Recent advancement in LaFeO3-mediated systems towards photocatalytic and photoelectrocatalytic hydrogen evolution reaction: A comprehensive review.

The present disrupted scenario of the world calls for urgent attention to the need for renewable resources as an energy source for harnessing and feeding uninterrupted power supply to mankind. Amidst this, Photocatalysis (PC) and Photoelectrocatalysis (PEC) are some of the most budding methods of exploiting solar energy. LaFeO3-based systems are eligible for PC/PEC Hydrogen (H2) generation, incorporating the process of water splitting, etc. It would be fair to mention that the above methods can mimic the natural process of photosynthesis. This review comprises an encyclopedia of recent advancements in LaFeO3 and modified systems towards sustainable Photocatalytic and Photoelectrocatalytic Hydrogen Evolution Reactions (HER). Besides the challenges, the review presents a clear and brief idea for the scientific research community on paving the future in upscaling and industrializing the LaFeO3-mediated green fuel (H2) generation to meet global energy needs.

Macroscopic Spontaneous Piezopolarization and Oxygen-Vacancy Coupled Robust NaNbO3/FeOOH Heterojunction for Pharmaceutical Drug Degradation and O2 Evolution: Combined Experimental and Theoretical Study.

Prompt recombination of photoproduced charges in bulk and surface of a photocatalyst significantly impedes catalytic efficiency. To address these challenges, FeOOH nanorods (NRs) anchored NaNbO3 (NNO) piezoelectric microcubes (MCs) have been fabricated for ciprofloxacin (CIP) degradation and oxygen evolution through water splitting by coupling macroscopic spontaneous piezoelectric polarization and a built-in electric field. The local electric field induced by surface oxygen vacancies (Ovs) and orientation of FeOOH NRs over NNO MCs afford the polarization electric field a significant boost, driving the quick separation/migration of charge carriers from bulk to the surface. The polarized NNO/FeOOH composite with ample Ovs demonstrates an outstanding piezophotocatalytic CIP degradation of 93% in 1 h, higher than pristine materials (NNO and FeOOH), and a high O2 evolution rate of 1155 µmol h-1. The effect of piezoelectric polarization on the catalytic activity is supplemented by theoretical simulations. This work offers an avenue for selective pollutant remediation and water splitting through the rational design of piezoelectric polarization-mediated heterostructure systems with surface Ovs.

Compositionally engineered Cd-Mo-Se alloyed QDs toward photocatalytic H2O2 production and Cr(VI) reduction with a detailed mechanism and influencing parameters.

With the exceptional advantages of safety, greenness, and low cost, photocatalytic H2O2 generation has kindled a wonderful spark, although being severely hampered by the terrible photoinduced exciton recombination, migration, and surface decomposition. Here, employing reflux method, the Cd-Mo-Se quantum dots of varying molar ratios of Cd and Mo were synthesized using thioglycolic acid as the capping ligand to regulate their growth. This type of metal alloying promotes rapid charge migration, improves light harvesting, and reduces the rate of charge recombination. The improved optoelectronic properties and boosted activity of Cd-rich ternary CMSe-1 QDs led to the observed exceptional photocatalytic H2O2 yield of 1403.5 µmol g-1 h-1 (solar to chemical conversion efficiency, 0.27%) under visible light, outperforming the other ternary and Se-based QD photocatalysts. Additionally, CMSe-1 shows 93.6% (2 h) hazardous Cr(VI) photoreduction. The enhanced catalytic performance of CMSe-1 corresponds to effective charge carrier separation and transfer efficiency, well supported by PL, TRPL, and electrochemical measurements. Photocatalytic H2O2 production was also studied under varying experimental conditions and the scavenger test suggests a superoxide radical intermediate 2-step single electron reduction pathway. The catalyst-assisted Cr(VI) reduction is substantiated by the zero-order kinetics as well as the determination of the pHPZC value. The catalyst can be employed for a maximum of four times while retaining its activity, according to the photostability and reusability test outcomes. This research presents interesting approaches for producing ternary QDs and modified systems for efficient photocatalytic H2O2 production and Cr(VI) reduction.

Defect Control via Compositional Engineering of Zn-Cu-In-S Alloyed QDs for Photocatalytic H2O2 Generation and Micropollutant Degradation: Affecting Parameters, Kinetics, and Insightful Mechanism.

