Using renewable biomass to synthesize valuable chemicals can reduce fossil fuel dependence and achieve carbon neutrality. Here, for the first time an infrared light-driven catalyst, Cu/Fe2O3, was designed to convert bioethanol to valuable acetaldehyde, accompanied by green hydrogen as a by-product, under both indoor IR light and natural sunlight. It achieves an initial acetaldehyde yield of 237 mmol g-1 h-1 under indoor IR irradiation and 205 mmol g-1 h-1 under real sunlight, with exceptional selectivity (97.7%) and nearly stoichiometric H2 byproduct production. Notably, the turnover number and initial turnover frequency surpass those of IR-driven systems by at least one order of magnitude and perform competitively with leading energy-intensive UV-vis-driven and thermocatalytic ethanol conversion processes operated up to 573 K. This high performance is attributed to: i) the construction of an efficient IR photons-to-phonons energy conversion channel within the ps timescale to drive localized thermocatalysis; and ii) the synergistic effect on the in situ formed of Cu/Fe2O3 interface, where Fe3+ sites promote dissociative ethanol adsorption, and Cu0 sites facilitates C─H bond cleavage.
Postharvest deterioration caused by ethylene (C2H4) is a major challenge for global food security, leading to significant losses of perishable products like bananas. In this study, we present the synthesis and optimization of a multicomponent photocatalyst based on montmorillonite (MMT), titanium dioxide (TiO2), and silver (Ag), designed for efficient ethylene remediation. The catalysts were prepared via wet impregnation and characterized using FE-SEM, EDS, and UV-vis reflectance spectroscopy, which confirmed the successful integration of components and a homogeneous elemental distribution. The bandgap energies were determined to be in the range of 3.02 to 4.10 eV, with MMT-rich samples showing values around 3.12 eV. Through a 23 factorial design, the performance was evaluated under three distinct scenarios: adsorption, artificial UV photocatalysis, and natural sunlight-driven photocatalysis. Sample Amt 09 (1.5% TiO2 and 1% Ag) achieved an ethylene removal of over 92% in the artificial UV photocatalysis scenario. Sample Amt 10 (5% MMT, 1.5% TiO2, and 1% Ag) stood out with high performance across all scenarios, suggesting synergistic effects between adsorption and catalytic degradation. Furthermore, an optimized formulation (5% MMT and 2.73% TiO2) achieved 65% ethylene removal under UV light and 47% under natural sunlight. These findings highlight the potential of MMT/TiO2/Ag composites as sustainable, light-driven solutions for postharvest management, offering a scalable platform to extend the shelf life of fresh produce and reduce global food waste.
暂无摘要（点击查看详情）
暂无摘要（点击查看详情）
In this work, a series of complexes with the general formula [RE2(nal)6(H2O)3]·9H2O (RE3+: Eu, Gd, and Tb) was successfully synthesized. The crystal structure of the Tb3+ compound was determined by single-crystal X-ray diffraction, revealing a bimetallic arrangement with distinct coordination environments. Photophysical properties indicate that the Tb3+ complex shows efficient sensitization through the S1 level of the nal ligand. The presence of an LMCT band in the Eu3+ complex does not result in significant luminescence quenching. This can be attributed to hydrogen-bonding interactions within its structure and to the nal ligand's high capacity as an indirect luminescence sensitizer. As a result, the Eu3+ complex exhibits a relatively high intrinsic quantum yield value (∼24%) for a highly hydrated system. The PMMA:(1%)-Eu3+ film shows a higher yield of highly luminescent films (54%) than the complex. In addition, the PMMA doped with Eu3+ and Tb3+ ions exhibits red and green emission under solar exposure. To the best of our knowledge, this behavior has not yet been reported in the scientific literature, considering the same ligand. These findings highlight the potential of these photonic materials as candidates for luminescent solar concentrator (LSC) devices.
