Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 mu mol g(-1) h(-1), making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Light-energy-driven semiconductor catalysis offers attractive ways to address environmental and energy crises. TiO2 is the most promising catalyst for photocatalysis, but the lack of charge-carrier separation efficiency severely limits its catalytic performance. In this study, we carried out crystal phase engineering to prepare in situ Z-scheme hetero-phase homojunction of anatase-rutile and clarified the structure-performance relationship. The efficiency of sulfamerazine removal by hetero-phase homojunction TiO2 nanotube arrays in a single-compartment photocatalytic fuel cell system was improved by 1.93 times compared to conventional anatase TiO2 nanotube arrays and the degradation pathways were revealed by the Fukui function combined with HP-LCMS. The successful construction of Z-scheme hetero-phase homojunction was confirmed by Raman, X-ray diffraction (XRD), and electron spin resonance (ESR), which combined with density functional theory (DFT) calculations revealed the key role of crystal phase engineering in the construction of hetero-phase homojunction. This work provides a novel strategy for the scientific design of titanium dioxide photocatalysts.

Nitrogen adsorption and activation have been recognized as the major bottleneck that limits the performance of photocatalytic nitrogen fixation. Herein, SnO2-loaded Fe-doped Bi2Sn2O7 nanocomposites are prepared via a one-step hydrothermal method and exhibit significantly enhanced photocatalytic activity towards N2 fixation to NH3, with an NH3 production rate as high as 346.83 mu mol g- 1 h-1, over six times that of pristine Bi2Sn2O7 (55.59 mu mol g- 1 h-1). Experimental studies and first-principles calculations indicate that Fe doping modulates the electronic structure of Bi2Sn2O7, where the d-pi* feedback at the Fe sites facilitates the dissociation of N---N bonds on Bi2Sn2O7 under weak nitrogen bonding conditions. Meanwhile, the heterojunction with the SnO2 phase modulates the electronic state of the Fe active sites, enhancing the orbital interactions between the Fe sites and nitrogen molecules, thereby making the composites more conducive to N2 adsorption/activation. This significantly reduces the energy barrier of the key nitrogen reduction step and boosts the kinetics of the subsequent hydrogenation reaction. Results from this work highlight the synergistic contributions of doping-regulated adsorption-activation and phase-enhanced Fe-N orbital interactions to the adsorption/activation of nitrogen for enhanced photocatalytic nitrogen fixation.

Metallic bismuth exhibits unique localized surface plasmon resonance (LSPR) and persistent catalytic activity, due to effective absorption in the UV-visible region that can trigger LSPR and promote the separation of photogenerated charge carriers, leading to efficient photocatalysis. In this study, Bi/Bi2Ce2O7 (Bi/BCO) heterojunctions are in situ constructed via hydrothermal treatment of cerium(III) chloride and bismuth(III) chloride in the presence of a calculated amount of mannitol. Among the series, Bi/BCO-2, prepared with a 4 mmol feed of mannitol, exhibits the greatest photocurrent under visible light irradiation, which is 18 times that of Bi2Ce2O7 (BCO) prepared in the absence of mannitol. In photocatalytic nitrogen fixation, the Bi/BCO-2 sample achieves the highest ammonium generation rate of 248.4 μmol g-1 h-1, 49 times greater than that of BCO. This is accounted for by the in situ formation of metallic Bi on BCO, where the LSPR effect, in synergy with oxygen vacancies in BCO, facilitates the adsorption and activation of nitrogen and intermediates and reduces the energy barriers of key steps in the catalytic reduction of nitrogen to ammonia.

