Boosting the activity for organic pollutants removal of In2O3 by loading Ag particles under natural sunlight irradiation.

A novel photocatalyst In2O3 with loading Ag particles is prepared via a facile one-step annealing method in air atmosphere. The Ag/In2O3 exhibits considerable photoactivity for decomposing sulfisoxazole (SOX), tetracycline hydrochloride (TC), and rhodamine B (RhB) under natural sunlight irradiation, which is much higher than that of pristine In2O3 and Ag species. After natural sunlight irradiation for 100 min, 70.6% of SOX, 65.6% of TC, and 81.9% of RhB are degraded over Ag/In2O3, and their corresponding chemical oxygen demand (COD) removal ratio achieve 95.4%, 38.4%, and 93.6%, respectively. A batch of experiments for degrading SOX with adjusting pollutant solution pH and adding coexisting anions over Ag/In2O3 are carried out to estimate its practical application prospect. Particularly, the as-prepared Ag/In2O3 possesses a superior stability, which exhibits no noticeable deactivation in decomposing SOX after eight cycles' reactions. In addition, the Ag/In2O3 coated on a frosted glass plate, also possesses a superior activity and stability for SOX removal, which solve the possible second pollution of residual powdered catalyst in water. Ag particles on In2O3 working as electron accepter improve charge separation and transfer efficiency, as well as the photo-absorption and organic pollutants affinity, leading to the boosted photoactivity of Ag/In2O3. The photocatalytic mechanism for degrading SOX and degradation process over Ag/In2O3 has been systemically investigated and proposed. This work offers an archetype for the rational design of highly efficient photocatalysts by metal loading.

Oxygen-deficient AgIO3 for efficiently photodegrading organic contaminants under natural sunlight.

Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO3 microsheets (AgIO3-OV) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO3 broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (•O2-). The AgIO3-OV possesses an outstanding degradation rate constant of 0.035 min-1, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm2, which is 7 and 3.5 times that of the pristine AgIO3 and C-AgIO3 (AgIO3 is calcined in air without generating Ov). In addition, the AgIO3-OV also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO3-OV. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO3-OV exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO3-OV under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO3-OV are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO3-OV catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO3-OV catalyst to treat organic contaminants in real water under natural sunlight illumination.

Bimetallic Au/Ag coated on In2O3 for the effective removal of emerging organic contaminants under natural sunlight irradiation.

Antibiotics-polluted wastewater, likely causing the spread of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs), can be effectively remediated by photocatalytic degradation driven by endless solar energy. Herein, bimetallic Au/Ag is deposited on In2O3 surface via a one-step sintering process followed by a controllable chemical reduction approach. Under natural sunlight irradiation, the optimal Au/Ag/In2O3 (UGI-1.0) photocatalyst possesses a considerable norfloxacin (NOR) degradation rate constant of 0.013 min-1, which is 3.25, 1.63, and 1.86 times higher than that of In2O3, Ag/In2O3, and Au/In2O3 respectively. The effect of many water characteristics (e.g., humic acid, water bodies, pH values, and coexisting anions) on the photodegradation performance of NOR over UGI-1.0 is investigated. Moreover, other persistent organic pollutants (ofloxacin, phenol, 2,4-dichlorophenol, and rhodamine B) can also be degraded over UGI-1.0, suggesting its universal oxidation capacity. To settle the challenge of powder photocatalyst recovery, the UGI-1.0 photocatalyst is coated on a frosted glass sheet, which exhibits outstanding activity and stability for degrading NOR. The bimetallic Au/Ag deposited on In2O3 promote its photo-absorption, and enhance its photoinduced charge separation and transfer efficiency by serving as electron accepter, leading to the boosted activity of Au/Ag/In2O3 catalysts. Particularly, the cultivation of staphylococcus aureus (S. aureus) and cabbage seeds reveals the efficient toxicity reduction of NOR by photocatalytic degradation and the nontoxic characteristic of UGI-1.0 catalyst. This work unveils the feasibility of UGI-1.0 to remediate real wastewater with the assistance of solar energy.

In Situ Construction of Manganese Oxide Photothermocatalysts for the Deep Removal of Toluene by Highly Utilizing Sunlight Energy.

