Vacancy-engineered Ga 3 In 5− x Ge 2+ x O 16 achieves carrier–phonon decoupling through Ge 4+ induces indium vacancies, enhancing electrical conductivity and suppressing lattice thermal conductivity, achieving a zT of 0.5 at 973 K in an indium-lean oxide.

The excessive use of tetracycline hydrochloride (TCH) poses a threat to ecological integrity and public health. This urgency necessitates the development of sensitive, accurate, and rapid sensing technologies for TCH detection. Herein, we developed a novel molecularly imprinted photoelectrochemical sensor based on CdS and oxygen vacancy-regulated TiO2 nanotube arrays (Ov-TNTs). The introduction of oxygen vacancies broadens the light absorption range of TiO2 and facilitates the effective separation of photogenerated electron-hole pairs. Additionally, the decoration with narrow-bandgap CdS QDs (2.4 eV) further enhances the visible-light harvesting capability of the sensor. Furthermore, a molecularly imprinted polymer (MIP) film with specific recognition capability, which offers the advantages of facile preparation, time efficiency, and low cost, was introduced onto the sensing platform to further optimize its performance and significantly enhance the sensor's selectivity and anti-interference ability. The proposed sensor exhibited excellent analytical performance for TCH detection, offering a wide linear range from 0.1 nM to 0.1 mu M and a low detection limit of 0.032 nM (S/N = 3). This strategy provides a universal platform for detecting other antibiotics through the replacement of molecularly imprinted films in aquatic environments.

Contact-electro-catalysis (CEC) provides a promising route for per- and polyfluoroalkyl substances (PFAS) remediation, yet the mechanistic role of chloride ions (Cl-) in real water matrices remains unclear. Here, we demonstrate that Cl- markedly enhances removal of perfluorooctanoic acid, perfluorooctanesulfonic acid, hexafluoropropylene oxide dimer acid, perfluorononyloxybenzene sulfonate, and 6:2 fluorotelomer sulfonate, achieving 97.04 -99.99% degradation and 96.90 -99.98% defluorination within 120 min at 200 mM Cl-. These rates were 1.43-2.29-fold higher than Cl--free systems. Mechanistic analyses reveal that hydroxyl radicals (•OH) oxidizes Cl- to generate chlorine radicals (Cl•), which selectively attack the carboxylate group of PFAS, enabling thermodynamically favorable decarboxylation followed by mineralization. Unlike conventional electrochemical methods, the Cl•-mediated pathway avoids oxychlorine and chlorinated byproducts. Zebrafish embryo assays further confirmed negligible toxicity of treated solutions. These results establish a sustainable paradigm that achieves high defluorination efficiency and operational safety, offering strong potential for PFAS remediation in saline and industrial waters.

Constructing special structure for metallic silicates makes active sites more dispersed and improves the utilization rate. However, complicated processes are usually not preferred, while the synergistic micro-mechanism of bimetal in silicates are still being ignored. Herein, a facile coprecipitation synthetic strategy is proposed to fabricate series of metallic silicate nanoparticles within 5 min, which exhibits extensive versatility and convenience. Among them, Cu-doped cobalt silicate (CuCoSi) is confirmed with best synergistic effect of bimetal in silicates. A comprehensive synergistic micro-mechanism at molecular and electronic levels is further proposed. Experimental and theoretical analysis suggests that the d orbital of Co-Co provides unique active site in CuCoSi. Cu doping improves the conductivity of the structure and transfers electrons to surrounding Co to cause relatively high electron occupation intensity at Fermi surface, promoting the activation progress. Cu doping further facilitates the formation of *O to generate 1O2 and CoIV=O by dissociation from H2O2* to H2O-O* on CuCoSi surface. As a result, CuCoSi is highly efficient in the paradigm of catalytic decomposition series of synthetic organic contaminants and various pathogenic microorganisms, along with an excellent recycling stability. Revealing of theoretical and experimental evidence is desirable for rational customized bimetallic silicate catalyst.

