Mesoporous Dual-Semiconductor ZnS/CdS Nanocomposites as Efficient Visible Light Photocatalysts for Hydrogen Generation.

The development of functional catalysts for the photogeneration of hydrogen (H2) via water-splitting is crucial in the pursuit of sustainable energy solutions. To that end, metal-sulfide semiconductors, such as CdS and ZnS, can play a significant role in the process due to their interesting optoelectronic and catalytic properties. However, inefficient charge-carrier dissociation and poor photochemical stability remain significant limitations to photocatalytic efficiency. Herein, dual-semiconductor nanocomposites of ZnS/CdS nanocrystal assemblies (NCAs) are developed as efficient visible light photocatalysts for H2 generation. The resultant materials, synthesized via a polymer-templated self-polymerization method, comprise a unique combination of ~5-7 nm-sized metal-sulfide nanoparticles that are interlinked to form a 3D open-pore structure with large internal surface area (up to 285 m2 g-1) and uniform pores (circa 6-7 nm). By adjusting the ratio of constituent nanoparticles, the optimized ZnS/CdS catalyst with 50 wt.% ZnS content demonstrates a remarkable stability and visible light H2-evolution activity (~29 mmol g-1 h-1 mass activity) with an apparent quantum yield (AQY) of 60% at 420 nm. Photocatalytic evaluation experiments combined with electrochemical and spectroscopic studies suggest that the superior photocatalytic performance of these materials stems from the accessible 3D open-pore structure and the efficient defect-mediated charge transfer mechanism at the ZnS/CdS nanointerfaces. Overall, this work provides a new perspective for designing functional and stable photocatalytic materials for sustainable H2 production.

All-Inorganic p-n Heterojunction Solar Cells by Solution Combustion Synthesis Using N-type FeMnO3 Perovskite Photoactive Layer.

This study outlines the synthesis and physicochemical characteristics of a solution-processable iron manganite (FeMnO3) nanoparticles via a chemical combustion method using tartaric acid as a fuel whilst demonstrating the performance of this material as a n-type photoactive layer in all-oxide solar cells. It is shown that the solution combustion synthesis (SCS) method enables the formation of pure crystal phase FeMnO3 with controllable particle size. XRD pattern and morphology images from TEM confirm the purity of FeMnO3 phase and the relatively small crystallite size (∼13 nm), firstly reported in the literature. Moreover, to assemble a network of connected FeMnO3 nanoparticles, ß-alanine was used as a capping agent and dimethylformamide (DMF) as a polar aprotic solvent for the colloidal dispersion of FeMnO3 NPs. This procedure yields a ∼500 nm thick FeMnO3 n-type photoactive layer. The proposed method is crucial to obtain functional solution processed NiO/FeMnO3 heterojunction inorganic photovoltaics. Photovoltaic performance and solar cell device limitations of the NiO/FeMnO3-based heterojunction solar cells are presented.

Controlling Solar Hydrogen Production by Organizing Porphyrins.

In this study, a highly efficient photocatalytic H2 production system is developed by employing porphyrins as photocatalysts. Palladium and platinum tetracarboxyporphyrins (PdTCP and PtTCP) are adsorbed or coadsorbed onto TiO2 nanoparticles (NPs), which act as the electron transport medium and as a scaffold that promotes the self-organization of the porphyrinoids. The self-organization of PdTCP and PtTCP, forming H- and J-aggregates, respectively, is the key element for H2 evolution, as in the absence of TiO2 NPs no catalytic activity is detected. Notably, J-aggregated PtTCPs are more efficient for H2 production than H-aggregated PdTCPs. In this approach, a single porphyrin, which self-organizes onto TiO2 NPs, acts as the light harvester and simultaneously as the catalyst, whereas TiO2 serves as the electron transport medium. Importantly, the concurrent adsorption of PdTCP and PtTCP onto TiO2 NPs results in the most efficient catalytic system, giving a turnover number of 22,733 and 30.2 mmol(H2 ) g(cat)-1 .

Interface Engineering of MoS2 -Modified Graphitic Carbon Nitride Nano-photocatalysts for an Efficient Hydrogen Evolution Reaction.

Understanding of photochemical charge transfer processes at nanoscale heterojunctions is essential in developing effective catalysts. Here, we utilize a controllable synthesis method and a combination of optical absorption, photoluminescence, and electrochemical impedance spectroscopic studies to investigate the effect of MoS2 nanosheet lateral dimension and edge length size on the photochemical behavior of MoS2 -modified graphitic carbon nitride (g-C3 N4 ) heterojunctions. These nano-heterostructures, which comprise interlayer junctions with variable area (i. e., MoS2 lateral size ranges from 18 nm to 52 nm), provide a size-tunable interfacial charge transfer through the MoS2 /g-C3 N4 contacts, while exposing a large fraction of surface MoS2 edge sites available for the hydrogen evolution reaction. Importantly, modification of g-C3 N4 with MoS2 layers of 39±5 nm lateral size (20 wt % loading) creates interfacial contacts with relatively large number of MoS2 edge sites and efficient electronic transport phenomena, yielding a high photocatalytic H2 -production activity of 1497 µmol h-1 gcat -1 and an apparent QY of 3.3 % at 410 nm light irradiation. This study thus offers a design strategy to improve light energy conversion efficiency of catalysts by engineering interfaces at the nanoscale in 2D-layered heterojunction materials.

Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the pore surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.

BTEX and MTBE adsorption onto raw and thermally modified diatomite.

The removal of BTEX (benzene, toluene, ethyl-benzene and xylenes) and MTBE (methyl tertiary butyl ether) from aqueous solution by raw (D(R)) and thermally modified diatomite at 550, 750 and 950 degrees C (D(550), D(750) and D(950) respectively) was studied. Physical characteristics of both raw and modified diatomite such as specific surface, pore volume distribution, porosity and pH(solution) were determined, indicating important structural changes in the modified diatomite, due to exposure to high temperatures. Both adsorption kinetic and isotherm experiments were carried out. The kinetics data proved a closer fit to the pseudo-second order model. Maximum values for the rate constant, k(2), were obtained for MTBE and benzene (48.9326 and 18.0996 g mg(-1)h(-1), respectively) in sample D(550). The isotherm data proved to fit the Freundlich model more closely, which produced values of the isotherm constant 1/n higher than one, indicating unfavorable adsorption. The highest adsorption capacity, calculated through the values of the isotherm constant k(F), was obtained for MTBE (48.42 mg kg(-1) (mg/L)(n)) in sample D(950).