As a green and sustainable synthetic route for preparing valuable organofluorine compounds, heterogeneous photocatalytic perfluoroalkylation using semiconductors as photocatalysts has drawn more and more attention for its advantages of more stable, easier to be recycled and relative broad spectral absorption. In this study, an efficient PbO2/PbBiO2Br S-scheme heterojunction nanosheet photocatalyst was fabricated by a facile photo-deposition process. This heterogeneous photocatalyst exhibits high activity, excellent stability and good compatibility in the photocatalytic perfluorobutylation of 3-substituted indoles. Moreover, this heterogeneous reaction can be easily scaled and the PbO2/PbBiO2Br photocatalyst can be easily recovered and recycled for several times, showing potential industrial application value. The PbO2/PbBiO2Br heterojunction not only facilitates the transfer of photo-excited charges but also preserves higher redox potentials for the reduction of the perfluorobutyliodide and oxidation of the radical intermediates, which may be the main reason for the superior performance of PbO2/PbBiO2Br to PbBiO2Br. This study not only develops an alternative photocatalyst for heterogeneous light-driven perfluoroalkylation reaction, but also gives a reference for fabricating robust and high-performance photocatalysts for heterogeneous organic synthesis.

To address the issues of high metal leaching and low activity observed in homogeneous single-metal peroxymonosulfate (PMS) activators, we developed a magnetic cobalt-zirconium oxocarbonate heterogeneous catalyst (CoZrOx@C). Interfacial engineering yielded a Co3O4@ZrO2 heterojunction, which effectively reduced metal leaching and significantly enhanced catalytic activity. In the CoZrOx@C/PMS system, 20 mg/L ciprofloxacin (CIP) was degraded by 96% within 30 min (k = 0.2773 min-1). The catalyst tolerated representative background constituents (Cl-, SO42-, HCO3-, NO3-, H2PO4-, humic acid) and retained 79.1% CIP removal after four reuse cycles. Both theoretical and experimental evidence confirmed efficient interfacial electron transfer within the Co3O4@ZrO2 heterojunction, which accounted for the activity enhancement. Co-O-Zr linkages stabilized the structure and suppressed Co2+ leaching. Toxicity assessment suggested low acute aquatic toxicity of the CIP transformation products. Quenching tests and electron paramagnetic resonance identified singlet oxygen (1O2) as the dominant oxidant; sulfate, hydroxyl, and superoxide radicals (center dot SO4-, center dot OH, center dot O2-), together with direct electron transfer, contributed secondarily. These findings highlight the potential of MOF-derived heterogeneous catalysts for antibiotic removal and provide insights for the design of advanced wastewater treatment systems.

To clarify the quantitative equivalence between point charge and transition metal, we evaluate the substitutability of +1 point charges for thirty monovalent transition metal cations (Sc+–Hg+) with four ligands (H2O, NH3, CO, N2). The point charge model reproduces the periodic binding energy trends of 3d/4d metal cation complexes, yet systematically underestimates the binding energies of their 5d counterparts. Wavefunction analyses, Wiberg bond indices, and natural population analysis results collectively confirm that the point charge model fails to capture the characteristic π-backbonding interactions and orbital-specific covalent character. Notably, range-separated or double-hybrid functionals are indispensable for obtaining reliable energetics when the ”derivation calculation method” is used for binding energy determination. Furthermore, in H2O + CO HCOOH, a positive point charge reduces the hydrogen-transfer barriers comparably to Cu⁺, Ag⁺, and Au⁺, provided no metal–hydrogen bonds form. Nevertheless, the model requires case-specific validation, not universal application in transition metal-catalyzed systems.