Continuous electron donor-acceptor covalent organic frameworks (D-A COFs) could serve as ideal platforms to investigate the correlation between the structures of organic polymers and their photocatalytic efficiency. In this report, we present a study on the correlation of the structures of D-A COFs with their catalytic efficiency. The two D-A COFs, COF-1 and COF-2, which structurally incorporate triazine and thiophene units linked by a vinylene bridge, were synthesized via a three-component Knoevenagel condensation reaction. The benzotrithiophene-based COF-1 exhibited superior optical and photoelectrical properties compared with the 1,3,5-tri-(thiophen-2-yl)-benzene-based COF-2. COF-1 and COF-2 demonstrated impressive photocatalytic hydrogen evolution reaction (HER) rates of approximately 69.1 and 56.6 mmol/g/h, respectively. The superior photocatalytic performance of COF-1 compared with that of COF-2 can be attributed to the distinct structural features of the benzotrithiophene and 1,3,5-tri-(thiophen-2-yl)-benzene units within the frameworks.
The electricity-free conversion of polymer waste into high-value functional materials represents an important step toward sustainable and circular manufacturing. Herein, we demonstrate a light-driven upcycling platform that directly transforms vulcanized waste tires into electrocatalyst supports for proton exchange membrane fuel cells (PEMFCs). In this process, waste tires form uniform composites with effective light absorbers such as MoS2 nanosheets, enabling near-infrared (NIR) light or natural sunlight to be converted into localized high-temperature thermal fields. By investigating the fundamental correlation between composite design, microstructure, and carbonization efficiency, we show that waste tires are turned into effective Pt catalyst supports via NIR- and sunlight-driven carbonization. The resulting PEMFCs deliver a maximum power density of 982 mW cm-2 (NIR) and 1048 mW cm-2 (natural sunlight), respectively, under H2/O2 operation, which are comparable to that of a benchmark Pt/C device (1024 mW cm-2). These results demonstrate that the light-driven carbonization enables the production of carbon supports with sufficient conductivity, Pt accessibility, and catalyst-layer compatibility for fuel-cell operation. Additionally, sunlight-based photothermal carbonization is accomplished in less than 1 min under ambient conditions, highlighting its potential as an alternative to conventional, energy-intensive, and time-consuming furnace-based carbonization. Ultimately, this light-driven upcycling strategy offers an efficient, self-sustained route for converting polymer waste into functional electrochemical materials.
Sustainable production of H2O2 coupled with pollutant removal is highly desirable for water treatment but remains challenged by inefficient oxygen supply and interfacial reaction limitations in conventional slurry systems. Here, a self-floating RP/wood membrane is developed to regulate interfacial transport and enable photocatalytic H2O2 production at the air-water interface. Resorcinol-formaldehyde@polypyrrole (RF@PPy, denoted as RP) were immobilized onto a wood scaffold through PVDF-assisted assembly, forming an RP/wood membrane with hierarchical porosity and asymmetric wettability. The aligned capillary channels of the wood substrate provide continuous water transport, while the catalytic layer remains exposed to air, establishing a stable gas-liquid-solid triphase interface that facilitates oxygen supply and photon utilization. As a result, the system exhibits environmental adaptability, with optimal H2O2 production under mildly acidic conditions (pH 5.81) and a high generation rate of 657.10 μM·h-1. After 14 days of immersion, the rate remains at 575.2 μM·h-1, indicating good structural stability. Notably, continuous H2O2 accumulation is achieved under natural sunlight irradiation, demonstrating its applicability under real outdoor conditions. The generated H2O2 can be directly utilized for pollutant degradation, achieving rapid pollutants removal under visible light and natural sunlight. The membrane maintains high reusability, with negligible catalyst loss after several cycles due to effective immobilization. This work provides a scalable and energy-efficient strategy for integrating solar energy utilization, green oxidant generation, and water purification, highlighting the potential of biomass-derived materials for sustainable environmental remediation.
