Colossal figure of merit and compelling HER catalytic activity of holey graphyne

Abstract

Herein, we have conducted a comprehensive study to uncover the thermal transport properties and hydrogen evolution reaction catalytic activity of recently synthesized holey graphyne. Our findings disclose that holey graphyne has a direct bandgap of 1.00 eV using the HSE06 exchange-correlation functional. The absence of imaginary phonon frequencies in the phonon dispersion ensures its dynamic stability. The formation energy of holey graphyne turns out to be - 8.46 eV/atom, comparable to graphene (- 9.22 eV/atom) and h-BN (- 8.80 eV/atom). At 300 K, the Seebeck coefficient is as high as 700 μV/K at a carrier concentration of 1 × 10¹⁰ cm^-2. The predicted room temperature lattice thermal conductivity (κ_l) of 29.3 W/mK is substantially lower than graphene (3000 W/mK) and fourfold smaller than C₃N (128 W/mK). At around 335 nm thickness, the room temperature κ_l suppresses by 25%. The calculated p-type figure of merit (ZT) reaches a maximum of 1.50 at 300 K, higher than that of holey graphene (ZT = 1.13), γ-graphyne (ZT = 0.48), and pristine graphene (ZT = 0.55 × 10^-3). It further scales up to 3.36 at 600 K. Such colossal ZT values make holey graphyne an appealing p-type thermoelectric material. Besides that, holey graphyne is a potential HER catalyst with a low overpotential of 0.20 eV, which further reduces to 0.03 eV at 2% compressive strain.