Spatially Separating Redox Centers and Photothermal Effect Synergistically Boosting the Photocatalytic Hydrogen Evolution of ZnIn2 S4 Nanosheets.

Spatially separated loading of reductive and oxidative cocatalysts is a useful strategy for expediting charge separation and surface reaction kinetics, which are two key factors for determining the photocatalytic efficiency. However, loading the spatial separation of dual cocatalysts on a 2D photocatalyst is still a great challenge. Herein, decorating the spatial separation of oxidative and reductive cocatalysts on ZnIn2 S4 nanosheets is realized by designing a ternary Co9 S8 @ZnIn2 S4 @PdS (CS@ZIS@PS) hollow tubular core-shell structure. Particularly, Co9 S8 and PdS functionally serve as the reduction and oxidation cocatalysts, respectively. Experimental results confirm that the spatial separation of Co9 S8 and PdS cocatalysts not only efficiently improve charge separation and accelerate surface reduction-oxidation kinetics, but also generate a photothermal effect to further enhance charge transfer and surface reaction kinetics. As a result, the optimized CS@ZIS@PS yields a remarkable H2 evolution rate of 11407 µmol g-1 h-1 , and the apparent quantum efficiency reaches 71.2% at 420 nm, which is one of the highest values among ZnIn2 S4 so far. The synergistic effect of spatially separated dual cocatalysts and photothermal effect may be applied to other 2D materials for efficient solar energy conversion.

Ultrathin ZnIn2 S4 Nanosheets Anchored on Ti3 C2 TX MXene for Photocatalytic H2 Evolution.

Photocatalysts derived from semiconductor heterojunctions that harvest solar energy and catalyze reactions still suffer from low solar-to-hydrogen conversion efficiency. Now, MXene (Ti3 C2 TX ) nanosheets (MNs) are used to support the in situ growth of ultrathin ZnIn2 S4 nanosheets (UZNs), producing sandwich-like hierarchical heterostructures (UZNs-MNs-UZNs) for efficient photocatalytic H2 evolution. Opportune lateral epitaxy of UZNs on the surface of MNs improves specific surface area, pore diameter, and hydrophilicity of the resulting materials, all of which could be beneficial to the photocatalytic activity. Owing to the Schottky junction and ultrathin 2D structures of UZNs and MNs, the heterostructures could effectively suppress photoexcited electron-hole recombination and boost photoexcited charge transfer and separation. The heterostructure photocatalyst exhibits improved photocatalytic H2 evolution performance (6.6 times higher than pristine ZnIn2 S4 ) and excellent stability.

Rapid Microwave-Assisted Synthesis of ZnIn2S4 Nanosheets for Highly Efficient Photocatalytic Hydrogen Production.

In this study, a facile and rapid microwave-assisted synthesis method was used to synthesize In2S3 nanosheets, ZnS nanosheets, and ZnIn2S4 nanosheets with sulfur vacancies. The two-dimensional semiconductor photocatalysts of ZnIn2S4 nanosheets were characterized by XRD, FESEM, BET, TEM, XPS, UV-vis diffuse reflectance, and PL spectroscopy. The ZnIn2S4 with sulfur vacancies exhibited an evident energy bandgap value of 2.82 eV, as determined by UV-visible diffuse reflectance spectroscopy, and its energy band diagram was obtained through the combination of XPS and energy bandgap values. ZnIn2S4 nanosheets exhibited about 33.3 and 16.6 times higher photocatalytic hydrogen production than In2S3 nanosheets and ZnS nanosheets, respectively, under visible-light irradiation. Various factors, including materials, sacrificial reagents, and pH values, were used to evaluate the influence of ZnIn2S4 nanosheets on photocatalytic hydrogen production. In addition, the ZnIn2S4 nanosheets revealed the highest photocatalytic hydrogen production from seawater, which was about 209.4 and 106.7 times higher than that of In2S3 nanosheets and ZnS nanosheets, respectively. The presence of sulfur vacancies in ZnIn2S4 nanosheets offers promising opportunities for developing highly efficient and stable photocatalysts for photocatalytic hydrogen production from seawater under visible-light irradiation.

Construction of Hollow Co3O4@ZnIn2S4 p-n Heterojunctions for Highly Efficient Photocatalytic Hydrogen Production.

Photocatalysts derived from semiconductor heterojunctions for water splitting have bright prospects in solar energy conversion. Here, a Co3O4@ZIS p-n heterojunction was successfully created by developing two-dimensional ZnIn2S4 on ZIF-67-derived hollow Co3O4 nanocages, realizing efficient spatial separation of the electron-hole pair. Moreover, the black hollow structure of Co3O4 considerably increases the range of light absorption and the light utilization efficiency of the heterojunction avoids the agglomeration of ZnIn2S4 nanosheets and further improves the hydrogen generation rate of the material. The obtained Co3O4(20) @ZIS showed excellent photocatalytic H2 activity of 5.38 mmol g-1·h-1 under simulated solar light, which was seven times more than that of pure ZnIn2S4. Therefore, these kinds of constructions of hollow p-n heterojunctions have a positive prospect in solar energy conversion fields.

Highly stable and durable ZnIn2S4 nanosheets wrapped oxygen deficient blue TiO2(B) catalyst for selective CO2 photoreduction into CO and CH4.

Developing new and highly stable efficient photocatalysts is crucial for achieving high performance and selective photocatalytic CO2 conversion. In this paper, we designed a one-dimensional oxygen-deficient blue TiO2(B) (BT) catalyst for improved electron mobility and visible light accessibility. In addition, hexagonal ZnIn2S4 (ZIS) nanosheets with a low bandgap and great visible light accessibility are employed to produce effective heterostructures with BT. The synthesized materials are tested for photocatalytic conversion of CO2 into solar fuels (H2, CO and CH4). The optimized composite yields 71.6 and 10.3 µmol g-1h-1 of CO and CH4, three and ten times greater than ZIS, respectively. When ZIS nanosheets are combined with a one-dimensional oxygen-deficient BT catalyst, improved electron mobility and visible light accessibility are achieved, charge carriers are effectively segregated, and the transfer process is accelerated, resulting in efficient CO2 reduction. The photocatalytic CO2 conversion activity of the constructed BT/ZIS heterostructures is very stable over a 10-day (240-hour) period, and CO and CH4 production rates increase linearly with time; however, as time goes on, the rates of H2 production decrease. Further, a five-time recycling test confirmed this, revealing essentially equal activity and selectivity throughout the experiment. As a result, CO2 to CO and CH4 conversion has high selectivity and longer durability. The band structure of the BT/ZIS composite is determined using Mott-Schottky measurement, diffuse reflectance spectroscopy, and valence band X-ray photoelectron spectroscopy. This research demonstrates a novel approach to investigating effective, stable, and selective photocatalytic CO2 reduction systems for solar-to-chemical energy conversion.