Search Results (396)

This study investigates the simultaneous elimination of ethyl acetate (EA), a representative volatile organic compound (VOC), and Escherichia coli aerosols from indoor air using a continuous-flow dielectric barrier discharge (DBD) plasma reactor coupled with a photocatalytic luminous textile system (Cu/TiO₂-coated fibers). The effects of applied voltage, relative humidity, and air-flow rate on pollutant removal and disinfection performance were systematically evaluated. Optimal DBD operation at 18 kV, 1 m³ h⁻¹ airflow, and 70% relative humidity achieved single-process removal efficiencies of 77% for EA and 2 log reduction (CFU mL⁻¹) for E. coli. When photocatalysis was coupled with DBD plasma, a significant combined effect was observed, increasing EA degradation to 87% and bacterial inactivation to 3.8 log (CFU mL⁻¹). The coupling enhanced active-species generation, improved CO₂ selectivity (up to 53%), and reduced residual ozone concentration. Humidity positively affected microbial inactivation due to °OH radical formation but slightly decreased VOC degradation by limiting ozone regeneration. Results demonstrate the efficiency and scalability of the DBD–photocatalysis hybrid system for multi-pollutant indoor air purification, offering rapid, low-temperature treatment suitable for industrial-scale applications. Full article

This work targets efficient visible-light-driven hydrogen evolution by construction of a dendritic CdS-based photocatalytic system decorated with Pt-Ni bimetallic cocatalysts (CdS@PtNi). The dendritic CdS was synthesized via a hydrothermal method, followed by in situ deposition of Pt and Ni using NaBH₄ chemical reduction, with cocatalyst loading tuned between 2 and 5 wt%. Among them, C@PN4 (4 wt% total metal loading) demonstrated the best performance, with a bandgap of ~2.15 eV. XRD results show that the samples retain the hexagonal CdS phase without significant impurities. SEM/TEM and elemental mapping confirm uniform dispersion of Pt and Ni, forming intimate interfaces with CdS. XPS results reveal positive shifts in S 2p and Cd 3d binding energies, indicating that the bimetallic cocatalyst promotes electron transfer from CdS to the metals and enhances interfacial coupling. Photoelectrochemical analysis shows C@PN4 features enhanced absorption above 500 nm, significantly reduced PL, extended carrier lifetime, higher transient photocurrent, and lower charge-transfer resistance, suggesting greater efficiency in charge separation and transport. Band structure analysis reveals a negative shift of the conduction band to a more reductive potential. In photocatalytic tests, C@PN4 achieves an H₂ yield of 15.6 mmol g⁻¹ over 4 h (3.9 mmol g⁻¹ h⁻¹), with <5% activity loss after four cycles. AQY reaches 0.0483% at 420 nm, with a monochromatic photon-to-hydrogen conversion efficiency (MPH) of up to 2.01%. Mechanistically, the Pt/CdS Schottky junction drives directional electron extraction, while Ni likely synergistically optimizes interfacial electronic distribution and facilitates water activation/dissociation; together, they accelerate surface reaction kinetics and suppress photocorrosion, achieving efficient and stable hydrogen evolution with low noble metal loading. Full article

Elucidating structure–activity relationships in semiconductor photocatalysis has been significantly impeded by the inherent limitations of ensemble-averaged characterization techniques, which obscure the spatiotemporal heterogeneity intrinsic to catalytic surfaces. Single-molecule fluorescence microscopy (SMFM) surmounts this bottleneck by offering nanometer-scale spatial resolution coupled with the capacity to resolve single-turnover events. Herein, we provide a comprehensive overview of the State-of-the-Art applications of fluorogenic probe-coupled SMFM in deciphering the microscopic mechanisms governing photocatalysis. We begin by delineating the operational principles of total internal reflection fluorescence (TIRF) microscopy and categorizing the response mechanisms of three distinct classes of fluorogenic probes: oxidative (e.g., Amplex Red, APF), reductive (e.g., Resazurin, DN-BODIPY), and acidic (e.g., furfuryl alcohol, thiophene) reporters. Subsequently, we highlight seminal studies wherein SMFM has been leveraged to visualize facet-dependent charge separation on model photocatalysts—including TiO₂, BiOBr, and InSe—to map the dynamic activity associated with surface defects and to precisely locate active sites during photoelectrochemical water splitting. Finally, we critically assess the prevailing technical challenges, such as limitations in probe specificity and background interference, while offering a perspective on prospective avenues for methodological refinement. This review is intended to serve as a methodological cornerstone for advancing mechanistic understanding in photocatalysis and for guiding the rational design of high-performance catalysts. Full article

