Enhancing the Photocatalytic Activity of Halide Perovskite Cesium Bismuth Bromide/Hydrogen Titanate Heterostructures for Benzyl Alcohol Oxidation.

Halide perovskite Cs3Bi2Br9 (CBB) has excellent potential in photocatalysis due to its promising light-harvesting properties. However, its photocatalytic performance might be limited due to the unfavorable charge carrier migration and water-induced properties, which limit the stability and photocatalytic performance. Therefore, we address this constraint in this work by synthesizing a stable halide perovskite heterojunction by introducing hydrogen titanate nanosheets (H2Ti3O7-NS, HTiO-NS). Optimizing the weight % (wt%) of CBB enables synthesizing the optimal CBB/HTiO-NS, CBHTNS heterostructure. The detailed morphology and structure characterization proved that the cubic shape of CBB is anchored on the HTiO-NS surface. The 30 wt% CBB/HTiO-NS-30 (CBHTNS-30) heterojunction showed the highest BnOH photooxidation performance with 98% conversion and 75% benzoic acid (BzA) selectivity at 2 h under blue light irradiation. Detailed optical and photoelectrochemical characterization showed that the incorporating CBB and HTiO-NS widened the range of the visible-light response and improved the ability to separate the photo-induced charge carriers. The presence of HTiO-NS has increased the oxidative properties, possibly by charge separation in the heterojunction, which facilitated the generation of superoxide and hydroxyl radicals. A possible reaction pathway for the photocatalytic oxidation of BnOH to BzH and BzA was also suggested. Furthermore, through scavenger experiments, we found that the photogenerated h+, e- and •O2- play an essential role in the BnOH photooxidation, while the •OH have a minor effect on the reaction. This work may provide a strategy for using HTiO-NS-based photocatalyst to enhance the charge carrier migration and photocatalytic performance of CBB.

Carbonized Polymer Dots for Controlling Construction of MoS2 Flower-Like Nanospheres to Achieve High-Performance Li/Na Storage Devices.

Despite being one of the most promising materials in anode materials, molybdenum sulfide (MoS2 ) encounters certain obstacles, such as inadequate cycle stability, low conductivity, and unsatisfactory charge-discharge (CD) rate performance. In this study, a novel approach is employed to address the drawbacks of MoS2 . Carbon polymer dots (CPDs) are incorporated to prepare three-dimensional (3D) nanoflower-like spheres of MoS2 @CPDs through the self-assembly of MoS2 2D nanosheets, followed by annealing at 700 °C. The CPDs play a main role in the creation of the nanoflower-like spheres and also mitigate the MoS2 nanosheet limitations. The nanoflower-like spheres minimize volume changes during cycling and improve the rate performance, leading to exceptional rate performance and cycling stability in both Lithium-ion and Sodium-ion batteries (LIBs and SIBs). The optimized MoS2 @CPDs-2 electrode achieves a superb capacity of 583.4 mA h g-1 at high current density (5 A g-1 ) after 1000 cycles in LIBs, and the capacity remaining of 302.8 mA h g-1 after 500 cycles at 5 A g-1 in SIBs. Additionally, the full cell of LIBs/SIBs exhibits high capacity and good cycling stability, demonstrating its potential for practical application in fast-charging and high-energy storage.

2D/1D MoS2 /TiO2 Heterostructure Photocatalyst with a Switchable CO2 Reduction Product.

Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO2 photoreduction. Herein, the charge transfer pathway and in turn the redox potential succeeded to regulate in 2D MoS2 /1D TiO2 heterostructure by varying the light wavelength range. Several in situ measurements and experiments confirm that charge transfer follows either an S-scheme mechanism under simulated solar irradiation or a heterojunction approach under visible light illumination, elucidating the switchable property of the MoS2 /TiO2 heterostructure. Replacing the simulated sunlight irradiation with the visible light illumination switches the photocatalytic CO2 reduction product from CO to CH4. 13 CO2 isotope labeling confirms that CO2 is the source of carbon for CH4 and CO products. The photoelectrochemical H2 generation further supports the switching property of MoS2 /TiO2 . Unlike previous studies, density functional theory calculations are used to investigate the band structure of Van der Waals MoS2 /TiO2 S scheme after contact, allowing to propose accurate charge transfer pathways, in which the theoretical results are well matched with the experimental results. This work opens the opportunity to develop photocatalysts with switchable charge transport and tunable redox potential for selective artificial photosynthesis.

