Constructing Novel 2D Composite Nanomaterials by Coupling Graphene or Silicene with TM3N2 MXene (TM = Nb, Ta, Mo, and W) to Achieve Highly Efficient HER Catalysts

MXenes have emerged as promising candidates for energy storage and catalyst design. Through detailed density functional theory (DFT) calculations, we designed a series of new 2D composite MXene-based nanomaterials by covering excellent TM₃N₂ MXenes (TM = Nb, Ta, Mo, and W) with graphene or buckled silicene. Our findings demonstrate that this coating can lead to high catalytic activity for hydrogen evolution reactions (HER) in these composite MXene-based systems, with silicene exhibiting superior performance compared to graphene. The relevant carbon and silicon atoms in the coated materials serve as active sites for HER due to complex electron transfer processes. Additionally, doping N or P atoms into graphene/silicene, which have similar atomic radii, but larger electronegativity than C/Si atoms, can further enhance the HER activity of adjacent carbon or silicon atoms, thus endowing the composite systems with higher HER catalytic performance. Coupled with their high stability and metallic conductivity, all these composite systems show great potential as electrocatalysts for HER. These remarkable findings offer new strategies and valuable insights for designing non-precious and highly efficient MXene-based HER electrocatalysts.