Solar hydrogen generation from organic substance using earth abundant CuS–NiO heterojunction semiconductor photocatalyst

This work explores the critical role of NiO co-catalyst assembled on the surface of a CuS primary photocatalyst which effectively improves interface properties and enhances solar-to-hydrogen production by prolonging lifetime of photo-excitons generated at the CuS surface. The nanoscale CuS/NiO heterojunction is formulated using hydrothermal and wet impregnation methods. The resultant CuS/NiO composite shows optical absorbance between 380-780 nm region. The type-II energetic structure formed at CuS/NiO heterojunction facilitates rapid charge separation and as a result, the CuS/NiO composite exhibits 13 folds higher photocatalytic water splitting performance than CuO and NiO. The champion CuO/NiO photocatalyst is first identified by screening the catalysts using a preliminary water splitting test reaction under natural Sunlight irradiation. After the optimization of the catalyst, it was further explored for enhanced photocatalytic hydrogen production using different organic substances dispersed in water (alcohols, amine and organic acids). The champion CuS/NiO catalyst(CPN-2) exhibited the photocatalytic hydrogen production rate of 52.3 mmol.h-1.g-1cat in the presence of lactic acid-based aqueous electrolyte and, it is superior than hydrogen production rate obtained in the presence of other organic substances (triethanolamine, glycerol, ethylene glycol, methanol) tested under identical experimental conditions. These results indicate that the energetic structure of CuS/NiO photocatalyst is favorable for photocatalytic oxidation of lactic acid or reformation of lactic acid. The oxidation of lactic acid contributes oxidative electrons for enhanced hydrogen generation as well as protects CuS from photocorrosion. The modification of surface property and energetic structure of CuS photocatalyst by the NiO co-catalyst improves photogenerated charge carrier separation and in turn enhances the solar-to-hydrogen generation. The recyclability tests showed the potential of CPN-2 photocatalystfor prolonged photocatalytic hydrogen production while continuous supply of lactic acid feedstock is available

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