Excessive use of chemicals poses a significant threat to the ecological environment and is a global concern. Therefore, development of effective technologies for their removal is crucial for environmental remediation. Herein, a facile one-step solvothermal method is described for the synthesis of defect-rich NH2-MIL-88B (DNMB) metal-organic frameworks by the addition of potassium sodium tartrate. Under visible light irradiation, the DNMB samples exhibit a much-enhanced activity towards the degradation of a wide range of pollutants, including antibiotics like tetracycline, sulfamethoxazole, and levofloxacin, and conventional organic pollutants like bisphenol A and rhodamine B, in comparison to the pristine counterpart. This is attributed to the formation of unsaturated Fe2+ sites in DNMB that facilitate the adsorption of oxygen, the Fe3+/Fe2+ redox cycle and on-site production of H2O2. The resulting self-Fenton system leads to enhanced performance in the effective degradation of the pollutants. The degradation mechanism was elucidated through a combination of theoretical calculations and experiments. The results of the experiments show that the self-Fenton system has broad-spectrum degradation capabilities for pollutants.

With the increasing energy crisis and environmental pollution problems, the development of solar-powered photocatalytic technologies for green and efficient removal of emerging pollutants from aquatic ecosystems has become an urgent need. Bismuth niobate (Bi3NbO7), as a bismuth-based photocatalyst, has attracted much attention due to its unique electronic structure and optical properties. However, Bi3NbO7 synthesized by the traditional hydrothermal method suffers from the problems of large size, limited active sites, and harsh preparation conditions, which severely limit its photocatalytic performance. In this study, small-sized Bi3NbO7 nanoparticles (BNO-Ov-3) enriched with oxygen vacancies were successfully synthesized by a one-step solvothermal method using ethylene glycol as the solvent and structure-directing agent. Glycol not only inhibited the grain growth and reduced the size from micrometers to nanometers, but also promoted the formation of oxygen vacancies through its reducing property. Compared with Bi3NbO7 synthesized by the conventional hydrothermal method, BNO-Ov-3 enhanced the degradation rate of tetracycline hydrochloride (TC) from 49.8% to 92.1% under visible light irradiation. The mechanism of the performance enhancement was revealed by XPS, EPR, and PL characterization: the synergistic effect of nanosize and oxygen vacancies effectively inhibited the photogenerated carrier complexation and promoted charge separation and transfer. This study provides a strategy for the controlled synthesis of bismuth niobate and lays a theoretical foundation for its application in photocatalysis.

Photocatalysis has been recognized as a viable technology for pollutant degradation in wastewater, owing to its ability to generate reactive radicals under photoirradiation. Among these, sulfate radicals (SO4·-) have been attracting significant attention due to their strong oxidizing properties; yet the specific mechanism of action has remained elusive thus far. In this study, defective NH2-MIL-88B (DNMB) is prepared via a facile hydrothermal procedure in the presence of potassium sodium tartrate and found to facilitate the production of sulfate radicals from sulfate anions under visible light irradiation, due to partial reduction of Fe3+ to Fe2+ in the NMB skeleton by the added tartrate that enriches the Fe3+/Fe2+ redox couples, in addition to other reactive species like superoxide radicals and hydroxy radicals. This effectively improves the degradation efficiency toward a variety of organic pollutants, including antibiotics such as tetracycline (TC), sulfamethoxazole (SMX), and levofloxacin (LEV), as well as common organic contaminants like bisphenol A (BPA) and rhodamine B (RhB), as compared to pristine NMB. Specifically, after 40 minutes of visible light irradiation, the degradation rate increases from 61.5% to 92.1% for TC, from 76.1% to 89.4% for SMX, from 60.5% to 75.2% for LEV, from 61.7% to 91.2% for BPA, and from 78.4% to 94.8% for RhB. The primary active species are identified to be sulfate radicals, with minor contributions from holes, superoxide radicals, and hydroxyl radicals, as demonstrated in quenching experiments and electron spin resonance measurements, and further confirmed by theoretical studies. Degradation pathways for the various pollutants are then proposed based on results from Fukui index calculations and liquid chromatography-mass spectrometry analysis. These results underscore the crucial role of structural engineering in driving the advancement of green and sustainable technologies for environmental engineering.

