The development of visible light-responsive semiconductors with enhanced charge separation is crucial for advanced photocatalysis. Herein, a Z-scheme heterojunction photocatalyst, Cu-Bi2WO6/Bi2Ti2O7, was constructed by introducing oxygen vacancies into Bi2WO6 through partial substitution of Bi3+ by Cu ions; it was followed by hydrothermal synthesis, during which Bi2Ti2O7 nanoparticles were grown in situ on flower-like Cu-doped Bi2WO6 microspheres. When compared with the conventional type-II Bi2WO6/Bi2Ti2O7, the optimised Zscheme system demonstrates markedly enhanced photocatalytic performance, achieving 99 % degradation of Rhodamine B and tetracycline within 60 min under simulated sunlight as well as effective sterilisation to Escherichia coli and Staphylococcus aureus. This improvement is attributed to the broadened spectral absorption range and the Z-scheme configuration, with the latter providing string redox potentials and promoting efficient electron-hole separation. The transformation of the charge transfer mechanism from a type-II heterojunction in Bi2WO6/Bi2Ti2O7 to a Z-scheme mechanism in Cu-Bi2WO6/Bi2Ti2O7 was validated through radical trapping experiments, Mott-Schottky measurements, X-ray photoelectron spectroscopy (XPS) and Density Functional Theory (DFT) calculations.

Traditional Fenton reaction is limited by strict pH and iron sludge. integrating photo-Fenton enables operation under mild conditions. We report a one-step hydrothermal synthesis of Fe-modified Bi2WO6 (Fe-BWO) to create an efficient photo-Fenton synergistic system for ciprofloxacin (CIP) removal under visible light. The Fe-BWO system achieved 83.7 % CIP degradation in 1 h, surpassing standalone photocatalysis and homogeneous Fenton. The degradation rate was 6 times that of photocatalysis and 1.5 times that of homogeneous Fenton. Crucially, the system exhibited excellent stability, wide pH applicability, and low H2O2 consumption OH, and ·O2- were confirmed as major reactive species. Mechanistic studies indicate that the narrowed band gap promotes electron migration, while H2O2-induced surface microenvironment variation (attributed to Bi(3-x)+ electron redistribution) is vital for molecular oxygen activation. This work offers novel insights into H2O2 activation and the impact of surface microenvironments in photo-Fenton processes.

Photoelectrochemical carbon dioxide reduction (PEC CO2R) enables direct solar-to-chemical conversion. However, few photocathodes are intrinsically stable light absorbers. The application of protective layers remains a critical approach for stabilizing photocathodes in corrosive environments. TiO2 is the most widely adopted stabilizer, yet its influence on catalytic performance remains poorly understood. Here, we examine TiO2-protected Cu2O photocathodes integrated with Au, Cu and Bi cocatalysts, combining experiments and simulations to unravel the role of the TiO2 overlayer. We find that TiO2 profoundly alters catalytic selectivity, suppressing CO and multicarbon (C2 +) pathways, while its impact on formate production with Bi, In and Sn cocatalysts is comparatively negligible. These results demonstrate that TiO2 is not an inert stabilizer, but an active component that reshapes interfacial reaction pathways. This work establishes critical design principles for integrating protective layers with photocathodes to achieve selective and efficient PEC CO2R.

As one of the most toxic heavy metals to humans and the environment, achieving simultaneous fluorescence detection and effective removal of Hg2+ presents a significant challenge. In this study, we combined the excellent photoelectric properties of benzothiadiazole groups with the porous structure of covalent organic polymers (COPs) to develop a novel covalent organic polymer material (BTD-MPD-COP) with enhanced fluorescence performance. The benzothiadiazole-modified sites in this material achieved the bifunctional application of BTD-MPD-COP for Hg2+ fluorescence detection with a detection limit of 35.65 µM and simultaneous removal with a capacity of 475 mg g-1. Furthermore, BTD-MPD-COP demonstrated remarkable Hg2+ selectivity and can be reused after desorption without significant reduction in its adsorption capacity. This indicates that BTD-MPD-COP possesses excellent dynamic reversibility in the adsorption of Hg2+. In summary, the development of functionalized bifunctional covalent organic polymer materials presents an effective strategy for simultaneous removal and detection of toxic heavy metal ions.

