Rational design of graphdiyne-supported single- and dual-atom electrocatalysts for highly efficient hydrogen evolution reaction: A DFT study

An efficient and low-cost electrocatalyst for hydrogen evolution reaction (HER) is very important for the development of clean energy technologies, and graphdiyne (GDY) has been observed to possess the promising catalytic activity when anchoring transition metal on GDY, making them one of the most highly efficient catalysts for HER. Herein, we report the rational design of transition metal (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) atoms anchored on graphdiyne as novel single- and dual-atom electrocatalysts for highly efficient and precise HER catalysis using density-functional theory (DFT) calculations. By exploring their structures and catalytic performance of HER, atomically dispersed transition metals (Cr, Mn, Fe, Co, and Ni) showed good catalytic activity, of which the single-atom catalysts (SACs) exhibit a superior catalytic performance with hydrogen adsorption free energies (ΔG H∗ ) from −0.295 to 0.178 eV, especially for Ni 1 /GDY (−0.110 eV). This catalyst makes water splitting to produce hydrogen with significant selectivity , and the electronic properties of hydrogen adsorption are performed to understand the HER performance. It is also predicted that the Volmer-Tafel mechanism is more advantageous than Volmer-Heyrovsky at low overpotentials based on Ni 1 /GDY catalyst. This study enables us to rationally design and search for highly efficient GDY-based HER electrocatalysts. • HER catalytic activity of transition metals anchored on GDY was systematically studied. • The structures of SACs and DACs for HER were rationally designed. • Ni 1 /GDY possesses better catalytic performance with the ΔG H∗ of −0.110 eV. • The HER mechanism via Volmer-Tafel pathway is optimal.