Addressing the stability-activity imbalance of natural enzyme-nanozyme self-cascade catalysis for tumor-specific therapy while inhibiting tumor metastasis via multiple killing mechanisms remains a challenge. Herein, we constructed a tumor microenvironment (TME)-responsive mannose-modified MoS2-tannic acid (TA)-Fe-glucose oxidase (GOx) nanoreactor (MTFGM) via a spatial confinement strategy relying on metal-polyphenol coordination and electrostatic interactions for addressing this issue. GOx was confined on MoS2 via hydrogen bonds and π-π stacking. TA's polyphenol network and mannose's shielding effect enhanced GOx stability by preventing off-target catalysis, while TA-Fe on MoS2 boosted peroxidase (POD)-like catalytic activity by facilitating Fe3+/Fe2+ electron transfer for cocatalysis. In the TME, GOx depleted glucose to self-supply H2O2 and gluconic acid, which activated the POD-like activity of MTFGM to decompose H2O2 into toxic hydroxyl radicals (•OH) with a maximum reaction rate 4-fold higher and turnover number 170-fold higher than pristine MoS2. Simultaneously, MoS2-TA-Fe's glutathione peroxidase-like activity plus H2Sn production continuously consumed glutathione (GSH) to break tumor antioxidant defense. This cascade synergistically induced four tumor-killing mechanisms: GOx-mediated metabolic starvation, •OH-triggered apoptosis, GSH depletion-driven ferroptosis, and cystine accumulation/H2Sn-induced disulfidptosis collectively disrupt tumor redox homeostasis and inhibit metastasis. Our work clarifies the structure-activity relationship of confinement-based cascade nanoreactors and provides a TME-responsive multiple cell death paradigm for tumor-specific therapy.

In this study, a nanocomposite with CeO2 loaded on L-tryptophan functionalized graphitic carbon nitride (CeO2/L-g-C3N4) was developed by a facile two-step method. Firstly, L-tryptophan functionalized graphitic carbon nitride (L-g-C3N4) was achieved via it-it stacking interactions through a physical ultrasonic treatment process, which had better dispersibility in water than Bulk-g-C3N4. Then the final product of CeO2/L-g-C3N4 was obtained by a hydrothermal co-precipitation technique with cerium nitrate as precursor. The characterization of morphology indicated that CeO2 nanoparticles evenly distributed on the surface of CeO2/L-g-C3N4, which might be attributed to L-tryptophan offering more bonding sites (-COOH) for the deposition of nanoparticles. The material exhibited excellent oxidase-mimicking activity, which could catalyze the colorless 3,3 ',5,5 '-tetrame- thylbenzidine (TMB) into the blue-colored oxidized TMB product (oxTMB), and a new hydroquinone (HQ) colorimetric sensing strategy was proposed. And theoretical simulations indicate that the increased enzymatic activity is mainly attributable to the reduced binding energy of absorbed intermediates. Additionally, due to the material's exceptional fluorescence properties, combined with the inner filter effect and redox reactions, a unique on-off-on fluorescence sensing mechanism had been successfully developed for the detection of Cr(VI) and SO32-.

The widespread use of antibiotics in human and animal health has caused significant water pollution and increased microbial resistance, posing risks to human health and ecosystems. In this study, Bi2MoO6 nanoflowers and UiO-66-NH2 octahedra (UN-BMO) composites were synthesized via a solvothermal method and applied for the first time to antibiotic adsorption. The 3 % UN-BMO composite demonstrated high adsorption capacities: 37.74 mg & sdot;g- 1 for ciprofloxacin hydrochloride (HCIP), 31.05 mg & sdot;g- 1 for tetracycline (TC), 79.86 mg & sdot;g- 1 for amoxicillin (AMX), and 85.54 mg & sdot;g- 1 for erythromycin (EM), with adsorption rates of 98.3 % (15 s), 97.6 % (30 min), 84.1 % (60 min), and 86.4 % (100 min), respectively. Kinetic and isotherm models indicated that HCIP adsorption involves both monolayer and multilayer coverage, with a mix of chemical and physical processes. TC primarily follows multilayer physical adsorption, while AMX shifts from multilayer physical adsorption at low temperatures to monolayer physical adsorption at higher temperatures. EM is characterized by monolayer adsorption. Thermodynamic analysis revealed that HCIP, AMX, and EM adsorption is endothermic, while TC adsorption is exothermic. FTIR and XPS analyses confirmed that HCIP, AMX, and EM adsorption is dominated by it-it interactions and hydrogen bonding, with TC adsorption also involving electrostatic interactions.

