Graphitic carbon nitride supported Ni–Co dual-atom catalysts beyond Ni1(Co1) single-atom catalysts for hydrogen production: a density functional theory study

Using density functional theory calculations we investigate the formation, structure and electronic properties of gh-C3N4-supported Ni–Co (Ni–Co/gh-C3N4) dual-atom catalysts and Ni1(Co1) single-metal catalysts, as a paradigmatic example of single-atom versus few-atom catalysts. An inverted mold assumption is proposed to identify the factors determining the number, shape and packing manner of metal atoms inside the pores of gh-C3N4. The area matching between virtual fragments and metal fillers and lattice inheritance from N coordination and metal aggregates allow for a stable Ni–Co/gh-C3N4, which would possess more active sites and a more complex structure–activity relation than single-atom doping. The hydrogen production behavior and catalytic activity of this catalyst are comprehensively discussed. Ni–Co/gh-C3N4 exhibits higher hydrogen evolution activity than Ni1(Co1)/gh-C3N4 at an appropriate H coverage, which is comparable to Pt under analogous conditions. This strategy, derived from the inverted mold assumption, is deemed to be a simple and easy-to-operate method for designing and building metal aggregates confined inside the pores of two-dimensional materials and in the cavities of nanoparticles for few-atom catalysts.