Surface engineering of colloidal quaternary chalcogenide Cu2ZnSnS4 nanocrystals: a potential low-cost photocatalyst for water remediation.

Colloidal route synthesis of quaternary compound CZTS (Cu2ZnSnS4) has been anticipated with an inimitable combination of coordinating ligands and solvents using the hot injection technique. CZTS is recognized as one of the worthiest materials for photo-voltaic/catalytic applications due to its exclusive properties (viz., non-toxic, economical, direct bandgap, high absorbance coefficient, etc.). This paper demonstrates the formation of crystalline, single-phased, monodispersed, and electrically passivated CZTS nanoparticles using a distinctive combination of ligands viz. oleic acid (OA)-trioctylphosphine (TOP) and butylamine (BA)-trioctylphosphine (TOP). Detailed optical, structural, and electrochemical studies were done for all CZTS nanoparticles, and the most efficient composition was found using ligands butylamine and TOP. CZTS nanocrystals were rendered hydrophilic via surface-ligand engineering, which was used for photocatalysis studies of organic pollutants. Malachite green (MG) and rhodamine 6G (Rh) for water remediation have great commercial prospects. The unique selling proposition of this work is the rapid synthesis time (~ 45 min) of colloidal CZTS nanocrystals, cost-effective ligand-exchange process, and negligible material wastage (~ 200 µl per 10 ml of pollutant) during photocatalytic experiments.

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.