The mecA genes pose a serious threat to human health. Their widespread detection in actual water samples is greatly hindered by their low concentration and complex matrix interference. Therefore, an electrochemiluminescence (ECL) biosensor based on a tetrahedral DNA framework (TDF) anchoring high-performance ECL luminophores is developed for ultrasensitive and anti-interference detection of mecA genes. The introduced TDF can immobilize probes that specifically recognize mecA genes and enhance the stability and durability of the biosensor. Importantly, the high-performance ECL luminophores combine ultrabright gold nanoclusters under the protection of Cys-Arg-Arg-Arg peptides and 6-aza-2-thiothymine (CR4/ATT/AuNCs, ultrahigh quantum yield), resulting in a ∼266-fold improvement in ECL intensity (compared with ATT/AuNCs). The conformational rigidity of CR4 and ATT is attributed to intra-cluster hydrogen bonds between them. This promotes ordered π-π stacking and markedly enhances the ECL quantum efficiency of CR4/ATT/AuNCs (∼3.26-fold). Benefiting from the unique nanoconfinement effect, uniformly sized covalent organic frameworks (COFs), as supporting substrates to inhibit the aggregation of CR4/ATT/AuNCs, contributes to the accumulation of reactive radicals, while its outstanding adsorption capacity efficiently increases the local concentrations of co-reactants and CR4/ATT/AuNCs to promote the decomposition of co-reactants to generate more reactive radicals. The biosensor with a low limit of detection (LOD, S/N = 3) of 0.72 fM has excellent repeatability, stability, and selectivity after further amplifying the reaction signal using catalytic hairpin assembly (CHA), achieving direct detection of mecA genes in wastewater samples.

The electrocatalytic hydrogen evolution reaction (HER) in neutral media is fundamentally limited by sluggish water dissociation. Here we report a Ru single-atom catalyst supported on hydrogen tungsten bronze (Ru & horbar;HxWO3) and show that its high activity originates from strong metal-support interaction (SMSI) at the Ru & horbar;O & horbar;W interface. The strong Ru-support coupling induces pronounced interfacial polarization, which restructures the local hydration layer and enriches activation-relevant interfacial water configurations for the Volmer step. As a result, Ru & horbar;HxWO3 achieves an ultralow overpotential of 14 mV at 10 mA cm-2, delivers a high Ru mass activity of 11.09 A mgRu -1 at 100 mV, and sustains stable HER operation for 80 h at 1 A cm-2 in neutral media. This work elucidates a complete mechanistic pathway, demonstrating how strong Ru-support coupling leverages interfacial electronic modulation to dynamically control hydration-layer structure, thereby accelerating HER kinetics in neutral media.

Water pollution is becoming increasingly severe,posing a serious hazard to human health and ecological security.Therefore,it is necessary to develop rapid,sensitive,and universal analytical methods to detect residual pollutants in actual water.Elec-trochemiluminescence(ECL)is a highly promising analytical technology for monitoring pollutants due to its inherent ad-vantages,such as zero background and ultrahigh sensitivity.Rare metals(rare earth metals,precious metals,and refractory rare metals)with unique electronic structures,significant catalytic activity,stable optical properties,and perfect conductivity can significantly enhance the performance of ECL sensors by regulating luminescence efficiency,signal amplification,and specific recognition.Regarding the different functional roles of rare metals in the construction of ECL sensors,their applications are divided into signal amplification materials,ECL nanoemitters,and resonance energy transfer receptors or donors.Focusing on key pollutants(high toxicity,strong bioaccumulation potential,and wide-ranging impacts)in aqueous environments as ana-lytes,this review classifies rare metal-based ECL sensors and emphasizes their recent advances.It analyzes the intrinsic pathways through which rare metals enhance ECL efficiency when employed as electrode modification materials,with particular emphasis on the structure-activity relationships between rare metal-based materials and ECL performance,clarifying the enormous potential of rare metal-based ECL sensors in breaking through the limitations of existing detection methods.This review also discusses the design methodologies meeting the application requirements of ECL sensors,such as diverse signal amplification strategies and innovative sensing modes in rare metal-integrated ECL sensors.Finally,it analyzes the current problems of rare metal-based ECL sensors in water pollutant detection and proposes potential optimization pathways for the future.