Silver (Ag)-decorated Bi2WO6 (BW) nanoflakes were developed as a visible-light-responsive plasmonic semiconductor photocatalyst for enhanced hydrogen evolution and efficient photocatalytic degradation of Congo red under natural sunlight irradiation. The Ag-Bi2WO6 (ABW) nanocomposites were characterized by UV-visible spectroscopy, XRD, XPS, TRPL analysis, BET analysis, Raman spectroscopy, FESEM and HRTEM. XRD showed the formation of the orthorhombic crystal phase of Bi2WO6 and the face-centered cubic structure of Ag. UV-visible spectroscopy showed the extended absorption of ABW composites in the visible range, whereas BW showed an absorption peak at 320 nm. Raman analysis confirmed the successful decoration of Ag onto BW, altering its vibrational mode and structural bonding. FESEM confirmed the nanoflake morphology with a densely packed and self-assembled plate/disc structure of BW and spherical Ag nanoparticles (diameter ∼6 nm) well-deposited on it. The high-resolution TEM results showed lattice fringes with interplanar spacings of ∼0.22 nm and 0.27 nm, corresponding to the (111) and (113) planes of Ag and BW, respectively. The ABW nanocomposite showed excellent photocatalytic activity, with 94% CR dye (25 ppm) degradation within 6 minutes under natural sunlight, along with a pseudo-first-order rate constant of 0.43 min-1. The obtained cumulative hydrogen production rate using BW and the ABW nanocomposites is 8231 µmol g-1 and 13 054 µmol g-1, respectively, within 4 hours under a mercury vapor lamp (400 W).
Most discarded packaging in the environment originates from petroleum-derived plastics, which are environmental pollutants. Many proposals for new packaging employ biodegradable materials; however, these materials often require additives to impart specific properties to the final products. Therefore, research related to degradation processes is necessary to ensure their environmental safety of them. The aim of this study was to investigate the degradation of pure poly-(butylene adipate-co-terephthalate) (PBAT) films and films added with 5% (w/w) Rosemary essential oil (REO) (Rosmarinus officinalis L.) under two different natural atmospheric conditions in a semiarid climate from northeastern Brazil. To this end, 66 rectangular samples with an area of 6.8 cm2 were exposed for 120 days under two conditions: condition (I) sunlight, wind, dust, humidity, and the presence of rain and condition (II) sunlight, wind, dust, humidity, and absence of rain. The samples were evaluated in terms of mass, thickness, solubility, opacity, visual appearance, and spectroscopic profile in the mid-infrared region using the carbonyl index (CI) and hydroxyl index (HI). An increase in solubility proportional to the water exposure time was also observed for both films, corroborating the visual analysis, which revealed the formation of fissures throughout the entire set of samples and a higher opacity in the oil-added films, especially under condition I. In addition, films exposed to condition I exhibited a greater mass loss than those under condition II. Differences in degradation between pure and REO-added films also became more evident, with a greater reduction in CI observed for the added samples under both conditions, indicating chemical degradation due to ester bond cleavage in PBAT. Principal component analysis indicated that up to 45 days, the samples exhibited high spectral similarity; however, thereafter, increasing discrimination between samples from the two experimental conditions was observed. This indicates that although the samples showed a similar degradation pattern over time, those exposed to condition I (with rain) were more strongly affected by climatic conditions and exhibited stronger evidence of chemical degradation.
Halauxifen-methyl is a new pre-emergent herbicide used to control weeds in corn and soybean crops. Although its use and commercialization have recently been authorized in Brazil, studies involving the development of extraction methods for this herbicide are still rare. Therefore, the present study aimed to optimize and validate liquid-liquid extraction with low-temperature partitioning (LLE-LTP) to determine halauxifen-methyl in water using high-performance liquid chromatography with diode array detection (HPLC-DAD). The optimal chromatographic conditions were acetonitrile and water (80 : 20 v/v) as the mobile phase, Kinetex column, flow of 0.2 mL min-1, injection volume of 10 µL and 250 nm as wavelength. The best extraction conditions were 4 mL of sample, acetonitrile and dichloromethane (7.5 : 0.5 v/v) as the extracting phase, with the addition of 0.2 g of NaCl salt and 90 min for freezing. The method validation showed that LLE-LTP was selective, precise, accurate, with a quantification limit of 0.448 µg L-1, linearity range of 0.448 to 120 µg L-1 and matrix effect of -11.19%. The study also revealed that the half-life of this herbicide in water is 6 days under sunlight and close to 50 days in the absence of sunlight. LLE-LTP proved to be efficient for monitoring halauxifen-methyl in water. The Analytical Eco-Scale metric assessment revealed it reached 84 points, meaning this method is classified as an excellent green analysis technique.
