Utilizing 2D materials to enhance H2 generation efficiency via photocatalytic reforming industrial and solid waste.

Sustainable valorization of industrial and solid wastes by utilizing them as feedstock to generate H2 via the photocatalytic reforming (PR) process holds great promise. It can also be an effective method to treat solid waste that otherwise would require tedious and expensive processes. This approach has the potential to offer energy solutions and form value-added chemicals. In this direction, developing photocatalysts and tuning their properties play an essential role in advancing the H2 generation efficiency. This Review article explores the application of 2D photocatalysts to generate H2 via PR of industrial waste (H2S) and solid waste, such as plastic and biomass. Despite having favorable optoelectronic properties, 2D photocatalysts are not widely employed for the PR process. The latest progress in employing 2D photocatalysts to realize efficient H2 evolution from biomass, plastic, and industrial waste such as H2S is detailed in this Review. A correlation between the properties of 2D photocatalysts with H2 evolution rate is discussed. We also emphasize understanding the mechanism involved in the PR process and the importance of 2D photocatalysts design. Such rational insight aids in further enhancing the H2 generation efficiency by effectively using solid/industrial waste as a feedstock.

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.

Light-driven transformation of biomass into chemicals using photocatalysts - Vistas and challenges.

Lignocellulosic biomass has become an important sustainable resource for fuels, chemicals and energy. It is an attractive source for alternative fuels and green chemicals because it is non-edible and widely available in the planet in huge volumes. The use of biomass as starting material to produce fuels and chemicals leads to closed carbon cycle and promotes circular economy. Although there are many thermo-chemical methods such as pyrolysis, liquefaction and gasification close at hand for processing lignocellulosic biomass and transforming the derived compounds into valuable chemicals and fuels, the photocatalytic method is more advantageous as it utilizes light and ambient conditions for reforming the said compounds. Appraisal of recent literature indicates a variety of photocatalytic systems involving different catalysts, reactors and conditions studied for this purpose. This article reviews the recent developments on the photocatalytic oxidation of biomass and its derivatives into value-added chemicals. The nature of the biomass and derived molecules, nature of the photocatalysts, efficiency of the photocatalysts in terms of conversion and selectivity, influence of reaction conditions and light sources, effect of additives and mechanistic pathways are discussed. Importance has been given also to discuss the complementary technologies that could be coupled with photocatalysis for better conversion of biomass and biomass-derived molecules to value-added chemicals. A summary of these aspects, conclusions and future prospects are given in the end.

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.