Photocatalytic H2 production via water splitting using semiconductor materials represents a promising strategy to address the energy crisis. In this work, ZnIn2S4/ZnO-In2O3 dual-Z-scheme heterojunctions were synthesized and evaluated for photocatalytic H2 production under simulated solar light irradiation. The ternary hybrids exhibited superior activity compared to individual semiconductor components. Photocatalytic H2 production rates reached 5229.94, 5216.09, and 3186.71 mu mol center dot g-1 center dot h-1 using Na2S-Na2SO3, lactic acid (LA), and triethanolamine (TEOA) as sacrificial agents, respectively. Furthermore, organic dyes such as rhodamine B (RhB), erythrosine B (ErB), and fluorescein sodium (FS) were employed to sensitize the ZnIn2S4/ZnO-In2O3 catalysts with TEOA as the sacrificial agent. Sensitization with 0.25 g center dot L-1 ErB achieved a H2 evolution rate of 6014.08 mu mol center dot g-1 center dot h-1, which was 4.51-fold, 38.42-fold, and 45.43-fold higher than that of single ZnIn2S4, ZnO, and In2O3, respectively. The boosted photocatalytic performance was attributed to the synergistic effect of semiconductor heterojunction and dye sensitization. Based on theoretical calculations, experimental data, and literature reports, a dual-Z-scheme heterojunction electron transfer mechanism and a dye-sensitized photo-catalytic H2 production mechanism were proposed.

Halobenzoquinones (HBQs) are emerging toxic disinfection byproducts widely present in drinking water. Although their reactions with amino acids have been reported, the detailed stepwise mechanisms remain unclear. Herein, density functional theory (DFT) was employed to systematically explore the transformation of HBQs by the anion of glycine (Gly-), the dominant species at environmental pH. Quantitative thermodynamic and kinetic parameters were obtained for the complete transformation pathway from parent HBQs to poly-Gly-derivatized products. Two major pathways, 1,4-addition (Michael addition) and SN2 substitution, were identified. 1,4-Addition dominates the initial reaction for mono-, di-, and trihalogenated HBQs, while SN2 is crucial for perhalogenated HBQs. Water exerts a dual catalytic effect on key proton-transfer steps. A regioselectivity rule was established, with the para-carbon showing the highest reactivity toward subsequent nucleophilic attack, rationalized by the lowest unoccupied molecular orbital (LUMO) distributions and steric effects. Condensed Fukui functions alone are insufficient for regioselectivity prediction. This work provides molecular-level insights into the transformation and detoxification of HBQs by Gly-, supporting their mass spectrometric identification and the design of amino acid-based water treatment strategies.

The adsorption and sensing performances of atmospheric toxic gases, including NH3, NO, NO2, and N(CH3)3, on monolayer MoB were systematically investigated using the density functional theory (DFT) calculations. The results show that NH3, NO, and N(CH3)3 preferentially adsorb on the Mo sites, whereas NO2 favors the B site. Monolayer MoB exhibits distinct adsorption behavior toward these gases, with adsorption energies of −0.543, −3.574, −4.164, and −1.043 eV for NH3, NO, NO2, and N(CH3)3, respectively. Mulliken population analysis indicates that all four N-containing gas molecules act as electron acceptors. Density-of-states analyses reveals obvious peak shifts and orbital hybridization, confirming significant electronic interaction between the gas molecules and MoB layer. Recovery-time analysis suggests that NH3 can desorb rapidly, indicating that monolayer MoB is promising as a reusable gas sensor for NH3 at room temperature. N(CH3)3 also exhibits a considerable sensing response, although its relatively long recovery time may limit rapid cycling. In contrast, NO and NO2 exhibit much stronger adsorption and much longer retention times, making monolayer MoB more suitable as an adsorbent for the capture and removal of these toxic gases. These findings suggest that monolayer MoB is a promising candidate for both gas sensing and gas adsorption applications, depending on the target gas species.

The energy storage performance of transition metal oxides (TMO) as electrode materials for supercapacitors exhibit a strongly morphology-dependent due to changes in the local electronic and microscopic geometric structure of the interface. Herein, MoO3 with morphology in nanoprisms (NP), nanostrips (NS), and nanobulks (NB) were prepared by different synthesis routes. The morphology and structural characteristics of the three obtained MoO3 were characterized by scanning electron microscopy, the high resolution transmission electron microscopy, Brunauer-Emmett-Teller techniques, X-ray diffraction, and X-ray photoelectron spectroscopy. And then, the significant effects of the morphologies of MoO3 on the electrochemical activity were assessed using cyclic voltammetry and galvanostatic charge-discharge measurements. The supercapacitors using MoO3-NP as electrode achieved the largest specific capacitance of 254.0 F g- 1 at a current density of 0.3 A g- 1 as compared to 123.3 F g- 1 of MoO3-NS, and 8.7 F g- 1 of MoO3-NB in 1 mol L- 1 Na2SO4 electrolyte. Among them, the MoO3-NP electrode has the highest pseudo-supercapacitive response and excellent cycling stability than the other electrodes, which is attributed to the morphology-dependent to enhance the electrical conductivity and promote the generation of active reaction sites. Therefore, the MoO3-NP electrode can be significantly applied to supercapacitors for cost reduction and energy conversion efficiency improvement.