One-Step Hydrothermal Synthesis of Anatase TiO2 Nanotubes for Efficient Photocatalytic CO2 Reduction.

The hydrothermal dissolution-recrystallization process is a key step in the crystal structure of titania-based nanotubes and their composition. This work systematically studies the hydrothermal conditions for directly synthesizing anatase TiO2 nanotubes (ATNTs), which have not been deeply discussed elsewhere. It has been well-known that ATNTs can be synthesized by the calcination of titanate nanotubes. Herein, we found the ATNTs can be directly synthesized by optimizing the reaction temperature and time rather than calcination of titanate nanotubes, where at each temperature, there is a range of reaction times in which ATNTs can be prepared. The effect of NaOH/TiO2 ratio and starting materials was explored, and it was found that ATNTs can be prepared only if the precursor is anatase TiO2, using rutile TiO2 leads to forming titanate nanotubes. As a result, ATNTs produced directly without calcination have excellent photocatalytic CO2 reduction than titanate nanotubes and ATNTs prepared by titanate calcination.

Sulfate radicals induced from peroxymonosulfate on electrochemically synthesized TiO2-MoO3 heterostructure with Ti-O-Mo bond charge transfer pathway for potential organic pollutant removal under solar light irradiation.

Here, a novel method for synthesis of heterostructured TiO2-MoO3 (MT) nanosheets photocatalyst by utilizing a facile electrochemical method and examined it's photocatalytic activity by the degradation of tetracycline hydrochloride (TCH), a model of organic pollutants, in the presence of peroxymonosulfate (PMS) under solar light irradiation (SL) was reported for the first time. The influence of several factors on the degradation efficiency including the initial concentration of TCH, solution pH, catalyst dosage, PMS concentration, and the existence of inorganic anions was explored. The MT-15/PMS system displayed a promising photocatalytic performance and up to 97% of TCH was degraded in 90 min the rate of the degradation reaction of MT-15/PMS was the highest (0.05299 min-1) compared to 0.00251, 0.00337, 0.00546, 0.00735, 0.01337min-1of TiO2-P25, TiO2-P25/PMS, MoO3, MoO3/PMS, and MT-15 respectively. The enhancement can be attributed to several reasons. First, the 2D morphology of the optimized heterostructure photocatalyst plays a significant role in providing much more active sites on its surface. Next, the boosted light absorption efficiency and higher photoproduced electron-hole pair separation ability, induced by the unique direct transformation of photogenerated electrons from the valance band of TiO2 to the conduction band of MoO3 via the Ti-O-Mo bond formed at the interface of MT heterostructure. Finally, the appropriate accessible reactive sites for the activation of PMS together with the synergistic effect between activation of PMS and photocatalytic processes eased the production of active species for the degradation of pollutants. Based on the scavenger experiments and EPR analysis, hydroxide and sulfate radicals were found to be the dominant free radical active species in the degradation process. Furthermore, the synergistic degradation reaction mechanism was proposed.

Strategies to Enhance ZnO Photocatalyst's Performance for Water Treatment: A Comprehensive Review.

Despite the photocatalytic organic pollutant degradation using ZnO started in 1910-1911, many challenges are still ahead, and several critical issues have to be addressed. Large band gap, and short life-time of photogenerated electrons and holes are critical issues negatively affect the photocatalytic activity of ZnO. Various approaches have been introduced to overcome these issues including intrinsic doping, extrinsic doping, and heterostructure. This review introduces unique and deep insights into tuning of the photocatalytic activity of ZnO. It starts by description of how to tune the photocatalytic activity of pristine ZnO through tuning its morphology, surface area, exposed face, and intrinsic defects. Afterward, the review explains how the Z-scheme approach succeed to address the redox weakened issue of heterojunction approach. In general, this review provides a clear image that helps the researcher to tune the photocatalytic activity of pristine ZnO and its heterostructure.

Sunlight-driven activation of peroxymonosulfate by microwave synthesized ternary MoO3/Bi2O3/g-C3N4 heterostructures for boosting tetracycline hydrochloride degradation.

