Comprehensive Insights into the Family of Atomically Thin 2D-Materials for Diverse Photocatalytic Applications.

2D materials with their fascinating physiochemical, structural, and electronic properties have attracted researchers and have been used for a variety of applications such as electrocatalysis, photocatalysis, energy storage, magnetoresistance, and sensing. In recent times, 2D materials have gained great momentum in the spectrum of photocatalytic applications such as pollutant degradation, water splitting, CO2 reduction, NH3 production, microbial disinfection, and heavy metal reduction, thanks to their superior properties including visible light responsive band gap, improved charge separation and electron mobility, suppressed charge recombination and high surface reactive sites, and thus enhance the photocatalytic properties rationally as compared to 3D and other low-dimensional materials. In this context, this review spot-lights the family of various 2D materials, their properties and their 2D structure-induced photocatalytic mechanisms while giving an overview on their synthesis methods along with a detailed discussion on their diverse photocatalytic applications. Furthermore, the challenges and the future opportunities are also presented related to the future developments and advancements of 2D materials for the large-scale real-time photocatalytic applications.

Direct Z-scheme mediated SmVO4/UiO-66-NH2 heterojunction nanocomposite for the degradation of antibiotic tetracycline hydrochloride molecules under sunlight.

The use of tetracycline hydrochloride (TCH) for veterinary, human therapy, and agriculture has risen in the past few decades, making it to become one of the most exploited antibiotics. However, TCH residue in the environment is causing issues related to the evolution of antibiotic-resistant bacteria. To address such a problem, photodegradation offers a potential solution to decompose these pollutants in wastewater and thereby mitigates negative environmental impacts. In this context, the research focuses on the use of the rare-earth metal oxide samarium orthovanadate (SmVO4) with nanorod structure, coupled with UiO-66-NH2 for the photocatalytic degradation. Their photocatalytic activity to degrade antibiotic TCH molecules is explored under simulated solar light irradiation. The integration of UiO-66-NH2 with SmVO4 enhanced the light absorption, recombination resistance, carrier lifetime (from 0.382 to 0.411 ns) and specific surface area (from 67.17 to 246 m2/g) of the composite system as confirmed from multiple analyses. The obtained results further indicated that SmVO4/UiO-66-NH2 nanocomposites could form a direct Z-scheme based heterojunction. Such mechanism of charge transfer leads to the effective degradation of TCH molecules up to 50% in 90 min under solar light, while it is degraded only 30% in the case of bare-SmVO4 nanorods. In this work, the incorporation of UiO-66-NH2 positively influences photoelectrochemical properties and improves the overall photoredox properties of SmVO4 for the degradation of complex compounds like antibiotic TCH molecules. Therefore, UiO-66-NH2 can be proposed as an effective material to sensitize the rare-earth based photocatalytic material.

Emerging Hybrid Nanocomposite Photocatalysts for the Degradation of Antibiotics: Insights into Their Designs and Mechanisms.

The raising occurrence of antibiotics in the global water bodies has received the emerging concern due to their potential threats of generating the antibiotic-resistive and genotoxic effects into humans and aquatic species. In this direction, the solar energy assisted photocatalytic technique offers a promising solution to address such emerging concern and paves ways for the complete degradation of antibiotics with the generation of less or non-toxic by-products. Particularly, the designing of hybrid photocatalyticcomposite materials has been found to show higher antibiotics degradation efficiencies. As the hybrid photocatalysts are found as the systems with ideal characteristic properties such as superior structural, surface and interfacial properties, they offer enhanced photoabsorbance, charge-separation, -transfer, redox properties, photostability and easy recovery. In this context, this review study presents an overview on the recent developments in the designing of various hybrid photocatalytic systems and their efficiency towards the degradation of various emerging antibiotic pharmaceutical contaminants in water environments.

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.

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.

Copper (0) Mediated Single Electron Transfer-Living Radical Polymerization of Methyl Methacrylate: Functionalized Graphene as a Convenient Tool for Radical Initiator.

Polymer nanocomposites have been synthesized by the covalent addition of bromide-functionalized graphene (Graphene-Br) through the single electron transfer-living radical polymerization technique (SET-LRP). Graphite functionalized with bromide for the first time via an efficient route using mild reagents has been designed to develop a graphene based radical initiator. The efficiency of sacrificial initiator (ethyl α-bromoisobutyrate) has also been compared with a graphene based initiator towards monitoring their Cu(0) mediated controlled molecular weight and morphological structures through mass spectroscopy (MOLDI-TOF) and field emission scanning electron microscopy (FE-SEM) analysis, respectively. The enhancement in thermal stability is observed for graphene-grafted-poly(methyl methacrylate) (G-g-PMMA) at 392 °C, which may be due to the influence ofthe covalent addition of graphene, whereas the sacrificial initiator used to synthesize G-graft-PMMA (S) has low thermal stability as analyzed by TGA. A significant difference is noticed on their glass transition and melting temperatures by DSC. The controlled formation and structural features of the polymer-functionalized-graphene is characterized by Raman, FT-IR, UV-Vis spectroscopy, NMR, and zeta potential measurements. The wettability measurements of the novel G-graft-PMMA on leather surface were found to be better in hydrophobic nature with a water contact angle of 109 ± 1°.