Halogen Edge-Passivated Antimonene Nanoribbons for Photocatalytic Hydrogen Evolution Reaction with High Solar-to-Hydrogen Conversion

Abstract

The photocatalytic hydrogen evolution reaction (HER) by the antimonene nanoribbon with the halogen edge passivation is investigated with the first-principles density functional theory calculations. Both the armchair and zigzag structures (represented by aSbNR_X/zSbNR_X; X = F, Cl, Br, and I) are fully relaxed, and the stability is confirmed by the ab initio molecular dynamics. The electronic and optical properties, together with the carrier mobility, the solar-to-hydrogen energy conversion efficiency (ηSTH), and the Gibbs free energy, are determined to examine the photocatalytic performance. The results demonstrate that both the valence band maximums and conduction band minimums of aSbNR_X and zSbNR_F match the redox potentials of the water-splitting HER for the hydrogen generation, although the valence band maximums of zSbNR_Cl/Br/I are out of the condition. The nanoribbons with hydrogen edge passivation have also been investigated as a contrast to confirm the effect of the halogen edge passivation on the electronic properties of the antimonene nanoribbons. The results demonstrate that all the considered antimonene nanoribbons possess apparent optical absorptions in the visible and ultraviolet light regions. The obvious tuning effect of the strain engineering on band edges and band gaps is also observed. Under the tensile strain larger than 4%, all the present antimonene nanoribbons can satisfy the redox potentials for the water-splitting HER. Remarkably, the tensile strain can promote ηSTH, and the maximum value can reach the theoretical limit of 17.51% under the tensile strain of 12%. The change of the Gibbs free energy for HER is approximately 0.65 eV. These results indicate that the newfound nanoribbons can be preferable candidates for the solar light photocatalytic water splitting for hydrogen production.

Z-Scheme photocatalytic solar-energy-to-hydrogen conversion driven by the HfS2/SiSe heterostructure

“…[18][19][20][21][22][23][24] Moreover, many of them were identified as being suitable photocatalytic materials for HER, and an example of such a material is antimonene nanoribbon with halogen edge passivation. 25 However, the solar-energy-to-hydrogen conversion efficiency (Z) is not satisfactory because of mutual constraints between the optical absorption and the redox potential of the band energy edges. 26 Recently, a number of investigations were performed to promote Z.…”

A review on passivation engineering for improving photocatalytic hydrogen evolution performance

“…Liu et al 104 investigated the halogen edge passivation effect of antimonene nanoribbons on the H 2 evolution reaction with rst-principles density functional theory calculations. It was found that both the armchair and zigzag structures of the antimonene nanoribbons can be relaxed to a more stable state by the halogen atom than the hydrogen atom-passivated ones due to the larger electronegativity and mass of the halogen atoms.…”

“…57 To date, the study on the effect of materials on passivation engineering has mainly focused on the ion-induced surface passivation system. Liu et al 104 studied the effect of edge passivation of halogen ions on the PHE of Sb nanoribbons. In all the samples, the introduction of halogen ions is useful for improving the stability and beneting the light absorption.…”