Design of direct Z-scheme heterojunction photocatalyst is considered as an effective strategy to fully use the high redox potential photogenerated charge carriers. This work reports a novel method for investigating the photosynergistic performance of the Z-scheme MoO3/Bi2O3/g-C3N4 (MBG) photocatalyst with peroxymonosulfate (PMS) for the solar degradation of tetracycline hydrochloride (TCH), a model of organic pollutants in wastewater. The results showed a better strategy to activate PMS via accelerating the redox cycle (Mo6+/Mo5+), which ultimately induces the successive generation of highly reactive oxygen species. The effect of dosage of the catalyst, PMS, pH of the solution, initial concentrations of TCH and the presence of inorganic anions were investigated. It was found that the degradation of the TCH under sunlight irradiation (SL) was strongly enhanced by the presence of the PMS as an electron acceptor. The MBG/PMS/SL system was able to degrade an initial concentration (40 mg/L) of the TCH solution within 140 min. The good reusability and stability of the MBG catalyst were evaluated by recycling the degradation experiment. The main free radicals are OH and SO4─ which played an important role in the degradation reaction were identified by scavenger experiments and confirmed by EPR spectroscopy. X-ray photoelectron spectroscopy (XPS) study revealed the role of molybdenum ion in the activation process of PMS. The possible synergistic degradation reaction mechanism was proposed.

Facile synthesis of flower-like hierarchical N-doped Nb2O5/C nanostructures with efficient photocatalytic activity under visible light.

Significant endeavors have been devoted in the past few years to establish efficient visible light-activated photocatalysts. Herein, we successfully synthesized a flower-like hierarchical nitrogen-doped and carbon-sensitized Nb2O5 (NBO) nanostructure (denoted N-NBO/C). The as-prepared N-NBO/C possessed a specific surface area of 260.37 m2 g-1 and single wire diameter of less than 10 nm. The effect of reaction parameters such as hydrothermal reaction time, temperature and concentration of hexamethylenetetramine (Hmta) on the morphology of NBO was systematically investigated to elucidate the growth mechanism. The carbon on the surface and the nitrogen in the framework of NBO are beneficial for light harvesting, visible light absorption, formation of oxygen vacancies, and electron-hole separation. The photocatalytic performance of the as-fabricated N-NBO/C nanostructures was estimated via the photodegradation of 30 mg L-1 RhB, where greater than 98% of RhB was decomposed within 30 min upon visible-light radiation. Hence, the obtained N-NBO/C nanostructure exhibits much higher photocatalytic activity for the decomposition of RhB upon visible light irradiation than that of pure niobium oxide (NBO), nitrogen-doped titanium oxide (N-TIO), and nitrogen-doped niobium oxide (N-NBO). This work supplies a versatile route for the synthesis of nitrogen-doped and carbon-sensitized metal-oxide nanostructures for possible utilization in solar energy transformation and environmental remediation.

Sunlight-Driven Combustion Synthesis of Defective Metal Oxide Nanostructures with Enhanced Photocatalytic Activity.

Synthesis of metal oxide nanostructures through combustion routes is a promising technique owing to its simplicity, rapidity, scalability, and cost-effectiveness. Herein, a sunlight-driven combustion approach is developed to synthesize pristine metal oxides and their heterostructures. Sunlight, a sustainable energy source, is used not only to initiate the combustion reaction but also to create oxygen vacancies on the metal oxide surface. ZnO nanostructures are successfully synthesized using this novel approach, and the products exhibit higher photocatalytic activity in the decomposition of methyl orange (MO) than ZnO nanostructures synthesized by the conventional methods. The higher photocatalytic activity is due to the narrower band gap, higher porosity, smaller and more uniform particle size, surface oxygen vacancies, as well as the enhanced exciton dissociation efficiency induced by the sunlight. Porous Fe3O4 nanostructures are also prepared using this environmentally benign method. Surprisingly, few-layer Bi2O3 nanosheets are successfully obtained using the sunlight-driven combustion approach. Moreover, the approach developed here is used to synthesize Bi2O3/ZnO heterostructure exhibiting a structure of few-layer Bi2O3 nanosheets decorated with ZnO nanoparticles. Bi2O3 nanosheets and Bi2O3/ZnO heterostructures synthesized by sunlight-driven combustion route exhibit higher photocatalytic activity than their counterparts synthesized by the conventional solution combustion method. This work illuminates a potential cost-effective method to synthesize defective metal oxide nanostructures at scale.