Photocatalytic H2O2 production and recalcitrant pollutant degradation are regarded as promising clean technology toward achieving sustainable solar-to-chemical energy conversion. Herein, nonstoichiometric Zn-Cu-In-S (ZCIS) quaternary alloyed quantum dots (QDs) are rationally fabricated via a reflux method toward H2O2 generation and ciprofloxacin degradation under visible light irradiation. The optimum catalyst (ZCIS-2) exhibits a notable H2O2 production of 1685.2 µmole h-1 g-1 (solar-to-chemical conversion efficiency (SCC), 0.19%), which is 5.3 times higher than that of CuInS2 (CIS), and a ciprofloxacin (CIP) degradation efficiency of 96% in 2 h. The observed improvement in activity corresponds to optimized exciton separation/transfer, broad photon absorption, tunable band alignment, and effective adsorption/activation. In addition, oxygen reduction goes through both direct two-electron single-step reduction and single-electron two-step superoxide radical pathways, whereas CIP degradation proceeds via direct •O2- and indirect •OH radical pathways, as confirmed by scavenger experiments. An appropriate amount of defects improves the adsorption/activation of O2 toward H2O2 and active oxygen species generation that facilitates CIP degradation. The effect of operational parameters, such as pH, surrounding environment, presence of ions, sacrificial agent, etc., on both H2O2 formation and CIP removal is vividly studied. Hence, the current study will provide an in-depth insight into O2 photoreduction and micropollutant removal, which encourages further advancement of potent alloyed quantum dot-oriented photocatalytic systems.

Robust direct Z-scheme exciton transfer dynamics by architecting 3D BiOI MF-supported non-stoichiometric Cu0.75In0.25S NC nanocomposite for co-catalyst-free photocatalytic hydrogen evolution.

Designing promising photocatalytic systems with wide photon absorption and better exciton separation ability is a cutting-edge technology for enhanced solar-light-driven hydrogen production. In this context, non-stoichiometric Cu0.75In0.25S nanocrystals (CIS NCs) coupled with three-dimensional (3D) BiOI micro-flowers (BOI MFs) were synthesized through an ultra-sonication strategy forming a CIS-BOI heterojunction, which was well supported by XRD, photocurrent, XPS and Mott-Schottky analyses. Further, the co-catalyst-free CIS-BOI binary hybrid shows improved hydrogen evolution, i.e., 588.72 µmol h-1, which is 3.2 times greater than the pristine CIS NC (183.97 µmol h-1). Additionally, the binary composite confers an apparent conversion efficiency (ACE) of 9.44% (8.90 × 1016 number of H2 molecule per sec), which is extensively attributed to the robust charge carrier separation and transfer efficiency via the direct Z-scheme mechanism (proved through superoxide and H2 evolution activity). Moreover, the broad photon absorption range and productive exciton separation over the CIS-BOI composite are substantially justified by UV-Vis DRS, PL, EIS and photocurrent measurements.

Boosting sluggish photocatalytic hydrogen evolution through piezo-stimulated polarization: a critical review.

To address the growing energy demand, remarkable progress has been made in transferring the fossil fuel-based economy to hydrogen-based environmentally friendly photocatalytic technology. However, the sluggish production rate due to the quick charge recombination and slow diffusion process needs careful engineering to achieve the benchmark photocatalytic efficiency. Piezoelectric photocatalysis has emerged as a promising field in recent years due to its improved catalytic performance facilitated by a built-in electric field that promotes the effective separation of excitons when subjected to mechanical stimuli. This review discusses the recent progress in piezo-photocatalytic hydrogen evolution while elaborating on the mechanistic pathway, effect of piezo-polarization and various strategies adopted to improve piezo-photocatalytic activity. Moreover, our review systematically emphasizes the fundamentals of piezoelectricity and piezo-phototronics along with the operational mechanism for designing efficient piezoelectric photocatalysts. Finally, the summary and outlooks provide insight into the existing challenges and outline the future prospects and roadmap for the development of next-generation piezo-photocatalysts towards hydrogen evolution.

Robust Photoelectrochemical Route for the Ambient Fixation of Dinitrogen into Ammonia over a Nanojunction Assembled from Ceria and an Iron Boride/Phosphide Cocatalyst.

