Ni_1−xCo_xSe₂C/ZnIn₂S₄ Hybrid Nanocages with Strong 2D/2D Hetero‐Interface Interaction Enable Efficient H₂‐Releasing Photocatalysis

Abstract

Designing a semiconductor‐based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron‐hole pairs is highly important for enhancing H2 releasing photocatalysis. Here, a new class of Ni1−xCoxSe2–C/ZnIn2S4 hierarchical nanocages with abundant and compact ZnIn2S4 nanosheets/Ni1−xCoxSe2C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero‐junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn2S4 and Ni1−xCoxSe2C, improving the separation and transfer of photo‐generated electron‐hole pairs. As a consequence, the distinctive Ni1−xCoxSe2C/ZnIn2S4 hierarchical nanocages without using additional noble‐metal cocatalysts, display remarkable H2‐relaesing photocatalytic activity with a rate of 5.10 mmol g−1 h−1 under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn2S4 nanosheets and bare Ni1−xCoxSe2C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn2S4 and Ni1−xCoxSe2C 2D/2D hetero‐interfaces can powerfully promote the separation of photo‐generated charge carriers and the electrons transfer from ZnIn2S4 to Ni1−xCoxSe2C.

Boosting Photocatalytic Hydrogen Production via Interfacial Engineering on 2D Ultrathin Z‐Scheme ZnIn2S4/g‐C3N4 Heterojunction

“…Importantly, literature survey reflects that the hydrogen evolution performance of ZIS-100CN is among the best in reported ZIS-and CN-based photocatalysts (Figure 4e and Table S3). [3][4][5]7,10,13,14,17] The photocatalytic performance manifests that the well-controlled interface and Z-scheme charge transfer in composite photocatalysts are beneficial to the carrier separation and the improvement of photocatalytic efficiency.…”

“…[3] Therefore, the rational design and precise synthesis of photocatalysts are still appealing research spots. [4] For single component photocatalysts, it is difficult to achieve abundant hydrogen production due to the contradiction between light absorption and redox potential in thermodynamics. [5] In contrast, the rational designed composite photocatalysts have more advantages.…”

Pulsed‐Laser‐Deposition Fabricated ZnIn2S4 Photodetectors with Excellent ON/OFF Switching Characteristics toward High‐Temperature‐Resistant Photodetection Applications

“…In addition, the diffraction pattern of the annealed ZIS nanofilm is even much more pronounced than that of the powder from the ZIS target (Section S3, Supporting Information), another evidence of the high crystallinity of the former. Importantly, the ZIS produced in this study exhibits much more pronounced and narrower XRD peaks as compared to those of previous studies, [ 34,35 ] revealing great superiority of the developed PLD based two‐step strategy in preparing multielemental 2DLMs.…”

“…Furthermore, only the diffraction peaks from the (002) family lattice planes are revealed, indicating that the PLD‐derived ZIS preferentially crystalizes along the c ‐axis. This has been rarely realized by the traditional approaches for synthesizing 2D ZIS, such as solvothermal approach, [ 26 ] hydrothermal synthesis, [ 36 ] microwave‐assisted method, [ 37 ] oil bath synthesis, [ 34 ] etc. Noteworthily, it has previously been unveiled that the carrier transport of van der Waals materials along the basal plane is several orders of magnitude more efficient than that along the normal direction of the basal plane.…”

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

“…Furthermore, the PHE rate of MoSA-ZIS HNTs can still maintain 82.2% after four successive cycles (Figure 3b), indicating no substantial photocatalyst deactivation during durability test. The little decrease of PHE performance is attributed to the inevitable photo-corrosion of ZnIn 2 S 4 [36,37], reflected by the slight binding energy shifts in XPS high resolution spectra of Zn 2p, In 3d and S 2p (Figure S17). It should be noted that there is no obvious change on the valence state of Mo for MoSA-ZIS HNTs.…”