Potassium-modified titanium dioxide (TiO₂–K) was synthesized and evaluated as a heterogeneous photocatalyst for fatty acid methyl ester (FAME) production from palm oil under UV irradiation. The catalyst was characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, and scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS). Potassium modification preserved the TiO₂ crystalline framework while producing marked changes in morphology and a significant decrease in surface area. Photocatalytic transesterification was optimized using a central composite design, evaluating the effects of catalyst loading and the methanol-to-oil molar ratio on FAME yield. The quadratic response surface model adequately described the experimental data and predicted an optimum FAME yield of approximately 98.96% under the evaluated conditions. Kinetic analysis showed that the reaction profile was well described by an apparent pseudo-first-order model, consistent with the use of excess methanol, while the Avrami–Weibull equation provided a flexible empirical representation of the conversion profile. Control experiments confirmed that irradiation and catalyst presence were required for measurable FAME formation. Overall, this study demonstrates the potential of TiO₂–K as a photocatalyst for light-assisted biodiesel production and provides an initial framework for process optimization and kinetic interpretation. Full article

Chlorophenols (CPs), such as 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP), are persistent and toxic organic pollutants commonly found in industrial effluents. This study investigates their photocatalytic degradation using a TiO₂-based heterogeneous catalyst under UV irradiation, in the presence of hydrogen peroxide. The degradation kinetics were analyzed using both pseudo-first order and nonlinear Langmuir–Hinshelwood (L–H) models, accounting for competitive adsorption and successive oxidation of intermediates. Gas chromatography–mass spectrometry (GC–MS) identified key intermediates, including hydroquinone, catechol, chlorocatechols, and benzoquinone. Nonlinear kinetic modeling of coupled differential equations accurately reproduced the temporal profiles of both the parent compounds and their intermediates, providing mechanistic insights into multi-step hydroxylation, dechlorination, and oxidation processes. The results demonstrate that photocatalytic oxidation effectively mineralizes chlorophenols within 500–600 min, and the developed kinetic model offers a predictive tool for optimizing photocatalytic remediation strategies for chlorinated aromatic pollutants. The novelty of this study lies in the development of a nonlinear Langmuir–Hinshelwood kinetic model integrating experimentally identified degradation intermediates, competitive adsorption phenomena, and parallel photocatalytic reaction pathways for both 4-chlorophenol and 2,4-dichlorophenol oxidation systems. Full article

Two-dimensional transition metal carbides and nitrides, known collectively as MXenes, are attractive photocatalyst candidates because their surface chemistry and atomic composition can be tuned over a wide compositional window. A crucial design quantity is the electronic bandgap, which selects whether a given MXene couples with solar radiation and aligns with the redox levels of water splitting. High-fidelity bandgap calculations using the PBE0 hybrid functional are computationally expensive, which has motivated several machine learning surrogates. To the best of our knowledge, this is the first study to integrate a continuous-depth Neural Ordinary Differential Equation backbone with multi-fidelity $\Delta$ learning, distribution-free split-conformal calibration, and uncertainty-aware Pareto screening into a single mathematically grounded pipeline for MXene bandgap prediction. In this work, we develop a physics-constrained neural ordinary differential equation (PC-NODE) that predicts MXene bandgaps from a compact 34-dimensional descriptor set, without relying on the density of states. The model couples a classifier head for the metal/semiconductor decision with a regression head for the gap magnitude, and enforces three physically motivated properties: non-negativity of the predicted gap and monotonicity between the low-fidelity Perdew–Burke–Ernzerhof (PBE) and the high-fidelity PBE0 estimates are obtained exactly through a softplus-parameterised $\Delta$ learning construction, while a hurdle coupling that drives metal predictions towards zero is enforced via a quadratic penalty and verified empirically. In short, two of the three physical constraints are guaranteed by construction, and the third is approximately enforced and verified empirically; the same distinction is maintained consistently in the methodology, the constraint audit and the conclusion. Trained on the 4356-structure MXgap database, a ten-seed ensemble reaches a mean absolute error of $0.186$ eV (per-seed $0.206\pm 0.006$ eV) and a coefficient of determination $R^2=0.880$ on the semiconductor test subset, with a classifier accuracy of $0.856$ and a Receiver Operating Characteristic Area Under the Curve (ROC-AUC) of $0.925$. A split-conformal calibration step then delivers prediction intervals whose empirical coverage matches the 90% target within 0.5 percentage points. Finally, an uncertainty-aware Pareto screening step applies the trained surrogate to a held-out subset of 396 lanthanum-based MXenes and identifies 74 candidates inside the photocatalytic water splitting window [1.23, 3.10] eV. The framework offers a mathematically grounded, data-efficient alternative to feature-heavy pipelines and is reproducible from the open MXgap resource. Full article