The practical application of bimetallic sulfide electrocatalysts for sustainable hydrogen production is still limited by insufficient control over their electronic structures and unfavorable adsorption energetics of reaction intermediates, resulting in inadequate activity and durability. To address these limitations, A ternary MnS-FeS2-NiS sulfide with dual heterojunctions was hydrothermally grown in situ on nickel foam. Density functional theory calculations show that the dual-heterojunction configuration promotes interfacial charge transfer and generates built-in electric fields at the heterointerfaces. Specifically, charge redistribution occurs across the MnS/FeS2 and NiS/FeS2 heterointerfaces, with electron density ultimately transferred toward NiS. This redistribution optimizes the binding strengths of key oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) intermediates, thereby enhancing catalytic activity and stability. In alkaline electrolyte, the MnS-FeS2-NiS/NF electrode exhibits excellent OER and HER performance. It requires overpotentials of only 139.8 mV for the OER and 159.2 mV for the HER to reach 10 mA cm-2. The electrode remains stable for more than 100 h in both reactions. The corresponding Tafel slopes are 36.62 mV dec-1 (OER) and 75.77 mV dec-1 (HER). The double-layer capacitances (Cdl) are 23.52 and 95.21 mF cm-2, respectively. In overall water-splitting tests, this electrode requires only 1.56 V to drive a current density of 100 mA cm-2 and exhibits excellent operational stability over 80 h. These results provide a feasible strategy for constructing dual-heterojunction catalysts for efficient water splitting.

Electrocatalytic CO2 reduction reaction (eCO(2)RR) is an effective solution for environmental and energy crises caused by excessive CO2 emission, consisting of multiple proton-coupled electron transfer (PCET) steps. Especially, to achieve industrial-level current densities, oriented and fast proton and electron supply is critical while challenging due to hydrogen evolution by-reaction (by-HER). In this work, functionalized conductive polymers are utilized to modify the traditional Cu-based gas diffusion electrode (GDE) regulating both local electron and proton transport for eCO(2)RR. Among which, pyrrole-3-methyl (PPy-3-CH3) modified Cu-GDE has achieved an excellent Faradaic efficiency for double-carbon (C-2) products above 80.0% in a wide working range of 300-600 mA cm(-2), due to its moderate activation energy barrier for electron and proton conduction. Specifically, the electron and proton transport via the facile Grotthuss mechanism, whose energy barriers are lower than the Vehicle mechanism. Furthermore, -CH3 groups could repel water, confine CO2 reactants and *CO intermediates nearby Cu catalytic sites, suppressing by-HER and augmenting carbon-carbon coupling. However, -COOH groups also act as proton hopping sites except -NH groups, increasing local protons and thus severe byHER. This work underscores importance of matched local electron-proton supply for electrocatalysts during PCET mediated electrocatalytic reaction, facilitating their industrial success.

Photocatalytic water splitting (PWS) for hydrogen production is a highly promising technology to address energy and environmental challenges and enable efficient solar energy conversion and storage. However, in light-driven PWS systems, rapid recombination of photogenerated electron-hole pairs due to low charge separation efficiency leads to unsatisfactory catalytic performance. Recently, introducing a magnetic field into PWS has proven effective in enhancing photocatalytic activity by suppressing charge recombination. Notably, nickel ions in Ni-MOF can act as magnetic response centers. Building on this, we report a dramatically enhanced PWS system using a ZnIn2S4/nickel-based metal-organic framework (ZnIn2S4/Ni-MOF) ferromagnetic heterojunction photo-catalyst under a static magnetic field. A series of ZnIn2S4/Ni-MOF catalysts with varied Ni-MOF content was synthesized; the optimized sample achieved a hydrogen evolution rate of 71.91 mmol & sdot;g-1 & sdot;h-1 under a 500 mT static magnetic field, 2.97 times higher than under visible-light irradiation alone. Systematic photo-electrochemical, magnetic, and DFT studies revealed that this enhancement stems from significantly prolonged carrier lifetimes due to spin-polarization effects of Ni ions under the magnetic field. This work offers new insights into designing high-efficiency heterojunction photocatalysts leveraging electron spin polarization.