The alternative use of electric energy by renewable energy to supply power for catalytic oxidation of pollutants is a sustainable technology, requiring a competent catalyst to realize efficient utilization of light and drive the catalytic reaction. Herein, in situ-synthesized manganese oxide heterostructure composites are developed through solvothermal reduction and subsequent calcination of amorphous manganese oxide (AMO). 95% of toluene conversion and 80% of CO2 mineralization were achieved over amorphous manganese oxide calcined at 250 °C (AMO-250) under light irradiation, and catalyst stability was maintained for at least 40 h. Highly utilization of light energy, uniformly dispersed nanoparticles, large specific surface area, improved metal reducibility, and oxygen desorption and migration ability at low temperature contribute to the good catalytic oxidation activity of AMO-250. Light activated more lattice oxygen to participate in the reaction via the Mars-van Krevelen (MvK) mechanism, and traditional e--h+ photocatalytic behavior exists over the AMO-250 heterostructure composite as an auxiliary degradation path. The reaction pathways of photothermocatalysis and thermocatalysis are close, except for the emergence of different copolymers, where light enhances the deep conversion of intermediates. A proof-of-concept study under natural sunlight has confirmed the feasibility of practical application in the photothermocatalytic degradation of pollutants.

Rational Design of Monolithic g-C3N4 with Floating Network Porous-like Sponge Monolithic Structure for Boosting Photocatalytic Degradation of Tetracycline under Simulated and Natural Sunlight Illumination.

In order to solve the problems of powder g-C3N4 catalysts being difficult to recycle and prone to secondary pollution, floating network porous-like sponge monolithic structure g-C3N4 (FSCN) was prepared with a one-step thermal condensation method using melamine sponge, urea, and melamine as raw materials. The phase composition, morphology, size, and chemical elements of the FSCN were studied using XRD, SEM, XPS, and UV-visible spectrophotometry. Under simulated sunlight, the removal rate for 40 mg·L-1 tetracycline (TC) by FSCN reached 76%, which was 1.2 times that of powder g-C3N4. Under natural sunlight illumination, the TC removal rate of FSCN was 70.4%, which was only 5.6% lower than that of a xenon lamp. In addition, after three repeated uses, the removal rates of the FSCN and powder g-C3N4 samples decreased by 1.7% and 2.9%, respectively, indicating that FSCN had better stability and reusability. The excellent photocatalytic activity of FSCN benefits from its three-dimensional-network sponge-like structure and outstanding light absorption properties. Finally, a possible degradation mechanism for the FSCN photocatalyst was proposed. This photocatalyst can be used as a floating catalyst for the treatment of antibiotics and other types of water pollution, providing ideas for the photocatalytic degradation of pollutants in practical applications.

Mechanical Effects of Elastic Crystals Driven by Natural Sunlight and Force.

Flexible crystals that can capture solar energy and convert it into mechanical energy are promising for a wide range of applications such as information storage and actuators, but obtaining them remains a challenge. Herein, an elastic crystal of a barbiturate derivative was found to be an excellent candidate, demonstrating plastic bending behavior under natural sunlight irradiation. 1 H NMR and high-resolution mass spectrum data of microcrystals before and after light irradiation demonstrated that light-induced [2+2] cycloaddition was the driving force for the photomechanical effects. Interestingly, the crystals retained elastic bending even after light irradiation. This is the first report of flexible crystals that can be driven by natural sunlight and that have both photomechanical properties and elasticity. Furthermore, regulation of the passive light output direction of the crystals and transport of objects by applying mechanical forces and light was demonstrated.

A green approach for the preparation of ZnO@C nanocomposite using agave americana plant extract with enhanced photodegradation.

The present study demonstrates the crucial role of agave americana extract in enhancing the optical properties of zinc oxide (ZnO) through thermal treatment method. Various analytical and surface science techniques have been used to identify the morphology, crystalline structure, chemical composition, and optical properties, including scanning electron microscopy, x-ray diffraction, high resolution transmission electron microscopy (HRTEM), x-ray spectroscopy (EDS) and UV-visible spectroscopy techniques. The physical studies revealed the transformation of ZnO nanorods into nanosheets upon addition of an optimized amount of agave americana extract, which induced large amount of amorphous carbon deposited onto ZnO nanostructures as confirmed by HRTEM analysis. The use of increasing amount of americana extract has significantly reduced the average crystallite size of ZnO nanostructures. The resultant hybrid system of C@ZnO has produced a significant effect on the ultraviolet light-assisted photodegradation of malachite green (MG) dye. The photocatalyst dose was fixed at 10 mg for each study whereas the amount of agave americana extract and MG dye concentration are varied. The functionality of hybrid system was greatly enhanced when the amount of agave americana extract increased while dye concentration kept at lower level. Ultimately, almost 100% degradation efficiency was achieved via the prepared hybrid material, revealing combined contribution from synergy, stabilization of ZnO due to excess of carbon together with the high charge separation rate. The obtained results suggest that the driving role of agave americana extract for surface modification of photocatalyst can be considered for other nanostructured photocatalysts.