A TiO₂/hydrazine system was investigated as a proof-of-concept platform for coupling chemical CO₂ capture with light-driven H₂ evolution under UV irradiation. Hydrazine served as the CO₂ capture agent, leading to the formation of carbamate-type intermediates, while TiO₂ acted as the photoresponsive solid. FT-IR, UV-Vis, and mass spectrometry analyses supported carbamate formation after CO₂ uptake and confirmed H₂ generation during irradiation, reaching a maximum of 33.2 μmol under the conditions evaluated. Deuterated experiments showed no detectable HD or D₂, indicating that H₂ evolution predominantly proceeded via hydrazine dehydrogenation rather than direct water splitting. On the basis of the available spectroscopic evidence, a tentative pathway involving carbamate intermediates and nitrogen-containing oxidation products is proposed. However, key control experiments required to confirm a strictly photocatalytic origin of H₂ evolution were not performed in the present exploratory study. Therefore, the observed behavior is more appropriately interpreted as preliminary photoinduced reactivity in a TiO₂/hydrazine/CO₂ system rather than definitive proof of a fully established photocatalytic mechanism. Overall, the results establish a preliminary proof of concept, while the limitations related to control experiments, product identification, quantification, and reproducibility are recognized. Full article

A comprehensive first-principles investigation of bulk and surface Cu defects in Zn-based chalcogenides (ZnO, ZnS, and ZnSe) is presented, aimed at assessing the effect of Cu doping on the optoelectronic properties of these materials and at addressing the photocatalytic activity towards the hydrogen evolution reaction (HER). Defect formation energies, adiabatic and optical charge-transition levels of the bulk materials are determined, and their dependence on growth conditions and Fermi-level position is analysed. The results indicate that, whereas ZnO supports both donor- and acceptor-like Cu defects with pronounced Jahn-Teller distortions, ZnS and ZnSe predominantly stabilise substitutional Cu as a mid-gap acceptor with weaker electron-lattice coupling and similar absolute transition levels. Calculated vertical transition energies rationalise the characteristic emission of Cu-doped samples in terms of defect-mediated optical cycles. The focus is then placed on surface energetics, which differ markedly from bulk behaviour and critically influence photocatalytic performance. Explicit modelling of HER demonstrates that Cu substitution dramatically reduces the overpotential on ZnS and ZnSe by tuning hydrogen adsorption toward the Sabatier optimum, while in ZnO the beneficial effect of Cu doping is diminished by the excessive strengthening of the adsorbate-surface interactions. Finally, the measured HER activities are rationalised by proposing a defect-mediated mechanism involving electron trapping at the surface Cu site, cooperative proton adsorption, and hydride formation. These findings establish defect thermodynamics and surface charge localisation as key design parameters for optimising materials engineering strategies in photocatalytic applications. Full article

With the rapid development of the edible fungus industry, the environmental pressure and resource waste caused by the massive generation of fungal residue have become increasingly prominent. Meanwhile, heavy metal wastewater pollution and the growing demand for clean energy pose dual challenges to sustainable development. This study focuses on Auricularia cornea var. Li. fungal residue, exploring the establishment of a multi-level resource utilization pathway integrating “porous carbon material preparation—heavy metal adsorption—photocatalytic hydrogen evolution.” Firstly, the Auricularia cornea var. Li. residue-based porous carbon material was examined by combining hydrothermal carbonization, activation and slow pyrolysis. In optimal conditions, the porous carbon obtained yielded a surface area of 675.56 m²/g and formed a composite pore structure consisting of micropores with coexisting micropore and mesopore. Secondly, we performed batch adsorption experiments to study the effects of solution pH, adsorbent dosage and contact time and the adsorption behavior via fitting adsorbing kinetic models. Under optimal conditions, Cd(II) removal efficiency reached 92.36% and an equilibrium adsorption capacity of 92.47 mg/g. We used Cd(II) adsorbed porous carbon as a cadmium source and converted into a CdS photocatalyst using a hydrothermal sulfidation process. The CdS prepared using sodium sulfide as a sulfur source gave an average hydrogen evolution rate of 668.01 μmol·g⁻¹·h⁻¹ and showed higher photocatalytic performance for water splitting to produce hydrogen. Full article