The nitrogen reduction reaction is of great scientific significance as a hydrogen fuel carrier as well as a source of value-added products; in context to this, photoelectrochemical (PEC) nitrogen fixation emerges as an effective and environmentally benign strategy to meet the need. Hence, the current work reports an effective catalytic system containing a low-cost iron boride-based cocatalyst onto the CeO2 nanosheet matrix for photoelectrochemical nitrogen reduction reaction. The harmonized electronic property and the ensemble effect of phosphorus and boron in FeB/P with unsaturated metal sites make it a site-selective cocatalyst for nitrogen adsorption and its polarization. Furthermore, the low Fermi level of iron borophosphide enhances the trapping of photogenerated electrons from CeO2 and productively provides it to the adsorbed nitrogen species. The observed peculiar photocurrent behavior confirms the interaction of photogenerated electrons with adsorbed nitrogen species and its subsequent reduction by the surrounding protonic environment. The optimized CeO2-FeB/P photoelectrocatalyst exhibited an excellent NH3 yield velocity, i.e., 9.54 µg/h/cm2 at -0.12 V vs RHE with a solar-to-chemical conversion efficiency of 0.046% under ambient conditions. The same catalyst is also very active under near-zero biasing conditions and possesses impressive durability even after multiple uses. This work might strategically direct a promising way for the exploration of new photoelectrocatalytic systems for effective PEC-nitrogen reduction reaction.

ZnFe2O4@WO3-X /Polypyrrole: An Efficient Ternary Photocatalytic System for Energy and Environmental Application.

Environmental protection and the necessity of green energy have become fundamental concerns for humankind. However, rapid recombination of photoexcitons in semiconductors often gets in the path of photocatalytic reactions and annoyingly suppresses the photocatalytic activity. In this study, a polypyrrole (PPY)-supported step-scheme (S-scheme) ZnFe2O4@WO3-X (PZFW15) ternary composite was fabricated by a multistep process: hydrothermal and calcination processes, followed by polymerization. During the formation of the heterojunction, the oxygen vacancy (OV) on WO3-X promotes effective separation and increases the redox power of the photogenerated excitons via the built-in internal electric field of S-scheme pathways between ZnF and WO3-X. The successful construction of the S-scheme heterojunction was substantiated through X-ray photoelectron spectroscopy, experimental calculations, radical trapping experiment, and liquid electron spin resonance (ESR) characterization, whereas the existence of OVs was well confirmed by EPR and Raman analyses. Meanwhile, the PPY served as a supporter, and the polaron and bipolaron species of PPY acted as electron and hole acceptors, respectively, which further enhances the charge-carrier transmission and separation in the ternary PZFW15 photocatalyst. The designed ternary nanohybrid (PZFW15) displays outstanding gemifloxacin detoxification (95%, 60 min) and hydrogen generation (657 µmol h-1), i.e., 1.5 and 2.2 times higher than the normal S-scheme ZFW15 heterostructure and pure ZnFe2O4 (ZnF), respectively, with an apparent conversion efficiency of 4.92%. The ESR and trapping experiments indicate that the generated •OH and •O2 - radicals from the PZFW15 photocatalyst are responsible for gemifloxacin degradation. This unique PPY-supported S-scheme heterojunction is also beneficial for the enhanced electron-transfer rate and provides abundant active sites for photocatalytic reactions.

Black titania an emerging photocatalyst: review highlighting the synthesis techniques and photocatalytic activity for hydrogen generation.

The TiO2 semiconductor photocatalyst is in the limelight of sustainable energy research in recent years because of its beneficial properties. However, its wide band-gap and rapid exciton recombination rate makes it a lame horse, and reduces its photocatalytic efficiency. Recently, researchers have developed facile methods for lowering the band-gap, so that it captures a wide range of solar spectrum, but the efficiency is still way behind the target value. After the discovery of black titania (B-TiO2), the associated drawbacks of white TiO2 and its modified forms were addressed to a large extent because it not only absorbs photons in a broad spectral range (UV to IR region), but also modifies the structural and morphological features, along with the electronic properties of the material, significantly boosting the catalytic performance. Hence, B-TiO2 effectively converts solar energy into renewable chemical energy i.e. green fuel H2 that can ultimately satisfy the energy crisis and environmental pollution. However, the synthesis techniques involved are quite tedious and challenging. Hence, this review summarizes various preparation methods of B-TiO2 and the involved characterization techniques. It also discusses the different modification strategies adopted to improve the H2 evolution activity, and hopes that this review acts as a guiding tool for researchers working in this field.

