Thickness-dependent catalytic activity of hydrogen evolution based on single atomic catalyst of Pt above MXene

Hydrogen as the cleanest energy carrier is a promising alternative renewable resource to fossil fuels. There is an ever-increasing interest in exploring efficient and cost-effective approaches of hydrogen production. Recent experiments have shown that single platinum atom immobilized on the metal vacancies of MXenes allows a high-efficient hydrogen evolution reaction (HER). Here usingab initiocalculations, we design a series of substitutional Pt-doped Tin+ 1CnTx(Tin+ 1CnTx-PtSA) with different thicknesses and terminations (n= 1, 2 and 3, Tx= O, F and OH), and investigate the quantum-confinement effect on the HER catalytic performance. Surprisingly, we reveal a strong thickness effect of the MXene layer on the HER performance. Among the various surface-terminated derivatives, Ti2CF2-PtSAand Ti2CH2O2-PtSAare found to be the best HER catalysts with the change of Gibbs free energy ΔGH*∼ 0 eV, complying with the thermoneutral condition. Theab initiomolecular dynamics simulations reveal that Ti2CF2-PtSAand Ti2CH2O2-PtSApossess a good thermodynamic stability. The present work shows that the HER catalytic activity of the MXene is not solely governed by the local environment of the surface such as Pt single atom. We point out the critical role of thickness control and surface decoration of substrate in achieving a high-performance HER catalytical activity.