The intrinsic incommensurate charge density wave in metal-organic frameworks has remained elusive due to the lack of direct evidence linking atomic-scale structural modulation to macroscopic electronic properties. Using high-quality Pr3HHTP2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) single crystals as a model system, we precisely resolve, for the first time, the incommensurately modulated structure of a conductive metal-organic framework at 100 K (modulation vector q = 0.39143(12) c*) via temperature-dependent single-crystal X-ray diffraction. The subsequent observation of a reversible metal-semiconductor transition around 350 K, which perfectly synchronizes with the disappearance of the structural modulation, provides convincing evidence for the electronic origin of the lattice distortion. Guest water molecules stabilize the modulated phase by synergistically regulating the relative rotation of the linkers and the interlayer spacing, thereby optimizing the inter-linker interactions. This work establishes a concrete experimental criterion for one-dimensional charge density wave in metal-organic frameworks and provides an ideal platform for probing coupled electronic-lattice modulations.

The inefficient coupling between the initial oxidation and subsequent deep degradation steps remains a critical bottleneck for achieving complete photocatalytic mineralization of toluene. In this study, we developed a "dynamic dual-catalytic system" with synergistic surface hydroxyl groups and metallic Bi-0 on a bismuth molybdate substrate. The optimized catalyst achieved 85.46% toluene conversion and 80.23% mineralization efficiency under light irradiation, which are 2.05 and 3.20 times higher than those of the pristine material, respectively. Through advanced in situ characterization and mechanistic studies, two complementary functions were elucidated: hydroxyl groups promote OH-mediated initial activation, enabling pre-oxidation of toluene, while metallic Bi-0 enhances charge separation and facilitates O-2(-) generation, leading to ring-opening reactions. These modifications operate in a synergistic and sequential manner to achieve complete mineralization of toluene. This work provides new insights into the role of organic intermediates in oxygen activation and proposes a promising strategy for developing next-generation photocatalysts for volatile organic compound elimination.

Indium is a critical dispersed metal that plays an indispensable role in high-tech industries such as semiconductors, liquid crystal displays (LCDs), and photovoltaics. However, due to the scarcity and uneven distribution of primary indium resources, as well as its low-grade occurrence associated with non-ferrous metal ores like lead and zinc, the efficient recovery of indium from secondary resources, including waste liquids, residues from non-ferrous smelting processes, and end-of-life electronic products, has become an inevitable choice. Adsorption method has shown significant potential for indium recovery due to its simplicity and applicability to low-concentration systems. Hence, this paper systematically summarizes recent progress in indium ion adsorption from the perspective of interfacial mechanisms and materials design. The fundamental mechanisms, including physical adsorption (electrostatic interactions, van der Waals forces, and pore confinement effects), cation exchange, and surface complexation, are first elucidated to clarify the adsorption behavior at solid-liquid interfaces. Subsequently, the structure-property relationships of representative adsorbents, including silicabased materials, nanomaterials, biomass and carbon-based materials, polymer adsorbents, and electroadsorption electrode materials, are critically evaluated. Finally, the key challenges, such as poor stability under strong acidic conditions, limited selectivity toward coexisting ions, and difficulties in low-cost large-scale fabrication, are discussed. Future perspectives are proposed with an emphasis on microstructure regulation, cooperative functional group design, and emerging artificial intelligence-assisted strategies, aiming to bridge mechanistic understanding and the rational development of efficient and sustainable indium adsorption materials.