A Mechanistic Approach on Oxygen Vacancy-Engineered CeO2 Nanosheets Concocts over an Oyster Shell Manifesting Robust Photocatalytic Activity toward Water Oxidation.

Lethargic kinetics is the foremost bottleneck of the photocatalytic water oxidation reaction. Hence, in this respect, the CeO2 coral reef made up of nanosheets is studied focusing on the oxygen vacancy that affects the water oxidation reaction. First, CeO2 was prepared in an oyster shell/crucible with the presence/absence of urea by a simple calcination technique to tune the oxygen vacancy. More oxygen vacancy was detected in CeO2 prepared from urea and oyster shell, which is evidenced from Raman and PL analyses. Further, the oyster shell-treated sample was found to be of nanosheet type with numerous pores as observed via TEM analysis. The theoretical approach was adopted to expose the role of oxygen vacancies and the fate of scavenging agents in the water oxidation mechanism. It was observed that an oxygen vacancy plays a vital role in minimizing the activation energy hump and opposes the reverse reaction. The apparent conversion efficiency of 7.1% is calculated for the oxygen evolution reaction. Oxygen vacancy, quantum confinement effect, and charge separation efficiency are mainly responsible for the better photocatalyzed water oxidation reaction and hydroxyl radical production. This investigation will help in providing valuable information toward designing cost-effective oxygen vacancy-oriented nanosheet systems and the importance of vacancy in the water-splitting reaction.

Architecting a Double Charge-Transfer Dynamics In2S3/BiVO4 n-n Isotype Heterojunction for Superior Photocatalytic Oxytetracycline Hydrochloride Degradation and Water Oxidation Reaction: Unveiling the Association of Physicochemical, Electrochemical, and Photocatalytic Properties.

To surmount incompatibility provoked efficiency suppression of an anisotype heterojunction and to pursue an improved intrinsic photocatalytic activity by manipulating oriented transfer of photoinduced charge carriers, an In2S3/BiVO4 (1:1) n-n isotype heterojunction was fabricated successfully through a simple two-step calcination method, followed by a wet-chemical deposition method. The formation of an n-n isotype heterojunction was confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy. The photocatalytic efficiency of the In2S3/BiVO4 catalyst was examined over degradation of oxytetracycline hydrochloride (O-TCH) and oxygen (O2) evolution reaction. Consequently, an n-n In2S3/BiVO4 isotype heterojunction exhibits a superior O-TCH degradation efficiency (94.6%, 120 min) and O2 evolution (695.76 µmol, 120 min) of multiple folds as compared to the pure BiVO4 and In2S3 solely. This is attributed to the proper band alignment and intimate interfacial interaction promoted charge carrier separation over the n-n isotype heterojunction. The intimate interfacial contact was confirmed by transmission electron microscopy (TEM), high-resolution TEM, and field emission scanning electron microscopy analysis. The proper band alignment was confirmed by Mott-Schottky analysis. The photoelectrochemical linear sweep voltammetric study shows a superior photocurrent density (269 µA/cm2) for In2S3/BiVO4 as compared to those for pristine BiVO4 and In2S3, which is in good agreement with the photocatalytic results. Furthermore, the superior charge antirecombination efficiency of the n-n isotype heterojunction was established by photoluminescence, electrochemical impedance spectroscopy, Bode analysis, transient photocurrent, and carrier density analysis. The improved photostability of the heterojunction was confirmed by chronoamperometry analysis. An orderly corelationship among physicochemical, electrochemical, and photocatalytic properties was established, and a possible mechanistic pathway was presented to better understand the outcome of the n-n isotype heterojunction. This study presents an effective way to develop new n-n isotype heterojunction-based efficient photocatalysts and could enrich wide applications in other areas.

Efficient Photon Conversion via Double Charge Dynamics CeO2-BiFeO3 p-n Heterojunction Photocatalyst Promising toward N2 Fixation and Phenol-Cr(VI) Detoxification.