Background and Objectives: Rheumatoid arthritis (RA) is a chronic systemic autoimmune disease in which persistent synovial inflammation and joint damage are influenced not only by immune dysregulation but also by environmental, genetic, and epigenetic factors. Vitamin D is a secosteroid hormone and has emerged as a key immunomodulatory hormone, with reported effects on innate and adaptive immune responses, with potential relevance to RA clinical activity and treatment. This narrative review synthesizes mechanistic and clinical evidence enlightening vitamin D's immunomodulatory role in RA pathogenesis and management. Methods: A comprehensive literature search was carried out on PubMed and MEDLINE databases using Medical Subject Headings (MeSH) terms: "Vitamin D", "Cholecalciferol", "Arthritis, Rheumatoid", "Seasons", "Epigenomics", "DNA Methylation", and "Therapy". The narrative review highlights evidence published mainly in the last 5 years on the link between vitamin D and RA, focusing on epigenetic interactions, circannual rhythms, and therapeutic implications. Results: Emerging data suggest that vitamin D-related epigenetic mechanisms (e.g., DNA methylation, histone acetylation, and microRNA regulation) and genetic polymorphisms have been associated with disease susceptibility and treatment outcomes. Latitude and seasonal fluctuations in serum 25-hydroxyvitamin D levels correlate with variations in RA disease activity, although results remain heterogeneous across studies. Overall, the available evidence supports an association between vitamin D deficiency and greater RA disease activity, while its adequate supplementation has been associated with improvements in inflammatory markers and selected clinical outcomes, especially when tailored to baseline status and individual risk factors, such as limited dietary intake and sunlight exposure. Conclusions: Current evidence emphasizes the need for further studies using standardized methods and larger, geographically diverse cohorts to define how best to leverage seasonal vitamin D variations in RA management, considering also the range of concomitant epigenetic modifiers that may influence the effects of vitamin D on the management of RA patients.
The planar-to-Dewar valence isomerisation of 4a,8a-azaboranaphthalene (BNNaph), a π-extended BN-doped analogue of azaborine, is investigated to evaluate how BN incorporation reshapes the minimum-energy pathway on the ground state. This process is, for example, relevant in the context of molecular solar thermal (MOST) energy storage, where absorbed sunlight is converted into chemical energy through reversible photoisomerisation. Structures and vertical excitations were computed using DFT and TD-DFT, minimum-energy pathways were mapped with nudged elastic band (NEB) calculations and pathway energetics were refined with state-averaged XMS-CASPT2. In addition, azaborine was examined as a comparison system, with particular emphasis on whether substituents at nitrogen and boron promote Dewar formation. Compared with the carbon analogue, the conversion pathway becomes asymmetric with a metastable intermediate stabilised by a transient boron-carbon contact. The transition structure closely resembles an S0/S1 conical intersection, which is consistent with a vibrationally activated nonradiative funnel. For tuning MOST properties, screening of single substituents across the whole molecule reveals predominantly red-shifted S1 energies together with increased oscillator strengths and indicates that appropriate substitution can improve Dewar formation in azaborine derivatives.
As a highly toxic chemical warfare agent and hazardous industrial byproduct, phosgene poses severe threats to public health and ecological safety, necessitating rapid, sensitive and portable detection strategies. Herein, a novel quinoline-based fluorescent probe (NPK) via an intramolecular charge transfer (ICT) mechanism is rationally designed. Upon specific recognition of phosgene through an intramolecular cyclization reaction, the emission wavelength of probe NPK significantly shifts into the near-infrared I region within 20 s, and the fluorescence color of the solution changes from green to red. Integrated with smartphone-based RGB colorimetric analysis, the NPK probe enables real-time, quantitative monitoring of phosgene in both liquid and vapor phases, with high sensitivity and selectivity (3.27 nM-liquid/0.082 ppm-vapor for phosgene). The practical utility is further validated by tracking in-situ phosgene generation from chlorinated organic solvents under sunlight‑oxygen coupled conditions. Notably, leveraging its superior solid-state fluorescence, NPK serves as an efficient and non-destructive fluorescent developer for high-fidelity, high-contrast latent fingerprint visualization. This work presents a multifunctional ICT-type fluorescent probe that provides a reliable and versatile platform for hazardous gas trace detection and forensic fingerprint imaging, offering new guidance for the design of high-performance multifunctional sensing materials.