This study examined the effect of the terminating groups (−O, −(OH) and −F) of MXenes on bisphenolA (BPA) adsorption, while also using the interlayer spacing of the membrane to increase its adsorption behavior. In the family of MXenes, Ti3C2Ox, Ti3C2(OH)x and Ti3C2Fx were constructed and simulated to determine their adsorption mechanisms for BPA in both gas and aqueous phase using the computational methods. Herein, the density functional theory (DFT) and Grand Canonical Monte Carlo (GCMC) methods were mainly used to analyze the adsorption energy of MXenes for gaseous BPA, examining factors such as structural properties, adsorption capacity, adsorption sites, as well as the influence of temperature and pressure on adsorption performance. The findings revealed that MXenes with −O and −(OH) terminating groups exhibited higher adsorption energies compared to those with −F, resulting in a greater adsorption capacity (specifically, Ti3C2(OH)x > Ti3C2Ox > Ti3C2Fx). These MXenes structural analysis suggested that the stronger adsorption energies of BPA on Ti3C2(OH)x and Ti3C2Ox were the Van der Waals force and hydrogen bond between MXenes and BPA. The results of molecular dynamic (MD) simulation analysis indicated that Ti3C2(OH)x and Ti3C2Ox still showed excellent adsorption capacity of BPA even in the presence of water competition adsorption. The adsorption capacity of BPA by MXenes increased with the increase of the membrane interlayer spacing, regardless of whether BPA was in gas phase or aqueous solution. Surprisingly, with the increase of interlayer spacing, the adsorbed BPA was more likely to stay in the void of the membrane Ti3C2Ox and Ti3C2(OH)x, and pass through the void of the film Ti3C2Fx to enter the penetration zone.

Photocatalytic H2 production from water provides hope for alleviating the energy crisis. In this work, ZnO/CuO composites were synthesized using a simple one-step hydrothermal method and employed as catalysts for H2 production. The photocatalytic performance of the ZnO/CuO composites was investigated using TEOA as a sacrificial agent under simulated sunlight irradiation. The effects of sacrificial agent concentration, catalyst dosage, and Zn/Cu molar ratio of the catalyst on H2 evolution were explored. Additionally, rhodamine B, erythrosine B, and eosin Y dyes were selected for sensitizing the ZnO/CuO composite to further improve photocatalytic efficiency. Under optimal conditions, a maximum H2 production of 6615.94 mu mol g- 1 h- 1 was achieved, which was 55.3 times and 74.6 times greater than those of pure ZnO and pure CuO, respectively. The p-n heterojunction established at the interface of ZnO/CuO, as well as the electron transfer from the dye sensitizer to the catalyst surface, contributed greatly to photocatalytic H2 production.

A novel and efficient approach has been developed for the preparation of 2-oxazolidinones through propargylamine–CO 2 coupling reactions employing a Cu( i )-functionalized covalent triazine framework (CTF)/ionic liquid as a recyclable catalytic system.

Artificial mimic enzymes have attracted wide attention for their superior characteristics to natural enzymes in extensive applications of diagnosis and therapy. In this paper, a nanozyme Cu-BDC@FeMo 6 was designed and fabricated by embedding polyoxometalate (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 ] & sdot;6H 2 O (FeMo 6 ) into a copper-based metal-organic framework (Cu-BDC). The integration of FeMo 6 and Cu MOF based on the synergies of oxidability of FeMo 6 and oxygen-driven reversible Cu + /Cu 2+ enhanced the peroxidase mimicking activity, which accomplished the sensitive visual monitoring of H 2 O 2 and dopamine (DA). The detection of H 2 O 2 was driven by CuBDC@FeMo 6 catalyzing the oxidation of TMB with colorimetric evolution to blue, and consecutive monitoring DA via the reverse process of reduction of ox-TMB was further achieved. The limit of detection (LOD) of H 2 O 2 and DA were 10 mu M and 2.27 mu M, with excellent stability, and outstanding selectivity. The mechanism of the catalysis was further evaluated, and the generation of O & sdot;- 2 played a crucial role in the catalysis for oxidation. The logic gate design was constructed to illustrate the process and application. This work provides a feasible reference for the reasonable design of simulated enzyme in biosensor applications.

