Tetrametallic mastery: Cluster-doped graphdiyne as a superior electrocatalyst for hydrogen evolution.

Hydrogen evolution reaction (HER) is a promising route for sustainable hydrogen production. However, its efficiency is limited by kinetic barriers. Herein, we employ density functional theory (DFT) calculations to demonstrate a new strategy of embedding tetrametallic transition metal clusters (3TM 1 -TM 2) into the pores of graphdiyne (GDY) to effectively optimize its HER performance. By screening 900 configurations, 10 prototypes displayed near-ideal hydrogen adsorption free energies. Among them, 3W–Hg@GDY with a ΔG H of −0.00035 eV was identified as the optimal candidate. Analysis of the electronic structure reveals hybridization between the metal d orbitals and GDY p orbitals near the Fermi level, creating partially filled impurity states to promote hydrogen adsorption. Additionally, coordination between the three TM 1 atoms and active TM 2 atom in the cluster enables precise tuning of TM 2 's electron density to achieve a moderate interaction with the adsorbed H, facilitating superior HER catalysis. Our findings showcase a new paradigm of cluster engineering for modulating GDY's reactivity that holds great promise as a universal approach for the design of high-performance GDY-based electrocatalysts beyond HER. Through screening 900 configurations of tetrametallic transition metal clusters embedded in graphdiyne via DFT calculations, we identified 10 prototypes displayed near-ideal hydrogen adsorption free energies. [Display omitted] • Screened 900 GDY-cluster configs; 10 show near-ideal HER adsorption energies. • 3 W–Hg@GDY: ΔG H -0.00035 eV, closest to ideal among prototypes. • Metal d-orbitals, GDY p-orbitals hybridization aids H adsorption. • Precisely tuned electron density on active site via coordination with three atoms enables optimal binding. [ABSTRACT FROM AUTHOR]