The widespread application of ionic liquids (ILs) as solvents and functional materials raises growing concerns about their environmental persistence and potential toxicity. This study demonstrates the efficient degradation (>96.2% in 20 min) of alkylimidazolium IL, 1-pentyl-3-methylimidazolium by the UV/NaClO process, which remains applicable across a broad pH range and in various real water matrices. By coupling feature-based molecular networking with in silico toxicological assessments, we identified transformation products (TPs) and uncovered potential toxicity risks correlated with structural evolution. Molecular docking showed that dealkylation and hydroxylation attenuate binding affinities with human serum albumin (HSA) and human acetylcholinesterase through diminished hydrophobic contacts. Subsequent molecular dynamics simulations explored the dynamic and thermodynamic behaviors of representative TPs, revealing potential impairment of HSA's transport function and pseudoenzymatic activities triggered by ring-opening. Particular attention is warranted regarding structural risks associated with cleavage at the C(4)═ C(5) bond of the imidazole heterocycle. This work first establishes an analytical-computational framework for mapping degradation pathways and evaluating TP risks, providing both mechanistic insights and practical guidance for the sustainable treatment of IL-containing wastewater.

Efficient removal of chlorophenolic pollutants remains challenging. Iron-modified biochar shows potential in photo-Fenton reactions but suffers from iron leaching and activity instability. Herein, Sycamore leaf Heat treat Char (SHC) was modified with ferric nitrate via low-temperature pyrolysis to construct SHC-Fe-0.2 with a stable Fe-O-C interface. This composite achieved efficient 2,4,6-trichlorophenol (TCP) photocatalytic degradation (removal rate 62.84%, photodegradation contribution 47.01%) and low iron leaching (<5%). Iron was stably immobilized as octahedrally coordinated amorphous Fe-O-C, enhancing electron transfer and reactive oxygen species (ROS) generation. Mechanistically, iron modification switched the degradation pathway from nonradical (O-1(2)-dominated) to radical (center dot OH, center dot O-2(-)-dominated) with a "Fe2+/Fe3+ cycle + surface electron transfer" synergism. This study provides insights for stable iron-carbon composites and deepens understanding of iron-carbon interface behavior.

Harnessing electron spin to suppress photogenerated carrier recombination represents a relatively underexplored frontier in photocatalytic hydrogen evolution. However, conventional photocatalysts are predominantly diamagnetic and respond weakly to external magnetic fields, limiting the exploitation of spin-dependent carrier dynamics. Here, we report for the first time the application of covalent organic frameworks (COFs) in photo-magnetic coupled hydrogen evolution. Specifically, a post-synthetic metalation strategy is developed to introduce high-spin Mn2+ ions (3d5, half-filled configuration) into a chemically robust sp2-carbon-linked COF (sp2c-COFdpy). The resulting sp2c-COFdpy-Mn exhibits intrinsic spin polarization with an unprecedented 100% spin polarization degree at the Fermi level, as revealed by density functional theory calculations. Under an external magnetic field of 500 mT, the material achieves a record photocatalytic hydrogen evolution rate of 208.48 mmol·g-1·h-1. Combined experimental and theoretical analyses demonstrate that the half-filled d5 configuration of Mn2+ maximizes unpaired electrons, inducing strong spin polarization and a large magnetic moment. The external magnetic field further activates negative magnetoresistance and spin-flip processes, synergistically suppressing electron-hole recombination and accelerating interfacial charge transfer to Pt cocatalyst sites. This work not only establishes the first example of COFs in photo-magnetic catalytic hydrogen evolution but also provides a general spin-engineering strategy for designing high-performance magnetically responsive photocatalysts.