The misuse of antibiotics resulted in their release into the environment and food chain, leading to environmental pollution and posing a threat to human health. Porous adsorption materials possessed characteristics such as a large specific surface area, high porosity, easy surface modification and novel functionality, which had demonstrated excellent efficacy in removing antibiotics. Adsorption, as a crucial technology for concentrating residual drugs in the environment and food substrates, has garnered significant attention from researchers in recent years. This review provided an overview of the performances of various porous materials (including carbon-based materials, organic porous materials, organic porous polymers, biopolymers, gel materials, composite materials and membrane technologies) as adsorbents for antibiotics removal. It also discussed factors influencing adsorption effectiveness (such as pH, initial concentration of antibiotics, temperature), adsorption mechanisms and the current application and research progress in antibiotic adsorption. Finally, the future research directions and trends were proposed along with suggestions for future research needs. The review offered valuable insights for future studies on isolating, enriching, adsorbing and removing prohibited or restricted antibiotic drugs from environmental samples, water sources, animal-derived foods and biological samples.

There is an abundance of organic aerosol (OA) in the atmospheric composition, and its variations can directly or indirectly influence weather, climate, and the environment. This paper designs and constructs a horizontally scanning fluorescence lidar system based on the principle of laser-induced fluorescence. By combining traditional lidar algorithms with neural network algorithms, this system is capable of inverting the concentration of OA in the atmosphere. Furthermore, by integrating meteorological data, a joint model incorporating convolutional neural networks (CNN), bidirectional long short-term memory (BiLSTM), and squeeze-and-excitation attention (SE) mechanisms, referred to as CNN-BiLSTM-SE, is developed to accurately calibrate and invert atmospheric OA concentrations. Experimental results demonstrate that the enhanced CNN-BiLSTM-SE neural network model exhibits robust performance under various weather conditions, including post-rain, clear, and hazy environments, effectively capturing the fluctuations in OA concentrations. The root mean square error values are 0.11545 post-rain, 0.12365 on clear days, and 0.15365 during hazy conditions, highlighting the model's consistent accuracy across diverse atmospheric scenarios. Additionally, numerical simulations of secondary organic aerosol (SOA) were performed in the Ningxia region of China using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to investigate SOA concentration variations under different meteorological conditions. The results reveal significant differences in the concentrations of SOA under varying weather conditions, which impact the composition of OA. By comparing and analyzing the lidar-measured data with the numerical simulation results from WRF-Chem, it was found that the OA concentrations calculated using the lidar exhibit a correlation of 0.79 with anthropogenic alkane emissions in the SOA simulated by WRF-Chem, and a correlation of 0.63 with the total SOA simulated by WRF-Chem. This study offers a practical tool and research approach for investigating OA concentrations, while also supporting environmental monitoring initiatives.

This study explores the role and impact of intelligent education products in the educational field. The research processes and categorizes review data to extract key insights and emerging trends using text mining techniques, including sentiment analysis, review classification, and Latent Dirichlet Allocation (LDA) topic modeling. Sentiment analysis reveals that users generally exhibit positive emotional attitudes toward the product. The LDA analysis revealed three findings: the role of learning devices in enhancing children's education, the impact of parental engagement on academic achievement, and the integration of AI technology in skill development and assessment optimization. The findings highlight that intelligent education products significantly enhance student engagement and play an important role in modern education. Furthermore, this study offers practical applications for optimizing device functionality and educational content and contributes to the advancement of intelligent education.