Architectural MCM 41 was anchored to the Schiff base Co(II) complex to enhance methylene blue dye degradation and mimic activity.

A sequence of Schiff base Cobalt (II) Mobile Composite Matter 41 heterojunction (SBCo(II)-MCM 41) was prepared by post-synthetic protocols. Various characterization techniques were used to characterize the above samples and MCM 41: Morphology, functional groups, optical properties, crystalline nature, pore diameter, and binding energy by scanning electron microscope (SEM), High-resolution transition electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), Ultra Violet-Visible Spectroscopy (UV), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) and X-ray Photoelectron Spectroscopy (XPS). After the encapsulation of SBCo(II) on the MCM 41, the intensity in the 100-plane in powder x-ray diffraction (XRD) decreased significantly; moreover, the light absorption behavior in UV analysis was improved. The change in the surface area and the decrease in the pore diameter of the sample were also demonstrated by the BET study. The XPS results confirmed the presence of Si, O, C, N, and Co in the SBCo(II)-MCM 41 complex. The photocatalytic performance of MCM 41 and SBCo(II)-MCM 41 materials tested by the degradation of methylene blue dye (MBD) shows that MCM 41 immobilization with SBCo(II)complex is rapidly degraded under natural sunlight irradiation. The optimized 10 mg SBCo(II)-MCM 41 catalyst concentrations showed effective enhancement with the highest efficiency of 98% achieved within 2 h compared to the other two SBCo(II)-MCM 41 concentrations. Moreover, the catalytic efficiency of SBCo(II)-MCM 41 showed a biomimetic reaction without using an oxidant, which exposed it as an effective catalyst for amine to imine conversion; it was useful in the medical field for enzymes with structural assembly.

Removal assessment of disinfection by-products (DBPs) from drinking water supplies by solar heterogeneous photocatalysis: A case study of trihalomethanes (THMs).

Solar heterogeneous photocatalysis was used to remove trihalomethanes (THMs) from drinking water. THMs, mainly trichloromethane (TCM), tribromomethane (TBM), bromodichloromethane (BDCM) and dibromochloromethane (DBCM) are one of the main class of disinfection by-products (DBPs). THMs were determined by HSGC-MS with detection limits (LODs) ranging from 0.5 µg L-1 to 0.9 µg L-1 for TCM and BDCM, respectively. Results show that a great proportion of THMs present in water are finally transferred to air as a result of their high volatility in the order TCM > BDCM > DBCM > TBM. The use of band-gap semiconductor materials (TiO2 and mainly ZnO) used as photocatalysts in combination with Na2S2O8 as electron acceptor and sulfate radical anion (SO4•-) generator enhanced the photooxidation of all THMs as compared to photolytic test. The time required for 50% of THMs to disappear (DT50) from water calculated for the most effective treatment (ZnO/Na2S2O8) were 12, 42, 57 and 61 min for TCM, TBM, BDCM, and DBCM, respectively. Therefore, solar heterogeneous photocatalysis can be considered as an interesting strategy for THMs removal, especially in sunny areas like Mediterranean basin.

SPF 100+ sunscreen is more protective against sunburn than SPF 50+ in actual use: Results of a randomized, double-blind, split-face, natural sunlight exposure clinical trial.