Two-dimensional (2D) semiconductors have drawn great interest for crafting high-performance photocatalysts due to their distinct structural advantages. However, constructing 2D semiconductor-based heterostructures with intimate coupling interfaces and efficient charge separation channels still remains a big challenge to now. Herein, we reported the defect-mediated fabrication of intimate 2D/2D/2D dual heterojunctions consisting of Cd0.15Zn0.85In2S4 (C0.15ZIS) photo-absorber layer integrated with spatially separated WS2 and Ti3C2 MXene (MNs) cocatalysts (MNs-C0.15ZIS-WS2). Noticeably, the MNs-C0.15ZIS-WS2 heterostructures exhibited a distinguished H2 evolution reaction (HER) activity of 31.29 mmol center dot g-1 center dot h-1 (corresponding to an apparent quantum yield of 22.3 % at 400 nm) under visible-light irradiation, evidently superior to those of Pt-loaded C0.15ZIS-MNs and most reported ZnIn2S4-based composite photocatalysts. The exceptional HER capability of MNs-C0.15ZIS-WS2 could be attributable to the synergistic charge separation of Schottky and Type-I dual heterojunctions as revealed by band structure analysis and density functional theory (DFT) calculation, superior visible-light harvesting ability of the unique 2D/2D/2D hierarchitectures, and abundant catalytically active sites stemming from the Oterminated MNs and defect-rich WS2 cocatalysts. Our study could inspire the exploitation of highly efficient photocatalysts through rational structural manipulation of 2D building blocks.

Electrodialysis (ED) performance depends critically on ion-exchange membranes, but commercial membranes suffer from severe degradation at high temperatures (>60 degrees C), restricting their industrial application. To address the inherent drawbacks of polybenzimidazole (PBI), high hydrophobicity and low conductivity, this study proposes a multi-level synergistic strategy combining topological structure design, functional group modification, and nanomaterial hybridization. A tri-branched PBI (tzPBI) framework was developed to enhance structural stability, while flexible propyl sulfonate groups improved hydrophilicity, and phosphotungstic acid (PTA) nanoparticles boosted ion transport. The prepared s-tzPBI/PTA membrane exhibited good dimensional stability, mechanical strength, and permselectivity, achieving a high NaCl removal ratio (Rd = 90.87 % at 20 degrees C). Remarkably, under 80 degrees C operation, Rd reached 96.60 %, with only <6.85 % degradation after 16-cycles ED process, far surpassing the commercial TR-CEM (24.30 % Rd loss). Post-high-temperature analysis revealed membrane failure mechanisms under extreme conditions. And the membranes after long-term testing were also compared and studied to explore the destructive behaviors caused by high temperature. In this work, synergistic optimization of high-temperature durability and structural stability was achieved, advancing the practical application of ion exchange membranes in harsh environments.

Semiconductor photocatalysts have been widely used to remove pollutants from industrial wastewater. Organic pollutants and heavy metal ions often coexist in polluted environments. However, the studies on water pollution have only focused on the treatment of single organic pollutants or heavy metal ions. Herein, a ZnO/CdS composite is synthesized using a simple hydrothermal method. The hybrid shows excellent photocatalytic performance for the simultaneous removal of rhodamine B (RhB) dye and hexavalent chromium (Cr(VI)) complex contaminants under visible‐light irradiation. Photocatalytic efficiencies of 98.93% for RhB degradation and 94.59% for Cr(VI) reduction are achieved after 120 min of irradiation. The ZnO/CdS composite exhibits superior photocatalytic activity compared with pristine ZnO and CdS. The Z‐scheme heterojunction formed between ZnO and CdS promotes the separation and transfer of photogenerated carriers, thus enhancing the photocatalytic performance of the composite. Reusability and stability investigations demonstrate >90% RhB degradation and Cr(VI) reduction after the 3rd cycle, suggesting the chemical stability of the ZnO/CdS composite with the potential for practical applications. According to the radical trapping experiment, RhB is decomposed by the co‐oxidation of h + and •O 2 − . Meanwhile, the Cr(VI) in K 2 Cr 2 O 7 is reduced to Cr(III) by e − .