For better exciton separation and high catalytic activity, the most trailblazing stratagem is to construct defect engineered low-dimensional p-n heterojunction framed photocatalytic systems. In this context, we have developed a rod-sheet (1D-2D) p-n heterojunction of MCeO2-BiFeO3 by a simple hydrothermal method and scrutinized its photocatalytic performance toward N2 fixation and phenol/Cr(VI) detoxification. The intimate contact between MCeO2 and BiFeO3 in the junction material is well established via X-ray diffraction (XRD), UV-vis diffuse reflectance spectrosopy (DRS), transmission electron microscopy (TEM), and photoelectrochemical studies. Further, scanning electron microscopy (SEM) and TEM pictures clearly support the decoration of MCeO2 nanorods over BiFeO3 sheets and also depict the junction boundary. Additionally, photoluminescence (PL), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and Raman measurements give solid evidence toward the presence of an oxygen vacancy. Moreover, the Mott-Schottky result indicates a feasible band edge potential favoring the p-n heterojunction with a built-in electric field between BiFeO3 and MCeO2 favoring a double charge dynamic. The MCeO2-BFO p-n junction displays a notable catalytic activity, i.e., 98.2% Cr(VI) reduction and 85% phenol photo-oxidation, and produces 117.77 µmol h-1 g-1 of ammonia under light irradiation. Electrochemical analysis suggests a four-electron/five proton-coupled N2 photoreduction pathway. The designed oxygen vacancy oriented p-n heterojunction suffering double charge migration shows significant catalytic performance due to effective electron-hole separation as justified via PL, electrochemical impedance spectra (EIS), and Bode phase analysis.

A type-II interband alignment heterojunction architecture of cobalt titanate integrated UiO-66-NH2: A visible light mediated photocatalytic approach directed towards Norfloxacin degradation and green energy (Hydrogen) evolution.

Environmental pollution and energy scarcity is a major issue of the current scenario which forbear the progress of developing world. To overcome these problems towards a sustainable future, the utilization of sunlight by means of photocatalysis can be regarded as a best and suitable pathway. To validate this purpose, design and development of efficient heterogeneous photocatalyst for harvesting solar energy should be the major research concern for scientific community. In this regard herein, we have prepared a series of stable and efficient CoTiO3/UiO-66-NH2 p-n junction mediated heterogeneous photocatalyst by hydrothermal method. The functionalised linker of UiO-66-NH2 provided an intimate interfacial contact with CoTiO3 by Co/TiON ionic interaction, as proved by HRTEM and XPS analysis. Moreover the inverted V-shaped Mott-Schottky plot confirmed the junction formation in the optimised CoTiO3/UiO-66-NH2 material. In addition, EIS and PL analysis also provides sufficient evidence about the hindrance of active species recombination in composite as a result of p-n hetero junction. LC-MS characterization technique traces the assorted intermediate species produced in the course of photodegradation of Norfloxacin and confirms its complete degradation to corresponding CO2, H2O and NH4+ by the optimised CoTiO3/UiO-66-NH2. The highest photo-catalytic activity obtained towards Norfloxacin degradation is 90.13% and H2 production is 530.87 µmol in 1 h. The enhanced photo-catalytic reaction follows Type-II p-n hetero junction charge transfer mechanism and thus, paves a new way to design MOF based heterojunction photocatalyst for diverse photo catalytic performance.

Enhanced photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n heterojunction towards ciprofloxacin degradation, hydrogen evolution and antibacterial studies.

Fusion of heterogeneous photocatalysts with conducting polymers has paid a rising stratagem in the field of photocatalysis owing to its biocompatibility and environment friendliness. In this work a series of polypyrrole (PPY) sensitized zinc ferrite/graphitic carbon nitride (ZFCN) n-n heterojunction (ZFCN@10PPY, ZFCN@20PPY, and ZFCN@30PPY) nanocomposite were fabricated by in-situ polymerization method. Due to low band gap of polypyrrole, it behaves as a photo-sensitizer, supplies surplus numbers of electrons to ZnFe2O4/g-C3N4 n-n heterojunction and improves the photocatalytic performance. The fabricated ZFCN@20PPY exhibits highest photocatalytic activity in comparison to others nanocomposites. The superior photocatalytic performance of ZFCN@20PPY was ascribed to the tunable band structure, synergistic effect of broad absorption upto NIR region, delayed electron-hole recombination and efficient charge transfer across the junction interface which has been well confirmed from UV-Vis DRS, PL and EIS measurement. Further the photocatalytic activity of ZFCN@20PPY was supported by both n-type and p-type photocurrent density i.e. 2.4 and 3.9 mA/cm2 respectively. ZFCN@20PPY shows good photocatalytic performance towards ciprofloxacin degradation (92%) and generation of hydrogen energy (567 µmol). Along with pollutant degradation and energy production ZFCN@20PPY also shows its potential towards antibacterial activities against human pathogenic bacteria like Escherichia coli. These newly designed polymer sensitized n-n heterojunction may offer a promising strategy for maximum light absorption and be authoritative in meeting the environmental claims in the future.

