Efficient electrocatalysts capable of simultaneously driving the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and oxygen evolution reaction (OER) remain rare, largely due to the conflicting adsorption requirements of key intermediates. Using first-principles calculations combined with microkinetic modeling, this work systematically investigates transition-metal-anchored 1,3,5-triethynylbenzene graphyne frameworks (TM-TEBs) as a platform for multifunctional electrocatalysis. Across the first-row transition metals, V-TEB, Co-TEB, and Ni-TEB exhibit favorable HER activity, while Ni-TEB uniquely achieves low overpotentials for both the ORR and OER. Activity trends are governed by metal-to-ligand charge transfer and the position of the metal d-band center, which together regulate intermediate binding energies and define the ORR/OER volcano relationships. Microkinetic simulations incorporating temperature and coverage effects predict overpotentials as low as 0.23 V for the ORR and 0.18 V for the OER on Ni-TEB, confirming its outstanding bifunctional performance beyond thermodynamic analysis. Coupled with its near-optimal hydrogen adsorption free energy, Ni-TEB emerges as a rare noble-metal-free trifunctional electrocatalyst. These results establish metalated graphyne frameworks as electronically tunable single-atom platforms for integrated electrocatalytic reactions.
Hu et al. (Mon,) studied this question.