Smart Fortified PHBV-CS Biopolymer with ZnO-Ag Nanocomposites for Enhanced Shelf Life of Food Packaging.

Thymus vulgaris leaf extract was used as a stabilizer and reducing agent in the green, facile, and biomimetic hydrothermal decomposition reaction for the fabrication of zinc oxide-silver nanocomposites (ZnO-Ag NCs). The nanocomposite (NC) as an active agent was integrated into poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-chitosan (PHBV-CS) in a highly precise ratio of solvent mixture by ultrasonication without the aid of any coupling agent to fabricate the novel degradable biopolymer (BP) nanocomposite via solvent casting method to enhance the mechanical properties and antimicrobial activity and with the lowest immigration rate to improve the shelf life of poultry items. The ZnO-Ag NCs as a nanoactive agent in the food packaging preserved food safety by controlling its spoilage. The morphology, physical, mechanical, barrier, antibacterial, and migration properties of the nanocrystals were assessed via several characterization methods to show the enhancement of the prepared polymer in various aspects of properties. The NCs BP were used for potential sensory evaluation of chicken breast refrigerated over a period of 15 days. The data demonstrated that these bio-based nanocomposites show great antimicrobial activity that offers perspectives for the replacement of traditional petrochemical-based polymers currently used for food packaging of poultry items.

Novel Green Biomimetic Approach for Synthesis of ZnO-Ag Nanocomposite; Antimicrobial Activity against Food-borne Pathogen, Biocompatibility and Solar Photocatalysis.

A simple, eco-friendly, and biomimetic approach using Thymus vulgaris (T. vulgaris) leaf extract was developed for the formation of ZnO-Ag nanocomposites (NCs) without employing any stabilizer and a chemical surfactant. T. vulgaris leaf extract was used for the first time, in a novel approach, for green fabrication of ZnO-Ag NCs as a size based reducing agent via the hydrothermal method in a single step. Presence of phenols in T. vulgaris leaf extract has served as both reducing and capping agents that play a critical role in the production of ZnO-Ag NCs. The effect of silver nitrate concentration in the formation of ZnO-Ag NCs was studied. The in-vitro Antimicrobial activity of NCs displayed high antimicrobial potency on selective gram negative and positive foodborne pathogens. Antioxidant activity of ZnO-Ag NCs was evaluated via (2,2-diphenyl-1-picrylhydrazyl) DPPH method. Photocatalytic performance of ZnO-Ag NCs was appraised by degradation of phenol under natural sunlight, which exhibited efficient photocatalytic activity on phenol. Cytotoxicity of the NCs was evaluated using the haemolysis assay. Results of this study reveal that T. vulgaris leaf extract, containing phytochemicals, possess reducing property for ZnO-Ag NCs fabrication and the obtained ZnO-Ag NCs could be employed effectively for biological applications in food science. Therefore, the present study offers a promising way to achieve high-efficiency photocatalysis based on the hybrid structure of semiconductor/metal.

Direct Z-Scheme Cs2O-Bi2O3-ZnO Heterostructures as Efficient Sunlight-Driven Photocatalysts.

Limited light absorption, inefficient electron-hole separation, and unsuitable positions of conduction band bottom and/or valence band top are three major critical issues associated with high-efficiency photocatalytic water treatment. An attempt has been carried out here to address these issues through the synthesis of direct Z-scheme Cs2O-Bi2O3-ZnO heterostructures via a facile, fast, and economic method: solution combustions synthesis. The photocatalytic performances are examined by the 4-chlorophenol degradation test under simulated sunlight irradiation. UV-vis diffuse reflectance spectroscopy analysis, electrochemical impedance test, and the observed transient photocurrent responses prove not only the significant role of Cs2O in extending light absorption to visible and near-infrared regions but also its involvement in charge carrier separation. Radical-trapping experiments verify the direct Z-scheme approach followed by the charge carriers in heterostructured Cs2O-Bi2O3-ZnO photocatalysts. The Z-scheme charge carrier pathway induced by the presence of Cs2O has emerged as the reason behind the efficient charge carrier separation and high photocatalytic activity.