Photocatalytic H₂O₂ production coupled with selective organic oxidation provides a promising strategy for simultaneously generating value-added oxidants and chemicals under mild conditions. Herein, Ni-modified defect-engineered NH₂-UiO-66 photocatalysts (Ni/UN) are constructed by introducing Ni species into a vacuum-treated NH₂-UiO-66 framework (UN). Compared with the original NH₂-UiO-66 and the defect-treated UN, Ni/UN exhibits weakened photoluminescence emission, enhanced transient photocurrent response, and reduced electrochemical impedance, indicating that the separation and transfer of photogenerated charge carriers have been improved. The band structure analysis further reveals that Ni/UN has a narrow band gap of approximately 2.52 electron volts and a slightly more negative conduction band position (−0.50 V), which is conducive to the photoinduced reduction reaction. The importance of O₂ in the photocatalytic process was demonstrated by changing the atmospheric conditions. Therefore, in the benzylalcohol system, under the oxygen atmosphere, Ni/UN achieved the highest H₂O₂ production rate of 3257 μmol g⁻¹ h⁻¹, accompanied by the continuous generation of benzaldehyde, with its content reaching 3420 μmol g⁻¹ after 60 min of irradiation. The scavenger experiment further indicates that photogenerated electrons and the active substances derived from oxygen are closely involved in the formation of H₂O₂, while the ·OH-related processes only play a limited contribution role. This study demonstrates an effective strategy for enhancing the performance of metal–organic framework (MOF)-based photocatalysts through defect engineering and metal coordination regulation, thereby achieving efficient photochemical production of hydrogen peroxide and the selective oxidation of benzyl alcohol. Full article

Three types of graphene–single crystal titanium dioxide composite (GR–TiO₂SCs) were prepared using the hydrothermal method, employing TiF₄ and graphite as raw materials with hydrofluoric acid serving as the morphology-directing agent. The phase composition and morphological features of the resultant composites were systematically characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction. These complementary characterization results clearly demonstrate that graphene and TiO₂ single crystals have been successfully hybridized to form a well-defined heterostructure, rather than a simple physical mixture. Photocatalytic performances were evaluated by monitoring the photodegradation behaviors of methylene blue, rhodamine B, and methyl orange solutions under simulated light irradiation, with real-time concentration variations recorded by UV–visible absorption spectroscopy. The composite sample in which TiO₂SCs were in situ grown and uniformly anchored onto graphene oxide substrates effectively suppressed the self-stacking and agglomeration of individual crystallites, thus delivering the best photocatalytic response. Increased exposure of the active catalytic interfaces of TiO₂SCs was found to play a key role in elevating the overall photocatalytic activity. The hierarchical assembly protocol developed in this work provides a feasible pathway for the rational design of functional composites with controllable microstructures and tailored properties, which can be further extended to the development of advanced sensing materials. Full article

The growing demand for sustainable water treatment technologies requires photocatalysts that combine low environmental impact, energy efficiency, and mechanistic robustness. In this work, $Ag/Zn$ nanocomposites were green-synthesized using Chlorella vulgaris polar extract as a bio-mediated reducing and stabilizing agent, eliminating hazardous reagents and high-energy processing steps. Structural characterization (XRD, FTIR, SEM, UV–Vis) confirmed the coexistence of crystalline wurtzite $ZnO$ with metallic $Ag$ and ${Ag}_{2}O$ phases. Photocatalytic activity was evaluated through Congo Red degradation under a sequential dark–light protocol, enabling clear separation of adsorption and photoactivated pathways. During the $60 \mathrm{m}\mathrm{i}\mathrm{n}$ dark stage, removal remained limited ($~9–11\%$), consistent with adsorption–desorption equilibration. Upon UV irradiation, a distinct kinetic transition occurred, leading to final removal efficiencies of $44–49\%$ after $180 \mathrm{m}\mathrm{i}\mathrm{n}$. Notably, performance remained stable across the investigated photon flux range, indicating operation beyond a strictly photon-limited regime and highlighting an intrinsically energy-resilient catalytic response. A mechanistic kinetic model integrating reversible adsorption with light-dependent degradation accurately reproduced all experimental profiles ($NRMSE=3.14\%$) and successfully predicted an independent dark-control experiment without additional fitting. By coupling green synthesis with quantitative kinetic validation, this study proposes a sustainability-oriented framework for designing photocatalysts that align low-impact fabrication with energy-conscious water remediation. Full article