Tetracycline hydrochloride (TCH) exists in various forms in aqueous solution due to pH changes, which not only alters the reactivity of TCH, but also affects the process of reactive oxygen species (ROS) attacking the molecule. Therefore, the rational design of piezo-photocatalytic materials coupled with a comprehensive understanding of the degradation mechanisms of various TCH species constitutes a critical approach to addressing tetracycline antibiotic contamination. In the design and preparation of piezo-photocatalysts, controlling the oxygen vacancy concentration is crucial as it governs the coupling efficiency between piezoelectric response and photocatalytic activity, as well as the strength of spontaneous polarization. Meanwhile, the morphology of the material is a key factor influencing the migration pathways of charge carriers. In this work, hollow spherical Bi4Ti3O12 was synthesized using an inorganic titanium source, demonstrating exceptional piezo-photocatalytic activity. The degradation rate was 1.57 and 5.29 times higher than that of traditional spherical and plate-like morphologies, with a rate constant of k = 0.127. In an innovative approach, density functional theory calculations of local softness and hyper-softness were employed to analyze the reactivity changes of TCH in its different deprotonated states toward reactive oxygen species. Combined with molecular electronegativity analysis, the factors influencing the degradation efficiency were identified. This study provides a solid foundation for developing efficient and environmentally friendly piezo-photocatalysts and offers new insights into the degradation mechanism of TCH. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The development of efficient and stable photocatalysts remains a key objective for advancing photocatalytic hydrogen (H2) evolution. This study introduces a rapid one-step synthesis to fabricate amine-functionalized Zn1-xCdxS over ZnS-ethylenediamine (ZC/Z-EDA) inorganic–organic hybrid materials. The incorporation of amine component serves dual functions. It facilitates the formation of Z-EDA nanosheets featuring a tunable band structure while simultaneously enabling the precise anchoring of ZC onto the Z-EDA surfaces. This precise anchoring establishes an intimate contact interface between the hybrid components. Within this engineered architecture, the coexistence of strategically induced defects, optimized interlayer charge transfer channels, and tailored type-II heterojunctions operates synergistically. This combination significantly enhances visible light absorption efficiency, promotes the separation and migration of photogenerated charge carriers, and isolates reactive sites. Consequently, the optimized ZC/Z-EDA hybrid demonstrates a 4338-fold increase in photocatalytic H2 evolution rate under visible light compared to pristine Z-EDA alone. Furthermore, it achieves an apparent quantum efficiency of 43.7

Zero-dimensional NiS cocatalysts were deposited onto ethylenediamine-intercalated two-dimensional ZnS (en)0.5/CdxZn1-xS (ZC) supports via combined solvothermal and precipitation methods, forming NiS/ZC organic-inorganic hybrid photocatalysts. Through integrating morphology control, ionic doping, cocatalyst modification, and heterojunction construction, the photoresponse of ZnS was broadened into the visible region. The multi-strategy synergy enhanced charge carrier separation/migration kinetics and increased active-site accessibility. Consequently, the optimized NiS/ZC catalyst achieved an exceptional hydrogen evolution reaction rate and sustained stability under visible light irradiation, accompanied by an apparent quantum yield (AQY) of 58.6 % at 420 nm.

