An in-situ NH4+-etched strategy for anchoring atomic Mo site on ZnIn2S4 hierarchical nanotubes for superior hydrogen photocatalysis

Abstract

Atomic sites co-catalyst (ASC) on photocatalytic materials possesses an attractive prospect to promote charge carrier separation and tune surface reaction kinetics, yet the synthesis of earth-abundant ASC under low temperature remains a great challenge. Here, a novel in-situ NH 4 + -etched strategy to anchor atomic Mo sites on ZnIn 2 S 4 hierarchical nanotubes (HNTs) with abundant mesopores under mild conditions for promoting charge carrier separation and enhancing light multi-reflections is developed for efficient photocatalytic H 2 evolution. Density functional theory calculations and linear sweep voltammetry demonstrate that the well-defined Mo-S 2 O 1 sites with distinctive coordination configuration and electronic property contribute to the enhanced separation of photo-generated charge carriers and reduced Gibbs free energy for H 2 evolution. Consequently, the well-defined MoSA-ZIS HNTs present an excellent photocatalytic activity with a rate of 29.9 μmol h −1 (5.98 mmol g −1 h −1 ), which is 7.3 times higher than that of ZnIn 2 S 4 nanosheets (NSs), to be among the best ZnIn 2 S 4 -based photocatalysts. The present strategy breaks the high-temperature limitation of conventional top-down thermal dissociation/emitting approach for anchoring non-noble metal atomic sites on catalyst support.in-situ NH 4 + -etched, hierarchical nanotubes, Mo single atoms, photocatalytic H 2 evolution

Application of One-Dimensional Nanomaterials in Catalysis at the Single-Molecule and Single-Particle Scale

“…No matter in the field of photocatalysis or electrocatalysis, because of the complexity of the catalytic system, it is necessary to comprehensively characterize the catalytic process and deeply reveal the mechanism of the catalytic process, which is crucial to further develop the design of functional catalytic materials and further improve the catalytic performance. As we know, the catalytic reactions always take place on the surface of the catalyst, and the finer we disperse the same mass of material, the more atoms on the surface are exposed, resulting in the catalyst with a larger specific surface (Liu et al, 2016b;Chao et al, 2021). Reducing the size of the catalyst to a single particle can not only increase the effective utilization rate of the catalyst but also greatly improve its catalytic activity.…”

ZnIn2S4‐Based Nanostructures in Artificial Photosynthesis: Insights into Photocatalytic Reduction toward Sustainable Energy Production

“…3D‐bottom image: Reproduced with permission. [ 87 ] Copyright 2021, Springer Nature. 3D‐top left image: Reproduced with permission.…”

“…[80][81][82] What is more, the surface areas of ZnIn 2 S 4 can be increased, and the active sites are highly exposed by constructing nanostructured ZnIn 2 S 4 with various dimensions to achieve remarkable improvement of photocatalytic activity. So far, nanostructured ZnIn 2 S 4 with various dimensionalities (Figure 10), such as 0D quantum dots (QD), [83] 1D nanowires [21] /nanotubes, [17] 2D nanosheets, [84] and 3D hierarchical structures [85][86][87] have become the hot research area and applied in many practical fields, such as photocatalytic water splitting for hydrogen, oxygen generation, and carbon dioxide reduction.…”

“…Copyright 2011, Royal Society of Chemistry. 3D-bottom image: Reproduced with permission [87]. Copyright 2021, Springer Nature.…”

The Potential Strategies of ZnIn2S4-Based Photocatalysts for the Enhanced Hydrogen Evolution Reaction

“…Compared with other ternary metal sulfides, ZnIn 2 S 4 is the only AB 2 X 4 series compound with a layered structure, non-toxic, and has a convenient synthesis process; the unique cone structure has a huge surface area for the photocatalytic reaction and also provides plenty of active sites, which makes ZnIn 2 S 4 have greater application value in the field of energy conversion ( Jie Wang et al, 2021 ; Man Wang et al, 2021 ). However, the high photoexcited charge recombination ratio makes ZnIn 2 S 4 unable to effectively utilize solar energy, and the photocatalytic efficiency is significantly limited ( Tu et al, 2018 ; Chao et al, 2021a ; Yijin Wang et al, 2021 ; Yu et al, 2022 ). Some potential strategies such as ion doping, morphology regulation, design defects, heterojunction structure design, and loading cocatalyst have been explored ( Figure 1 ).…”