BACKGROUND: The value of additional photoprotection provided by use of high-sun protection factor (SPF) sunscreens is controversial, and limited clinical evidence exists. OBJECTIVE: To compare the sunburn protection provided by SPF 100+ and SPF 50+ sunscreen in conditions of actual use. METHODS: A total of 199 healthy men and women (≥18 years) participated in a natural sunlight, single-exposure, split-face, randomized, double-blind study in Vail, Colorado. Each participant wore both sunscreens simultaneously during activities, with no use restrictions other than designation of the treatment area. Erythema was clinically assessed on the day following exposure. Comparative efficacy was evaluated through bilateral comparison of sunburn between treatment areas and erythema score, as evaluated separately for each treatment area. RESULTS: Following an average 6.1 ± 1.3 hours of sun exposure, investigator-blinded evaluation identified 55.3% of the participants (110 of 199) as more sunburned on the SPF 50+ protected side and 5% (10 of 199) on the SPF 100+ protected side. After exposure, 40.7% of the participants (81 of 199) exhibited increased erythema scores (by ≥1) on the SPF 50+ protected side as compared with 13.6% (27 of 199) on the SPF 100+ protected side. LIMITATIONS: Single-day exposure may not extrapolate to benefits of longer-term protection. CONCLUSION: SPF 100+ sunscreen was significantly more effective in protecting against sunburn than SPF 50+ sunscreen in actual use conditions.

Synergistic effect of Fe doping and oxygen vacancy in AgIO3 for effectively degrading organic pollutants under natural sunlight.

In this work, a series of hydrogenated Fe-doped AgIO3 (FAI-x) catalysts are synthesized for photodegrading diverse azo dyes and antibiotics. Under the irradiation of natural sunlight with a light intensity of ∼60 mW/cm2, the optimum FAI-10 exhibits a considerable rate constant for decomposing methyl orange (MO) of 0.067 min-1, about 7.4 times higher than that of AgIO3 (0.009 min-1), and 24.6% and 83.8% of MO can be decomposed over AgIO3 and FAI-10 after irradiation for 40 min. In the amplification photodegradation experiments with using 0.5 g catalyst and 400 mL MO dye solution (10 mg/L), FAI-10 possesses greatly higher photoreactivity to common semiconductors (ZnO, TiO2, In2O3 and Bi2MoO6), and the photodegradation rates over FAI-10 are 92%. Particularly, the FAI-10 shows superior stability, the activity of which remains unaltered after 8 continuous cycles. Foreign ions and water bodies have slight effect on the activity of FAI-10, but the MO degradation rates are decreased by adjusting pH values, especially when pH = 11 because of the strong electrostatic repulsion between MO and FAI-10. FAI-10 can also effectively decompose another azo dye (rhodamine B (RhB)) and diverse antibiotics (sulflsoxazole (SOX), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)). The activity enhancement mechanism of FAI-10 has been systemically investigated and is ascribed to the promoted photo-absorption, charge separation and transfer efficiency, and affinity of organic pollutants, owing to the synergistic effect of Fe doping and oxygen vacancy (Ov). The photocatalytic mechanisms and process for decomposing MO are verified and proposed based on radical trapping experiments and liquid chromatography-mass spectrometry (LC-MS). This work opens an avenue for the fabrication of effective photocatalysts toward water purification.

Aqueous photolysis of naproxen exposed to UV and natural sunlight: Formation of excited triplet and photosensitizing product.

Photochemical transformation is an important attenuation process for the non-steroidal anti-inflammatory drug naproxen (NPX) in both engineered and natural waters. Herein, we investigated the photolysis of NPX in aqueous solution exposed to both ultraviolet (UV, 254 nm) and natural sunlight irradiation. Results show that N2 purging significantly promoted NPX photolysis under UV irradiation, suggesting the formation of excited triplet state (3NPX*) as a critical transient. This inference was supported by benzophenone photosensitization and transient absorption spectra. Sunlight quantum yield of NPX was only one fourteenth of that under UV irradiation, suggesting the wavelength-dependence of NPX photochemistry. 3NPX* formed upon irradiation of NPX underwent photodecarboxylation leading to the formation of 2-(1-hydroxyethyl)-6-methoxynaphthalene (2HE6MN), 2-(1-hydroperoxyethyl)-6-methoxynaphthalene (2HPE6MN), and 2-acetyl-6-methoxynaphthalene (2A6MN). Notably, the conjugation and spin-orbit coupling effects of carbonyl make 2A6MN a potent triplet sensitizer, therefore promoting the photodegradation of the parent NPX. In hospital wastewater, the photolysis of NPX was influenced because the photoproduct 2A6MN and wastewater components could competitively absorb photons. Bioluminescence inhibition assay demonstrated that photoproducts of NPX exhibited higher toxicity than the parent compound. Results of this study provide new insights into the photochemical behaviors of NPX during UV treatment and in sunlit surface waters.