The retina is both metabolically active and exposed to light, resulting in persistent heat generation. However, the quantitative contributions of metabolic and irradiative heat sources, and the mechanisms responsible for dissipating this thermal load, remain incompletely characterized. Here we develop a steady-state quantitative thermal balance model of the retina that integrates heat production from metabolic activity and light absorption with multiple heat dissipation pathways into a unified energy balance framework. Metabolic heat was estimated from reported ATP consumption rates under dark- and light-adapted conditions, while irradiative heat input was quantified based on environmental luminance, pupil size, and ocular optics. These inputs were incorporated into a lumped energy balance in the form of Q_"in" =Q_"out" , allowing calculation of the retinal temperature elevation relative to blood, ∆T. Heat dissipation pathways, including conduction to surrounding tissue, choroidal blood perfusion, convection, and radiation, were expressed as thermal conductances, G, and analysed within the same framework,∆T=Q_out/G. Under sunlight, total retinal heat input reached approximately 10 mW, approximately threefold higher than at night. Despite this, the predicted steady-state retinal temperature elevation remained very small (~ 10-3 K), suggesting that heat is dissipated highly efficiently. The analysis shows that conduction and choroidal blood perfusion dominate retinal heat removal under physiological conditions, whereas radiation and convection contribute negligibly. The results suggest that retinal heat redistribution via conduction plays a major role in retinal thermal homeostasis, whereas choroidal blood perfusion primarily contributes to subsequent systemic heat removal rather than acting as a dominant limiting mechanism itself. This analysis provides quantitative support for the long-standing hypothesis that the choroid functions as a heat sink for the retina.
The repurposing of waste industrial materials for use in environmental remediation is of great interest in terms of the circular economy as well as public health and safety efforts. Herein, an innovative approach is presented to synthesize a cobalt-functionalized waste silica (Co-MS) utilizing a green, solvent-deficient method (SDM), using industrial waste micron-sized silica (MS) as a sustainable support material. The resulting Co-MS composite is evaluated as a photocatalyst for the removal of methylene blue (MB) under natural sunlight, offering an energy-efficient and environmentally friendly treatment method. Comprehensive characterization confirmed the formation of multiple-valence-state cobalt nanoparticlesCo, CoO, and Co3O4 on the waste silica support. The resulting optimal composite includes 9.1 wt % cobalt oxide species and shows a polyoxide nature with finely dispersed cobalt oxide nanoparticles that are less aggregated compared to bulk Co3O4 and show an improved photocatalytic performance under solar light. Incorporation of cobalt oxide species into MS also results in an S BET increase from 43 m2 g-1 for bulk Co3O4 to 91 m2 g-1 for the Co-MS composite. The selected composite Co-MS thus achieves 87.5% MB removal efficiency within 1 h, demonstrating its potential as a low-cost, sustainable photocatalyst for wastewater treatment applications.
Photoelectrochemical (PEC) oxidation of cyclohexanone (CYC) to adipic acid offers a new sustainable synthesis approach, while efficient and selective transformation continues to pose a significant challenge. Moreover, traditional PEC systems typically require both sunlight and an external bias to ensure efficient and stable chemicals production, resulting in low energy utilization efficiency and 1-fold application scenarios. Herein, we construct a high-performance photoanode for PEC synthesis of adipic acid from CYC by modifying TiO2 nanorods array with NiFeCu (oxy)hydroxides (NiFeCu(OH)2/TiO2), achieving 5.6 μmol cm-2 h-1 adipic acid production with 95.7% selectivity at 1.0 V vs. reversible hydrogen electrode (RHE), outperforming the selectivity of the reported works for PEC CYC oxidation to adipic acid at low applied potentials. We demonstrate that the Cu modification in NiFe(OH)2/TiO2 promotes the generation of adsorbed hydroxyl radicals (OH*) to form reactive Ni/Fe2+ δ -OH* species, facilitating the activation of C α -H bonds in CYC and the subsequent C-C cleavage to obtain adipic acid. It is notable that we achieved PEC CYC oxidation with redox flow batteries (denoted as PEC open-loop flow battery), in which value-added adipic acid is produced and electricity is discharged spontaneously (at a voltage of ∼1.3 V with a capacity of 1.1 Ah L‒1). This work underscores the potential for sustainable light-driven adipic acid synthesis and solar energy storage.