Bandgap engineering via boron and sulphur doped carbon modified anatase TiO2: a visible light stimulated photocatalyst for photo-fixation of N2 and TCH degradation.

The present research reports the synthesis of two-dimensional (2D) sheet/flake-like nanostructures of crystalline carbon modified TiO2 (CT), B-TiO2 (B-CT), and S-TiO2 (S-CT) using a facile one-pot synthesis method. The crystallinity and phase purity (anatase) of the prepared nano-photocatalyst were characterised using X-ray diffraction, selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) analysis. Furthermore, the morphological details and elemental content of the sample were studied via scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), respectively. Additionally, the optoelectronic features of all of the prepared specimens were measured via UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL), impedance and Mott-Schottky studies. After successful characterisation, their photocatalytic performance was tested towards dinitrogen photo-fixation and tetracycline hydrochloride (TCH) degradation under visible light illumination. Moreover, the effective charge separation and greater availability of the active surface area led to the robust photocatalytic activity of the fabricated B-CT compared to the CT and S-CT samples, which correlates well with the PL, impedance and surface area analysis. B-CT displays the highest photocatalytic activity, i.e. 32.38 µmol L-1 (conversion efficiency = 0.076%) of ammonia production, and 95% tetracycline hydrochloride (10 ppm) degradation. Here, we have effectively designed a novel and productive pathway towards the enhancement of the photocatalytic performance of visible photon active TiO2-based materials for energy and environmental sustainability.

Facile synthesis of ZnFe2O4@RGO nanocomposites towards photocatalytic ciprofloxacin degradation and H2 energy production.

The production of Hydrogen energy through the splitting of water is a promising pathway for clean environment and sustainability. Herein we have synthesized a series of ZnFe2O4 (ZFO)@Reduced Graphene Oxide (RGO) nanocomposites by hydrothermal followed by calcination method and studied its application towards hydrogen energy production and ciprofloxacin degradation. Powder X-ray diffraction (XRD) study and X-ray photoelectron spectroscopy (XPS) analysis indicate the good crystallinity and suitable chemical environment for the photocatalytic process. Among all the samples, ZFO@3%RGO showed 73.4% of CIP degradation under solar irradiation of 1 h, which is 1.67 times higher than that of pure ZFO nanoparticles. CIP degradation process follows first order kinetics with a good rate constant of 0.021 min-1 which is 2.3 times greater than ZFO. The photocatalyst ZFO@3%RGO illustrated maximum H2 energy production i.e. 410.32 µmol/h, which is 1.35 times more than that of neat ZFO nanoparticles. ZFO@3%RGO demonstrates the highest photocurrent density of 0.6 mA/cm2 under light illuminations, which is 250 times superior to that of the pristine photocatalyst. Bode phase analysis confirmed that ZFO@RGO shows 13 times higher charge separation efficiency in comparison to neat ZFO. The best photocatalytic activity of ZFO@3%RGO nanocomposite is due to its high light absorption capacity, low photogenerated exciton recombination, high electron-hole separation, and high photocurrent density.

HPW-Anchored UiO-66 Metal-Organic Framework: A Promising Photocatalyst Effective toward Tetracycline Hydrochloride Degradation and H2 Evolution via Z-Scheme Charge Dynamics.