Glucose-mediated one-pot hydrothermal synthesis of hollow magnesium oxide-zinc oxide (MgO-ZnO) microspheres with enhanced natural sunlight photocatalytic activity.

Glucose -mediated one-pot hydrothermal method has been utilized to synthesize hollow spherical MgO-ZnO (xMgO-(1-x)ZnO, x = 0, 0.2, 0.4, 0.6) microstructures which are highly efficient in high-energy ultraviolet (UV) region of natural sunlight. In this process, glucose formed roundish spheres, and simultaneously metal precursors were coated on that spheres during the hydrothermal reaction. X-ray diffraction analysis (XRD) supports the formation of highly crystalline wurtzite structure of MgO-ZnO for Mg loading less than 20%. Higher concentration of Mg produces wurtzite hexagonal ZnO and cubic MgO in the composites. The widening in band gap energy of synthesized MgO-ZnO microspheres compared to ZnO was analyzed by UV-visible diffuse reflectance spectroscopy (UV-DRS) result. Brunauer-Emmett-Teller (BET) surface area analysis showed that with the increase in Mg loading, the specific surface area increases up to 14.27 times as compared to pristine ZnO. The synthesized catalysts were used as an efficient photocatalyst towards the degradation of rhodamine B (RhB), methylene blue (MB), and phenol under natural solar irradiation. Results illustrated that MB and RhB dye solutions were 100% degraded by 0.6 MgO-ZnO in 100 min and 150 min, respectively, whereas pure ZnO samples showed only 65% and 79% degradation. Also, for phenol solution, 0.6 MgO-ZnO showed enhanced degradation efficiency of 72% in 240 min in comparison with 58% degradation shown by ZnO. Additionally, the MgO-ZnO catalysts were stable and showed excellent degradation efficiency up to four consecutive cycles which open a new direction towards potential industrial applications. Hence, the novelty of the current work is to prepare hollow MgO-ZnO microspheres by a single-step hydrothermal process where separate carbon template preparation is not required and to utilize these hollow microspheres as a highly efficient photocatalyst by harnessing the high-energy UV fraction of natural sunlight.

Effect of experimental parameters on photocatalytic degradation efficiency of TiO2 nanoparticles synthesized by electrochemical method towards Rhodamine B dye solution under natural sunlight.

In this study, ~ 40 nm anatase TiO2 nanoparticles were successfully prepared by a simple electrochemical method by using succinic acid as a non-ammonia-based electrolyte solution and titanium sheets as electrodes. The effect of experimental parameters such as conductivity (2-12 mS/cm), pH of the initial solution (5-9), current applied (0.05-2 A), and reaction time (1-4 h) on catalyst productivity has been investigated. The analysis shows that at an optimum conductivity of 8 mS/cm and pH 7, an increase in applied current and reaction time maximizes the productivity of TiO2 nanoparticles. The obtained catalyst was used for photocatalytic degradation of rhodamine B (RhB) under natural sunlight irradiation. The effect of experimental parameters on photocatalytic degradation has also been studied. The result displayed that degradation efficiency was enhanced by ~ 3 times in the alkaline region compared to the normal pH condition and increased with an increase in catalyst loading and decreased with the initial concentration of RhB dye. Investigation of the photocatalytic mechanism by radical trapping experiments showed that RhB photocatalytic degradation was mainly dominated by hole and superoxide radicals, whereas hydroxyl radical plays a minor role. Moreover, the catalyst reusability analysis revealed good stability and showed excellent degradation up to four consecutive cycles with nearly negligible loss of photocatalytic efficiency. Thus, the present work offers a new opportunity in terms of maximization of productivity as well as sunlight-driven photocatalytic activity of the catalyst for their industrial application.

Integrating Enrichment, Reduction, and Oxidation Sites in One System for Artificial Photosynthetic Diluted CO2 Reduction.