Redox homeostasis is a key reason for reactive oxygen species (ROS) tolerance in tumors. Complex reactive species interactome is closely related to the limited effectiveness of ROS-mediated cancer therapy. Engineering redox dyshomeostasis amplifier by disturbing the interactome of ROS with reactive sulfur species (RSS) remains a great challenge. Herein, a gelatin/cRGD-modified redox dyshomeostasis amplifier based on MoSx/gamma-MnS (MMS) hollow nanoflowers polysulfide nanocomposite was constructed by a one-pot solvothermal process for an elevated intracellular ROS level through near-infrared (NIR)-II light-activated cancer-specific polysulfideintensive chemodynamic therapy (CDT). The NIR-II light accelerated H2S-H2S2-3 (typical RSS) release in acidic tumor microenvironment (TME). Density functional theory calculations divulged that overexpressed H2O2 in acidic TME can augment the release of H2S-H2S2-3, triggered by low activation energy of the MMS, consequently depleting glutathione (GSH) level. The form and quantity of H2S-H2S2-3 can be analyzed by the advanced technology of in-situ synchrotron radiation (SR) X-ray absorption near-edge structure spectrum combined with high-performance liquid chromatograph-mass spectrometer. Simultaneously, Mn2 +-releasing CDT efficiency was enhanced to produce hydroxyl radicals (& sdot;OH), breaking redox homeostasis to induce ROS accumulation in the TME. Then, the ROS amplified oxidative stress damage through synchronous ferroptosis-apoptosis, potentially eradicating tumor without metastasis.

Bacterial infections significantly hinder wound healing. Despite the widespread use of antibiotics, their limited efficacy and the growing issue of drug resistance necessitate the development of new antibacterial agents with enhanced therapeutic effects and wound healing properties. We developed DNA-templated nano zinc oxide (ZnO) as an effective antibacterial wound treatment. Through systematic studies, we found both DNA nucleobases and phosphate backbone contribute to ZnO formation and stabilization. Using C20 DNA (20-base oligonucleotide) as the optimal stabilizer, we created uniformly sized ZnO nanoparticles. Subsequent interfacial modification with 15% hydrogen peroxide (H2O2) yielded H-ZnO with enhanced colloidal stability, photocatalytic activity, and bacterial adhesion. These modifications significantly increased the antibacterial properties of H-ZnO compared to ZnO, while also regulating Zn2+ release. The sustained release of Zn2+ not only enhanced the biosafety of the nanoparticles but also promoted wound healing. As a result, H-ZnO effectively promoted wound healing with reduced fibrotic response of both ordinary and bacterial-infected wounds without noticeable toxicity. The H-ZnO gel formulation demonstrated superior antibacterial activity and wound healing promotion, making it a promising candidate for clinical application in treating infected wounds.

Effective teaching practices are essential for enhancing classroom instruction and student learning. However, a comprehensive understanding of the factors influencing teachers' instructional practices remains elusive. This study employs machine learning (ML) to identify the most significant predictors influencing the instructional practices of secondary school teachers in Shanghai, China. Using data from the Teaching and Learning International Survey (TALIS) 2018, we identified key factors that distinguish teachers with high and low levels of instructional practices. The study combined data-driven and domain knowledge methods to identify the most influential features, and then analysed their impact on teachers' instructional practices using the Shapley Additive exPlanations (SHAP) and Gradient Boosting Machine (GBM) interpretative framework. The findings identified 10 key features, such as Small group work (tt3g42g) and Quieten the class for the lesson (tt3g42l), that distinguished teachers with high and low levels of instructional practices. This discovery enhances classroom teaching quality and teacher performance.

In the recent decade, many educators and researchers have employed Inquiry-Based Learning (IBL) to enhance students' learning performance. While extensive empirical studies have explored the impact of IBL on students' learning performance, the conclusions drawn from these studies are not always consistent. This meta-analysis study provides a comprehensive evaluation of the effects of IBL on students' learning performance. The analysis consists of 22 educational experimental and quasi-experimental studies with a total of 33 effect sizes samples published between January 2013 and June 2024. The results revealed that IBL significantly improved students' learning performance with a medium effect size (g = 0.574). Furthermore, this study investigates the impact of six moderating variables on the outcomes: inquiry types, participants, activity goals, inquiry tools, inquiry environment, and inquiry methods by the application of activity theory. The results indicated that activity goals significantly moderated students' learning performance. These findings support the use of IBL to improve learning performance especially in high school and college engineering education.