Toward enhanced alkaline hydrogen electrocatalysis with transition metal-functionalized nitrogen-doped carbon supports

Superior catalyst supports are crucial to developing advanced electrocatalysts toward heterogeneous catalytic reactions. Herein, we systematically investigate the role of transition metal-functionalized N-doped carbon nanosheets (M-N-C, M = Mn, Fe, Co, Ni, Cu, Mo, and Ag) as the multifunctional electrocatalyst supports toward hydrogen evolution/oxidation reactions (HER/HOR) in alkaline media. The results demonstrate that all the M-N-C nanosheets, except Cu-N-C and Ag-N-C, can promote the alkaline HER/HOR electrocatalytic activity of Pt by accelerating the sluggish Volmer step, among which Mn plays a more significant role. Analyses reveal that the promotion effect of M-N-C support is closely associated with the electronegativity of the metal dopants and the relative filling degree of their d-orbitals. For one, the metal dopant in M-N-C with smaller electronegativity would provide more electrons to oxygen and hence tune the electronic structure of Pt via the M-O-Pt bonds at the interface. For another, the transition metal in M-N4 moieties with more empty d orbitals would hybridize with O 2p orbitals more strongly that promotes the adsorption of water/hydroxyl species. The results demonstrate the conceptual significance of multifunctional supports and would inspire the future development of advanced electrocatalysts.