ZnO–ZnCr₂O₄ heterojunction nanocomposites were synthesized via co-precipitation with nominal spinel loadings of 10, 20, and 30 wt.% (denoted ZnCr-10, ZnCr-20, ZnCr-30) to evaluate structure–property–performance relationships in photocatalytic dye degradation. Rietveld refinement of XRD data revealed actual crystalline phase fractions of 12.1%, 32.4%, and 39.9% ZnCr₂O₄, respectively, with systematic morphological evolution from dispersed nanoparticles (ZnCr-10) to densely agglomerated structures (ZnCr-30) observed by SEM. Optical analysis demonstrated that ZnCr-10 (apparent band gap 3.09 eV) retains ZnO-dominated absorption with moderate interfacial electronic coupling, while ZnCr-20 shows enhanced visible response (2.89 eV) through interface-mediated transitions. ZnCr-30 exhibits strong sub-bandgap absorption (1.63 eV) originating from defect states rather than intrinsic band narrowing. Photoluminescence studies under UV excitation revealed optimal radiative recombination suppression in ZnCr-10, consistent with efficient interfacial charge separation, whereas excessive loading (ZnCr-30) introduced defect-mediated recombination centers. Photocatalytic degradation of Rhodamine B (5 mg/L, 0.5 g/L catalyst, solar irradiation) followed the order: ZnCr-10 (k = 0.0307 min⁻¹) > ZnO (0.0203 min⁻¹) > ZnCr-20 (0.0230 min⁻¹) > ZnCr₂O₄ (0.0166 min⁻¹) > ZnCr-30 (0.0113 min⁻¹). The optimal ZnCr-10 performance is attributed to balanced interfacial contact between phases enabling charge separation without excessive agglomeration or defect accumulation. Operational parameters (pH 7, 50 mg/100 mL, 100 µL H₂O₂) were optimized, achieving 98% degradation in 60 min. This study demonstrates that photocatalytic enhancement in ZnO–spinel heterojunctions is governed by interfacial architecture and defect management rather than optical absorption alone, providing design principles for efficient solar-driven environmental remediation. Full article

The efficient photocatalytic generation of hydrogen peroxide (H₂O₂) from pure water remains a formidable challenge, primarily due to the rapid recombination of photogenerated electron–hole pairs and insufficient redox potentials inherent in single-component photocatalysts. To address these issues, we designed and synthesized a heterojunction material comprising cadmium sulfide nanoparticles loaded on carbon spheres (CS@CdS). Under conditions utilizing pure water and ambient air, the CS@CdS composite achieves an H₂O₂ production rate of 1305 μmol·g⁻¹·h⁻¹, which is 3.1 and 3.6 times higher than that of pure CdS and CS, respectively, without the need for any sacrificial agents or external oxygen supply. Systematic characterization reveals that CS and CdS form a tightly coupled electronic interface, which significantly accelerates charge carrier separation and effectively prolongs the lifetime of photogenerated carriers, thereby boosting photocatalytic performance. Furthermore, the CS component extends the visible-light absorption range of the composite and functions as an electron acceptor to suppress charge recombination, collectively endowing CS@CdS with enhanced photocatalytic activity. Mechanistic studies indicate that H₂O₂ production over CS@CdS proceeds predominantly via a two-step single-electron oxygen reduction reaction (ORR) pathway. This work offers a viable strategy for constructing CS-based heterojunction photocatalysts for efficient H₂O₂ synthesis. Full article

Antibiotic contamination of water, particularly tetracycline (TC), poses significant environmental risks and requires sustainable treatment solutions. This study reports a green and cost-effective synthesis of a ZnO/chitosan nanocomposite (ZnO/CS) for photocatalytic TC removal. ZnO nanoparticles were synthesized using lime juice as a natural stabilizing agent and subsequently incorporated into a chitosan matrix. The physicochemical properties of the composite were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) surface area analysis. The results confirmed the successful formation of hexagonal wurtzite ZnO and strong interfacial interactions between ZnO nanoparticles and the –NH₂/–OH functional groups of chitosan. The incorporation of chitosan significantly increased the specific surface area from 10.7 to 21.7 m² g⁻¹ and reduced the band gap from 3.18 to 3.03 eV, thereby improving visible-light absorption. The photocatalytic performance was evaluated under varying pH, initial TC concentration, and catalyst dosage, with optimal conditions identified at pH 6, 20 mg/L TC, and 1 g/L catalyst. Under these conditions, the ZnO/CS nanocomposite achieved 94.1% TC degradation within 120 min under visible-light irradiation. Scavenger experiments revealed that •OH and •O₂⁻ radicals are the dominant reactive species, and a possible degradation mechanism was proposed. These findings demonstrate the potential of the green-synthesized ZnO/CS nanocomposite for antibiotic removal from aqueous environments. Full article