Artificial photosynthetic diluted CO2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon-resources recycling utilization. Herein, a three-in-one photocatalytic system of CO2 enrichment, CO2 reduction and H2 O oxidation sites is designed for diluted CO2 reduction. A Zn-Salen-based covalent organic framework (Zn-S-COF) with oxidation and reductive sites is synthesized; then, ionic liquids (ILs) are loaded into the pores. As a result, [Emim]BF4 @Zn-S-COF shows a visible-light-driven CO2 -to-CO conversion rate of 105.88 µmol g-1 h-1 under diluted CO2 (15%) atmosphere, even superior than most photocatalysts in high concentrations CO2 . Moreover, natural sunlight driven diluted CO2 reduction rate also reaches 126.51 µmol g-1 in 5 h. Further experiments and theoretical calculations reveal that the triazine ring in the Zn-S-COF promotes the activity of H2 O oxidation and CO2 reduction sites, and the loaded ILs provide an enriched CO2 atmosphere, realizing the efficient photocatalytic activity in diluted CO2 reduction.

Ag3PO4-anchored La2Ti2O7 nanorod as a Z-Scheme heterostructure composite with boosted photogenerated carrier separation and enhanced photocatalytic performance under natural sunlight.

Developing wide spectra-responsive photocatalysts has attracted considerable attention in the photocatalytic technology to achieve excellent catalytic activity. Ag3PO4, with strong response to light spectra shorter than 530 nm, shows extremely outstanding photocatalytic oxidation ability. Unfortunately, the photocorrosion of Ag3PO4 is still the biggest obstacle to its application. Herein, the La2Ti2O7 nanorod was used to anchor Ag3PO4 nanoparticles in this study, and a novel Z-Scheme La2Ti2O7/Ag3PO4 heterostructure composite was constructed. Remarkably, the composite showed strong responsive to most of the spectra in natural sunlight. The Ag0 formed in-situ acted as the recombination center of photogenerated carriers, which promoted their efficient separation and contributed to the improved photocatalytic performance of the heterostructure. When the mass ratio of Ag3PO4 in the La2Ti2O7/Ag3PO4 catalyst was 50%, the degradation rate constant of Rhodamine B (RhB), methyl orange (MO), chloroquine phosphate (CQ), tetracycline (TC), and phenol under natural sunlight irradiation were 0.5923, 0.4463, 0.1399, 0.0493, and 0.0096 min-1, respectively. Furthermore, the photocorrosion of the composite was greatly inhibited, 76.49% of CQ and 83.96% of RhB were still degraded after four cycles. Besides, the holes and O2•- played a significant role in RhB degradation, and it included multiple mechanisms of deethylation, deamination, decarboxylation, and cleavage of ring-structures. Moreover, the treated solution can also show safety to the water receiving environment. Overall, the synthesized Z-Scheme La2Ti2O7/Ag3PO4 composite exhibited immense potential for removing various organic pollutants through photocatalytic technology under natural sunlight irradiation.

Heterostructure charge transfer dynamics on self-assembled ZnO on electronically different single-walled carbon nanotubes.

The charge transfer kinetics of the catalyst particles play a key role in advanced oxidation processes (AOP) for the complete destruction of recalcitrant and persistent contaminants in water. Here, a significant improvement in the photocatalytic performance is observed in the Single-Walled Carbon Nanotube (SWCNT)-ZnO heterostructure photocatalyst. The charge transfer dynamics and factors affecting AOP are studied using ZnO nanoparticles self-assembled onto three electronically different SWCNTs (metallic, semiconducting, and pristine) via the precipitation method, introducing a heterojunction interface. The creation of the SWCNT/ZnO heterostructure interface improves charge transfer and separation, resulting in a charge carrier lifetime of 7.37 ns. Also, surface area, pore size, and pore volumes are increased by 4.2 times compared to those of ZnO. The nanoparticles-coated face-mask fabric used as the floating photocatalyst exhibited high stability and recyclability with 99% RhB degradation efficiency under natural sunlight and 94% under UV light after the 5th cycle. The surface and crystal defects-oxygen or zinc defects/interstitials open new reaction active sites that assist in charge carrier transfer and act as pollutant absorption and interaction sites for enhanced performance. The ideal band edge positions of the valence band and conduction band favor the generation of H2O/OH•, OH·/OH, and O2/HO2• reactive oxygen species. OH• radicals are found to play a vital role in this AOP by using ethanol as an OH• scavenger.

Induced defect and ZnO nano-flower formation by N, N, dimethylformamide solvent for natural sunlight responsive floating photocatalytic advanced oxidation process.