Interfaces serve as powerful, versatile platforms that have significantly advanced the development of novel materials. However, bottom‐up construction of reactive interfaces for controlled synthesis of crystalline porous materials still remains a substantial challenge. Here, we constructed a stable, morphology‐tunable reactive interface by spontaneous self‐assembly of amphiphilic moiety derived from Schiff base reactions, featuring the surfactant‐free stabilization and versatile interface morphology readily adjusted by hydrophobic chain length (C4–C12) of aliphatic amines. Such interface confinement lowers nucleation barriers while the localized monomer enrichment speeds reactions, thus enabling a mild, facile, and controlled synthesis of covalent organic frameworks (COFs) with diverse mesoscopic architectures (spherical/ribbon/sheet). Further introducing colloidal SiO 2 nanospheres on the interfaces can co‐assemble and form stable nanoscale Pickering emulsions, yielding hierarchical porous COFs with tunable, large mesopores (17‐40 nm) beyond the intrinsic pore size limitation. The resulting asymmetric hemispherical hollow mCOF PEA (BET surface area of 561.9 m 2 g −1 ) as a potential iodine host (30.18 wt.% loading) delivered remarkable electrochemical performance with an initial capacity of 202.9 mAh g −1 (96.16% of theoretical value) and retained 132.8 mAh g −1 after 2500 cycles, profited from their mesoporosity and asymmetric morphology with an increased surface area, exposed more active sites and enhanced ion transport ability.

The continuous rise in atmospheric carbon dioxide (CO 2 ) poses a major threat to the global climate.

In this study, a heterojunction composite (NCDs/ZnFe2O4), prepared from nitrogen-doped carbon dots and ZnFe2O4 sourced from the extraction of blast furnace slag, was tested for its ability to degrade organic pollutants (Rhodamine B (Rh B) and phenol) through photocatalytic degradation. Utilizing blast furnace slag as an iron source not only reduces costs but also aligns with the principles of resources recycling. The structural, optical, and electrochemical properties of the composite were thoroughly investigated by means of XRD, FTIR, XPS, SEM, TEM, EIS, BET, PL, and UV-vis/DRS analyses. The results show that the NCDs/ZnFe2O4 composite exhibits enhanced absorption intensity in the visible region and red-shifted absorption wavelengths compared to ZnFe2O4. Specifically, an optimal composition of 3 wt% NCDs in the composite based on the mass of ZnFe2O4 showcased excellent photocatalytic activity, resulting in a degradation rate of Rh B as high as 92.99%. Furthermore, the catalytic degradation rate remained stable at 92.51% even after five cycles, demonstrating good stability. The investigation of the photocatalytic mechanism of Rh B degradation by NCDs/ZnFe2O4 reveals that holes, superoxide anion radicals, electrons, and hydroxyl radicals are the primary active species, among which superoxide anion radicals exhibit the strongest oxidizing ability. Furthermore, the NCDs/ZnFe2O4 composite also demonstrates excellent photocatalytic performance for degrading phenol in wastewater. This study introduces a novel approach to developing an efficient system for the degradation of organic pollutants in wastewater.

This work pioneers precise fluorination engineering in pyrene-based covalent organic frameworks (COFs) to unlock exceptional photocatalytic hydrogen (H2) evolution. Through systematic modulation of fluorine substitution patterns, we synthesized three distinct COFs: non-fluorinated (TF0CN-COF), fully fluorinated (TF1CN-COF), and partially fluorinated (TF0.5CN-COF). While TF0CN-COF's symmetric donor-acceptor structure permits intramolecular charge transfer, it suffers from weak electron localization and scarce active sites. Conversely, TF1CN-COF's full fluorination enhances carrier separation but its over-symmetry diminishes polarization and passivates catalytic centers. Critically, the partially fluorinated TF0.5CN-COF induces strong polarization that disrupts framework symmetry, generating a directional built-in electric field to localize electron density. Remarkably, the optimized TF0.5CN-Cu achieves a record hydrogen evolution rate of 10.5 mmol h-1g-1, representing a 47.8 fold enhancement over TF0CN-COF. The work establishes a noble-metal-free paradigm leveraging irreversible C--C linkages for stability and asymmetric fluorination for electronic control. By elucidating fluorination-mediated structure-property relationships, this study provides a blueprint for designing efficient COF photocatalysts through active-site and band-structure synergy.