Photocatalytic Water Splitting: How Far Away Are We from Being Able to Industrially Produce Solar Hydrogen?

Solar water splitting (SWS) has been researched for about five decades, but despite successes there has not been a big breakthrough advancement. While the three fundamental steps, light absorption, charge carrier separation and diffusion, and charge utilization at redox sites are given a great deal of attention either separately or simultaneously, practical considerations that can help to increase efficiency are rarely discussed or put into practice. Nevertheless, it is possible to increase the generation of solar hydrogen by making a few little but important adjustments. In this review, we talk about various methods for photocatalytic water splitting that have been documented in the literature and importance of the thin film approach to move closer to the large-scale photocatalytic hydrogen production. For instance, when comparing the film form of the identical catalyst to the particulate form, it was found that the solar hydrogen production increased by up to two orders of magnitude. The major topic of this review with thin-film forms is, discussion on several methods of increased hydrogen generation under direct solar and one-sun circumstances. The advantages and disadvantages of thin film and particle technologies are extensively discussed. In the current assessment, potential approaches and scalable success factors are also covered. As demonstrated by a film-based approach, the local charge utilization at a zero applied potential is an appealing characteristic for SWS. Furthermore, we compare the PEC-WS and SWS for solar hydrogen generation and discuss how far we are from producing solar hydrogen on an industrial scale. We believe that the currently employed variety of attempts may be condensed to fewer strategies such as film-based evaluation, which will create a path to address the SWS issue and achieve sustainable solar hydrogen generation.

Gram-scale synthesis of ZnS/NiO core-shell hierarchical nanostructures and their enhanced H2 production in crude glycerol and sulphide wastewater.

Design and development of the efficient and durable photocatalyst that generates H2 fuel utilizing industrial wastewater under solar light irradiation is a sustainable process. Innumerable photocatalysts have been reported for efficient H2 production, but their large-scale production with the same efficiency of H2 production is a challenging task. In this study, a few gram-scale syntheses of ZnS wrapped with NiO hierarchical core-shell nanostructure via the surfactant-mediated process has been reported. Morphology and crystal structure analysis of ZnS/NiO showed spherical shaped hierarchical core-shell with cubic and face-centered cubic crystal structures. The surface examination confirmed the presence of Zn2+, S2-, Ni2+ and O2- ions in the nanocomposite. The photocurrent and photoluminescence studies of pristine and nanocomposites revealed that core-shell material is non-corrosive with a prolonged life-time of photo-excitons. Parametric studies on photocatalytic H2 generation in lab-scale photoreactor using crude glycerol in water recorded a high rate of H2 generation of 9.3 mmol h-1.g-1 of catalyst under the simulated solar light irradiation. Optimized reaction parameters are extended to a demonstrative photoreactor containing aqueous crude glycerol produced 18.5 mmol h-1 of H2 generation under the natural solar light irradiation. The same nanostructures were further tested with the simulated sulfide wastewater and the optimized catalyst showed H2 production of 350 mL h-1. The experimental results of time-on stream and catalytic stability demonstrated that ZnS/NiO hierarchical core-shell nanostructures can be recyclable and reusable for the continuous photocatalytic H2 generation.

Metal chalcogenide-based core/shell photocatalysts for solar hydrogen production: Recent advances, properties and technology challenges.

Metal chalcogenides play a vital role in the conversion of solar energy into hydrogen fuel. Hydrogen fuel technology can possibly tackle the future energy crises by replacing carbon fuels such as petroleum, diesel and kerosene, owning to zero emission carbon-free gas and eco-friendliness. Metal chalcogenides are classified into narrow band gap (CdS, Cu2S, Bi2S3, MoS2, CdSe and MoSe2) materials and wide band gap materials (ZnS, ZnSe and ZnTe). Composites of these materials are fabricated with different architectures in which core-shell is one of the unique composites that drastically improve the photo-excitons separation, where chalcogenides in the core can be well protected for sustainable uses. Thus,the core-shell structures promote the design and fabrication of composites with the required characteristics. Interestingly, the metal chalcogenides as a core-shell photocatalyst can be classified into type-I, reverse type-I, type-II and S-type nanocomposites, which can effectively influence and significantly enhance the rate of hydrogen production. In this direction, this review is undertaken to provide a comprehensive overview of the advanced preparation processes, properties of metal chalcogenides, and in particular, photocatalytic performance of the metal chalcogenides as a core-shell photocatalysts for solar hydrogen production.

Monodispersed core/shell nanospheres of ZnS/NiO with enhanced H2 generation and quantum efficiency at versatile photocatalytic conditions.

This investigation is first to elucidate the synthesis of mono-dispersed ZnS/NiO-core/shell nanostructures with a uniform thin layer of NiO-shell on the ZnS-nanospheres as a core under controlled thermal treatments. NiO-shell thickness varied to 8.2, 12.4, 18.2, and 24.2 nm, while the ZnS-core diameter remained stable about 96 ± 6 nm. The crystalline phase and core/shell structure of the materials were confirmed using XRD and HRTEM techniques, respectively. Optical properties through UV-vis spectroscopy analysis revealed the manifestation of red-shift in the absorption spectrum of core/shell materials, while the XPS analysis of elements elucidated their stable oxidation states in ZnS/NiO core/shell structure. The optimized ZnS/NiO-core/shell showed 1.42 times higher H2 generation (162.1 mmol h-1 g-1cat) than the pristine ZnS-core (113.2 mmol h-1 g-1cat), and 64.5 times higher than the pristine NiO-shell (2.5 mmol h-1 g-1cat). The quantum efficiency at wavelengths of 420, 365 nm, and 1.5 G air mass filters was found to be 13.5%, 25.0%, and 45.3%, respectively. Water splitting experiments was also performed without addition of any additives, which showed enhanced H2 gas evolution of 1.6 mmol h-1 g-1cat under the sunlight illumination. Photoelectrochemical measurements revealed the stable photocurrent density and minimized charge recombination in the system. The performed recyclability and reusability tests for five recycles demonstrated the excellent stability of the developed photocatalysts.