The increasing disposal of dyes and face-mask propel to hunt for a solution to fight water pollution while assisting sustainability. This research overcomes the key challenges associated with implementing photocatalytic water treatment by using natural sunlight active photocatalyst, changing slurry system, eliminating the use of external triggering sources, and reusing face-mask fabric coated with ZnO to act as a floating photocatalyst. Unique morphological structures-cauliflower, hydrangea, and petals-likes are obtained with the variation in synthesis medium (Diethylene glycol (DEG), N, N-dimethyl formamide (DMF), H2O) and methods (precipitation, solvothermal) which are found to be dependent on the solvent properties. With the use of DMF having a higher dielectric constant and formation of dimethyl amine via hydrolysis, it influences in forming petals and flower-like morphologies, unlike DEG solvent. The ZnO-coated face-mask fabric is used as the floating photocatalyst under natural sunlight observing comparable 91% degradation efficiency in 100 min with that of 99% efficiency in the UV light-illuminated slurry system. The formation of petals-like structures, defects from the liberation of DMF molecules from the ZnO surface by calcination, larger pore sizes and pore volumes provided a synergistic effect on enhancing the degradation efficiency in these cases.

The role of size-controlled CeO2 nanoparticles in enhancing the stability and photocatalytic performance of ZnO in natural sunlight exposure.

In order to enhance the photocatalytic performance and stability, the various proportions of the size controlled cerium oxide (CeO2) nanoparticles were dispersed at the pre-synthesized ZnO. Although, the expected dual absorption onsets, probably due to the diminutive difference between the bandgaps of CeO2 (∼2.9 eV) and ZnO (∼3.1 eV), were not observed however, a blue shift in the bandgap energy of ZnO was witnessed with the increasing surface density of CeO2 particles. The delayed excitons recombination process with the increasing concentration of CeO2 nanoparticles was verified by the PL spectra. The structural investigation by Raman and XRD analysis revealed the surface attachment of CeO2 particles without altering the rock-salt lattice of ZnO. The morphological and fine microstructural analysis established the uniform distribution of evenly sized CeO2 particles at the surface of ZnO with the discrete fringe patterns of both the entities whereas the XPS analysis confirmed the majority of Ce4+ in dispersed CeO2. In comparison to pure ZnO, cyclic voltammetric (CV) analysis, under illumination, exposed the supportive role of surface residing CeO2 particles in eradicating the photo-corrosion of ZnO whereas the chronopotentiometry (CP) predicted the prolonged life-span of the excitons. Compared to pure ZnO, an appreciably high activity was revealed for 10% CeO2 loading as compared to pure ZnO for the removal of mono and di-nitrophenol derivatives and their mixtures under natural sunlight exposure. The variations in the removal rates in the mixture as compared to individual nitrophenol exposed the structure-based priority of ROS for the respective phenol. The significantly enhanced photocatalytic activity of the composite catalysts revealed the incremental role of surface-mounted CeO2 entities in boosting the generation of ROS under sunlight irradiation. The experimental observations were correlated and compiled to establish the mechanism of the removal process.

MnIn2S4 nanosheets growing on rods-like ß-MnO2 via covalent bonds as high-performance photocatalyst for boosting Cr(VI) photocatalytic reduction under visible light irradiation: Behavior and mechanism study.

It is an urgent and onerous task to develop catalysts for photocatalytic reduction of Cr(VI) in wastewater under wide pH range. In this work, a novel hierarchical Z-scheme MnO2/MnIn2S4 (MISO) heterojunction photocatalyst with MnIn2S4 nanosheets growing on the surface of ß-MnO2 nanorods is constructed for efficient photocatalytic reduction of Cr(VI). The optimized 2.0-MISO photocatalyst exhibits the almost 100% reduction efficiency in the pH range of 2.1-5.6 under visible light irradiation, and the apparent rate constant is 0.05814 min-1, which is 29.96 and 3.27 times higher than the pure ß-MnO2 and MnIn2S4, respectively. A efficient photocatalytic reduction of Cr(VI) to Cr(III) species on 2.0-MISO photocatalyst in actual industry wastewater (286.7 mg/L) up to 99.8% is achieved. Under natural light, the 2.0-MISO photocatalyst also shows rapid reduction of Cr(VI) species. The photocorrosion of MnIn2S4 was significantly hindered by the construction of heterojunction. And the O2- and e- species are the main active species during the Cr(VI) photoreduction process. The connection mode between MnIn2S4 and ß-MnO2 is verified by DFT calculations and a possible photocatalytic mechanism is also proposed.