Oxidative stress, characterized by an imbalance between excessive reactive oxygen species (ROS) production and impaired antioxidant defenses, is closely linked to the pathogenesis of various otorhinolaryngological disorders. Mitochondria, as the primary site of cellular energy production, play a crucial role in modulating oxidative stress. Mitochondrial dysfunction exacerbates ROS generation, leading to cellular damage and inflammatory responses. In otorhinolaryngological diseases, oxidative stress is strongly associated with conditions such as hearing loss, allergic rhinitis, and chronic sinusitis, where oxidative damage and tissue inflammation are key pathological features. Recent studies have highlighted the potential of antioxidant therapies to mitigate oxidative stress and restore homeostasis, offering promising avenues for alleviating symptoms in these diseases. However, despite the encouraging results from early-stage research, the clinical efficacy of antioxidant interventions remains to be fully established. This review provides an overview of the role of oxidative stress in otorhinolaryngological diseases and evaluates the therapeutic potential of antioxidant strategies.

The modification and composite formation of MXenes by doping with transition metal compounds as counter electrode (CE) catalysts is an effective strategy for improving the power conversion efficiency (PCE) of dyesensitized solar cells (DSSCs). Herein, Ti3C2@WO3 composites were prepared by the hydrothermal method using two-dimensional titanium carbide MXenes (2D-Ti3C2) doped with tungsten trioxide (WO3) at mass ratios of 3:1, 2:1, 1:1, and 1:2. The effects of WO3 on the electrocatalytic activity of the Ti3C2@WO3 as CE catalysts are evaluated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Tafel polarization. And then, DSSCs with the four different Ti3C2@WO3 catalysts yield PCEs of 6.75 % (3:1), 7.89 % (2:1), 7.56 % (1:1) and 6.40 % (1:2) for the regeneration of I3- /I- shuttles by the photocurrent-photovoltage tests, respectively. The excellent performance of Ti3C2@WO3 can be ascribed to the ordered interlayer structure of 2D-Ti3C2 MXene and the doping of WO3 results in the generation of a larger number of active sites due to changes in the microelectronic and geometric structures. Meanwhile, the two-phase interface between 2D-Ti3C2 and WO3 exist the built-in electric field to accelerate the diffusion of I3- /I- shuttle. Thus, Ti3C2@WO3 composites are expected to become the ideal Pt-free CE catalysts in the assembled DSSCs.

In this study, a nitrogen/oxygen co -doped carbon fiber cloth with a hierarchical porous structure was synthesized by one-step carbonization and in situ activation method and acted as binder -free electrode materials for supercapacitors. Cotton fiber cloth served as the carbon precursor, while molecular dispersed CaCl 2 . 6H 2 O and urea functioned as activator and N dopant, respectively. The influence of molar concentration of CaCl 2 . 6H 2 O and urea on the microstructure and capacitive performance of the resulting products were investigated. CaCl 2 . 6H 2 O has an expansion effect on pores, resulting in reduction of micropores. Hence, the specific surface area of the resulting porous carbon increased first and then decreased with the increase of CaCl 2 . 6H 2 O concentration. In addition, the erosion of NH 3 and CO 2 (produced by the decomposition of urea) at high temperature on the surface of the samples promoted the formation of porous structure. Urea plays the dual role of doping and activation agent. The morphology and structure analysis shown that the activated samples exhibited hierarchical pore structure, large specific surface area, and high heteroatom content. The optimal sample NAC-20 exhibited good capacitive performance, including high specific capacitance of 260.9 F g -1 at 0.1 A g -1 and good rate performance. Moreover, the symmetric supercapacitor exhibited a maximum energy density and power density of 16.2 Wh kg -1 and 19.0 kW kg -1 , respectively, in 6 M KOH electrolyte. In this work, a green, low-cost molten salt activation method was proposed to synthesis biomass derived porous carbon materials for energy storage devices.