N-isopropyl-N'-phenyl-1,4-phenylenediamine (IPPD) is a critical rubber antioxidant and a promising alternative to N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD). Its photochemical fate at soil-mineral interfaces remains insufficiently elucidated, particularly regarding the mineral-dependent transformation behaviors. In this study, the phototransformation of IPPD on the surfaces of silica (SiO2) and montmorillonite (MMT) was systematically investigated under simulated sunlight irradiation. IPPD underwent rapid degradation following pseudo-first-order kinetics, with significantly different transformation rates and pathways observed between SiO2 and MMT systems. The degradation process was notably regulated by surface pH, moisture content, natural organic matter, and coexisting ions. Mechanistic investigations via quenching experiments and electron paramagnetic resonance (EPR) spectroscopy demonstrated that direct photolysis was the dominant pathway in the SiO2 system, whereas reactive oxygen species (1O2 and •OH) governed the photodegradation process in the MMT system. Multiple transformation products (TPs) were generated in both systems, with IPPD quinone (IPPD-Q) identified as a common intermediate. Notably, Vibrio fischeri bioluminescence assays revealed a distinct "toxicity peak" during the photolysis process, and computational toxicology further suggested that specific TPs exhibited enhanced acute toxicity, carcinogenicity, and endocrine-disrupting potential compared to the parent compound IPPD. These findings clarify the critical role of mineral types in governing the interfacial photochemical behavior, environmental persistence, and hazard of IPPD, and provide compelling support for the inclusion of matrix-specific transformation products in the environmental risk assessments of rubber additives.
Titanium dioxide is used as a white pigment in cosmetics and other products, but it possesses photocatalytic activity and has become problematic for decomposing sebum when exposed to sunlight. Consequently, titanium phosphate has been investigated as a new white pigment, with expectations for its biocompatibility. However, this pigment had the drawback of having particles that were too large. Therefore, in this study, as a new process for cosmetic pigments, we prepared samples where titanium hydroxide and titanium phosphate were coprecipitated, and we attempted to create a mixed material of titanium oxide and titanium phosphate by heating. This method aimed to suppress photocatalytic activity and produce a novel pigment with particle sizes suitable for cosmetics. With this method, thorough rinsing with water is necessary to remove the sodium sulfate. Even in samples with a low phosphorus ratio of Ti/P = 10/1, photocatalytic activity was sufficiently suppressed. Under this Ti/P = 10/1 condition, the drawback of excessively large particle sizes typically found in phosphate pigments is not particularly noticeable. This study is expected to contribute to the development of new white pigments for use in cosmetics.
This study reports the synthesis of ZnO nanoparticles via a simple co-precipitation method and their evaluation for solar-driven photocatalytic degradation of organic dyes. XRD analysis confirmed the formation of a hexagonal wurtzite phase with good crystallinity, while Raman spectroscopy further supported the structural integrity of ZnO. Transmission electron microscopy (TEM) revealed the morphology and particle-size distribution of the synthesized nanoparticles, and selected-area electron diffraction (SAED) indicated their polycrystalline nature. The photocatalytic performance of ZnO nanoparticles was investigated under natural sunlight using three model dyes: Methylene Blue (MB), Rhodamine B (RhB), and Crystal Violet (CV). UV-Visible spectroscopy showed a progressive decrease in dye concentration, following pseudo-first-order kinetics. The degradation efficiencies reached approximately 98% for MB, 93% for RhB, and 96% for CV within 160 min. XPS analysis suggests the presence of oxygen vacancy-related defect states, which may contribute to enhanced photocatalytic activity by influencing charge carrier dynamics. Overall, the study demonstrates the effectiveness of ZnO nanoparticles for solar-driven dye degradation under natural conditions. However, further investigations, including detailed optical characterization and stability studies, are required to fully assess their practical applicability in wastewater treatment.