The abolition of environmental pollutants and production of hydrogen (H2) from water using a heterogeneous photocatalyst is a demanding science of the current scenario to solve the increasing environmental pollution and worldwide energy catastrophe in modern life. To validate this purpose, the design of low-cost and durable semiconductor-based photocatalysts with great light absorption capacity becomes the most challenging issue for researchers. Regarding this, herein the phosphotungstic acid (HPW)-anchored Zr6O4(OH)4(BDC)6 (UiO-66) metal-organic framework (MOF), i.e., HPW@UiO-66, has been prepared by a hydrothermal method and is efficient, stable, and capable of harvesting solar energy toward the degradation of tetracycline hydrochloride (TCH) and H2 production in the presence of a sacrificial donor. The ionic interaction between HPW and UiO-66 plays a key role toward the photostability and charge-transfer mechanism of the composite and is well characterized with X-ray diffraction, UV diffuse-reflectance spectroscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy. A total of 30 wt % HPW@UiO-66 shows a maximum degradation of about 87.24% of a 20 ppm TCH solution in 60 min of solar-light irradiation and about 353.89 µmol/h of H2 production. The conduction- and valence-band potentials are well characterized with Mott-Schottky measurement and a delay charge recombination process through electrochemical impedance spectroscopy. The proposed mediator-free Z-scheme-oriented electron-hole migration route is well supported by photoluminescence, and the scavenger test well explains the better charge-carrier separation and high catalytic performance of the prepared composite. This research will bestow an advantageous blueprint to fabricate novel and challenging photocatalysts toward the photocatalytic treatment of environmental pollutants and H2 evolution.

Synergistic ZnFe2O4-carbon allotropes nanocomposite photocatalyst for norfloxacin degradation and Cr (VI) reduction.

Development of highly efficient robust catalyst for pollutant abetment still remains an ongoing scientific challenge in the field of visible light driven photocatalysis. In this work a series of ZnFe2O4 (ZFO)/carbon derivatives (ZFO@CNT, ZFO@GO, ZFO@Fullerene) nanocomposite were fabricated by one-pot hydrothermal method followed by calcination. The detail anatomical featured such as crystal geometry, morphology, elemental composition, light absorption performance, electron-hole recombination properties and photocurrent density were characterized by XRD, SEM, HRTEM, XPS, UV-Vis DRS, PL and electrochemical analysis respectively. The photocatalytic performances of ZFO@carbon nanocomposites were studied for the degradation of antibiotics (Norfloxacin) and hexavalent Chromium under open sun light illumination and the obtained results suggested that loading of carbon derivatives of ZFO nanoparticles enhance the visible light absorption capacity and excitation separation efficiency. Among the fabricated composites, ZFO@CNT exhibits the highest activity in comparison to other nanocomposites. The highest activity of ZFO@CNT is due to low photoexcited electron-hole recombination and high charge transfer properties of ZFO@CNT as confirmed via PL and impedance measurement. Further, the fabricated ZFO@CNT nanocomposite exhibited highest photocurrent density i.e. 2.25 mA/cm2 which was 225 times higher than that of neat ZFO. The optimal photocatalytic efficiency was shown by ZFO@CNT i.e. 91.36% degradation of 50 ppm norfloxacin and 82% reduction of 10 ppm Cr (VI) in 90 min and 60 min respectively under solar light irradiation.

Pyrochlore Ce2Zr2O7 decorated over rGO: a photocatalyst that proves to be efficient towards the reduction of 4-nitrophenol and degradation of ciprofloxacin under visible light.

In the present study, a series of Ce2Zr2O7@rGO nanocomposites were synthesized using a simple solution combustion method followed by a photoreduction technique. The as-prepared samples were well characterised using various analytical techniques to determine the morphological, optical, structural, electrochemical and compositional properties. The presence of oxygen defects was observed from Raman and photoluminescence spectra. The photoreduction of GO to rGO was determined from Raman and Fourier-transform infrared (FTIR) spectroscopy results. The role of rGO proved to be quite significant for the enhanced photocatalytic activity of the nanocomposites. The synergistic communication between Ce2Zr2O7 and rGO accelerates the photoreduction of 4-nitrophenol along with the degradation of ciprofloxacin under visible light irradiation. Of the rGO nanocomposites, 3 wt% GO loaded Ce2Zr2O7 reduces 99% of 20 ppm of 4-nitrophenol to 4-aminophenol in 120 min and decomposes 10 ppm of ciprofloxacin by up to 89% in 60 min. The significant enhancement in the activity of the Ce2Zr2O7@rGO nanocomposite was ascribed to the effective charge separation of excitons through π-conjugation of graphene at the interface, which is well supported by the impedance, photoluminescence and photocatalytic results.