Artificial mimic enzymes have attracted wide attention for their superior characteristics to natural enzymes in extensive applications of diagnosis and therapy. In this paper, a nanozyme Cu-BDC@FeMo6 was designed and fabricated by embedding polyoxometalate (NH4)3[FeMo6 O18(OH)6]·6H2O (FeMo6) into a copper-based metal–organic framework (Cu-BDC). The integration of FeMo6 and Cu MOF based on the synergies of oxidability of FeMo6 and oxygen-driven reversible Cu+/Cu2+ enhanced the peroxidase mimicking activity, which accomplished the sensitive visual monitoring of H2O2 and dopamine (DA). The detection of H2O2 was driven by Cu-BDC@FeMo6 catalyzing the oxidation of TMB with colorimetric evolution to blue, and consecutive monitoring DA via the reverse process of reduction of ox-TMB was further achieved. The limit of detection (LOD) of H2O2 and DA were 10 μM and 2.27 μM, with excellent stability, and outstanding selectivity. The mechanism of the catalysis was further evaluated, and the generation of O2·- played a crucial role in the catalysis for oxidation. The logic gate design was constructed to illustrate the process and application. This work provides a feasible reference for the reasonable design of simulated enzyme in biosensor applications.

Designing high temperature proton exchange membranes (HTPEMs) with high H+ conductivity and long durability has been challenging. Here, a comb-shaped polybenzimidazoles (CbPBI) and crosslinkable polyoxy (benzenesulfonic acid) phazenes (PBSP) proton conductors are prepared, then they are used to fabricate a series of PBSP-CbPBI membranes with good comprehensive performances. CbPBI provides high flexibility and large free volume, which facilitates the construction of proton transport channels. And PBSP is the bifunctional proton conductor and crosslinker that introduces abundant sulfonic acid groups while retaining the crosslinkable property. By strongly chemical binding with CbPBI, the basicity of the imidazole ring is enhanced, avoiding the leaching of PBSP, thus enabling the overall crosslinked membrane to exhibit a durable intrinsic proton conductivity. Benefiting from the construction of the dual crosslinked network (covalent and ionic crosslinking), the oxidative stability, dimensional stability, and fuel-blocking properties of the PBSP-CbPBI membranes perform well. The proton conductivity of PBSP(50)-CbPBI membrane reaches 0.163, 0.084, 0.057, and 0.043 S/cm, respectively, at 180 degrees C and different relative humidity (100 % RH, 50 % RH, 30% RH, and 0 RH). Enduring hotwashing for 96 h, the less decay of membrane in conductivity and weight demonstrates good durability. The design strategy such as the construction of monolithic crosslinked macromolecular structures in PBSP-CbPBI membranes shows wide application prospects in HTPEMs.

In this study, a vitamin C-regulated CoAl-layered double hydroxide with abundant oxygen vacancies was synthesized via a simple hydrothermal process. The resulting CoAl-layered double hydroxide was employed to activate peroxydisulfate for removal of sulfamethoxazole. The effect of the experimental parameters such as pH, catalyst dose and peroxydisulfate concentration on sulfamethoxazole removal was investigated. The current system exhibited excellent catalytic performance for sulfamethoxazole removal in a broad pH range (i.e., pH 3.0-11.0). Under the optimized condition, 94.2% of sulfamethoxazole was degraded within 15 min, accompanied by a 67.6% reduction in chemical oxygen demand. The effective sulfamethoxazole degradation could be attributed to four pathways. Firstly, the ≡ Co2+ in catalyst reacted with peroxydisulfate to generate reactive species, including SO4•-, •OH, O2•- and 1O2, which could degrade sulfamethoxazole. Secondly, the oxygen vacancies could modulate intrinsic electrons, resulted in the surface activation of catalyst and accelerated charge transfer, which was favorable for the degradation of sulfamethoxazole. Thirdly, the presence of vitamin C not only promoted the formation of oxygen vacancies but also expanded the interlayer spacing of layered double hydroxide. A large interlayer spacing facilitated the diffusion of peroxydisulfate and pollutants in the interlayer and improved the utilization efficiency of the active site. Lastly, the high-valent cobalt species exhibited excellent oxidation ability and enhanced the catalyst performance through continuously being employed as an electron acceptor. This study provided a valuable insight for the design and application of Co-based catalysts in peroxydisulfate-based advanced oxidation processes.