Co2P/Nitrogen-Doped Carbon Nanotubes (M = Fe, Ni, Cu) Hydrogen Evolution Hybrid Catalysts

The enhancement of catalytic performance of cobalt phosphide-based catalysts for the hydrogen evolution reaction (HER) is still challenging. In this work, the doping effect of some transition metal (M = Fe, Ni, Cu) on the electrocatalytic performance of the M–Co2P/NCNTs (NCNTs, nitrogen-doped carbon nanotubes) hybrid catalysts for the HER was studied systematically. The M–Co2P/NCNTs hybrid catalysts were synthesized via a simple in situ thermal decomposition process. A series of techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometry, transmission electron microscopy, and N2 sorption were used to characterize the as-synthesized M–Co2P/NCNTs hybrid catalysts. Electrochemical measurements showed the catalytic performance according to the following order of Fe–Co2P/NCNTs > Ni–Co2P/NCNTs > Cu–Co2P/NCNTs, which can be ascribed to the difference of structure, morphology, and electronic property after doping. The doping of Fe atoms promote the growth of the [111] crystal plane, resulting in a large specific area and exposing more catalytic active sites. Meanwhile, the Feδ+ has the highest positive charge among all the M–Co2P/NCNTs hybrid catalysts after doping. All these changes can be used to contribute the highest electrocatalytic activity of the Fe–Co2P/NCNTs hybrid catalyst for HER. Furthermore, an optimal HER electrocatalytic activity was obtained by adjusting the doping ratio of Fe atoms. Our current research indicates that the doping of metal is also an important strategy to improve the electrocatalytic activity for the HER.