Testing luteolin is essential to promote its appropriate clinical use, regulate the quality of pharmaceuticals and safeguard public health. In this work, the activated loofah sponge carbon/poly(3,4-ethylenedioxythiophene)-gold nanocomposites (LSAC/PEDOT-Au) were successfully prepared through an efficient and straightforward method. The surface morphology and structural characteristics of the synthesized nanocomposites were systematically characterized. A glassy carbon electrode (GCE) modified with LSAC/PEDOT-Au nanocomposites was fabricated as a novel luteolin sensor. At the optimal experimental conditions, the LSAC/PEDOT-Au/GCE exhibited a high sensitivity of 3.3 & times; 10-9 mol dm-3 and a wide linear range of 0.05-2 and 2-40 & micro;mol dm-3 toward luteolin oxidation, demonstrating satisfactory selectivity and stability. In addition, the developed LSAC/PEDOT-Au/GCE was further evaluated for its ability to detect luteolin in honeysuckle samples, yielding highly satisfactory results.

The hydrogen evolution reaction (HER) is a cornerstone of green hydrogen production, yet its efficiency is constrained by the sluggish kinetics of water splitting. High-entropy catalysts (HECs), single-phase materials incorporating multiple principal elements, have emerged as a transformative solution. Their unique attributes including vast compositional flexibility, tunable electronic structures, and synergistic multi-element interactions, enable them to overcome the activity, stability, and cost limitations of conventional catalysts. Despite rapid performance advancements, the rational design of HECs is fundamentally hampered by critical knowledge gaps, particularly in identifying true active sites under operando conditions and predicting long-term stability. This work critically assesses these challenges, systematically summarizing the latest progress in HECs design, synthesis, and structure–activity relationships. By bridging fundamental principles with practical applications, we provide a forward-looking perspective on key research directions. Distinct from recent progress-focused reviews, this work establishes a strategic roadmap by systematically diagnosing seven grand challenges across the science-to-technology pipeline and proposing corresponding countermeasures. This framework aims to guide future research efforts toward the rational design and practical deployments of HECs for practical and cost-effective green hydrogen production.

Silicon suboxide (SiOx) is a viable alternative to pure silicon (Si) for anode of lithium-ion batteries, offering reduced volume expansion and low cost, but it still struggles with low electrical conductivity and initial coulombic efficiency. To address these challenges, a ternary KFC/SiOx@C composite anode are reported by using Kapok fiber carbon (KFC) as microtube substrate. Hydrophilic treatment enhances surface reactivity of the KFC microtube, enabling the sol-gel growth of SiOx with interfacial Si-O-C bonds, followed by polydopamine coating and carbonization. The resulting KFC/SiOx@C anode manifests excellent discharge capacity (1465.1 mAh g- 1 at 0.5 A g- 1), cyclability (reversible capacity of 733.9 mAh g- 1 after 500 cycles, and rate capability (484.5 mAh g- 1 at 2 A g- 1). The synergistic effects of the buffering KFC microtubes, robust interfacial bonding, and conductive carbon network are identified as key factors for the enhanced performances. This work provides a green and economical strategy for developing advanced SiOx-based anodes.

Anion exchange membrane water electrolysis (AEMWE) is attracting increasing attention for hydrogen production, as it operates under alkaline conditions and enables the use of low-cost catalysts. However, the development of anion exchange membranes (AEMs) is still hindered by the trade-off between high ionic conductivity and dimensional stability. Herein, crosslinked ether-free poly(triphenyl alkyl)-based AEMs incorporating flexible dual-cation side chains are developed. A hydrophobic crosslinked network constructed with 1,6-hexanediamine effectively suppresses excessive membrane swelling. The intrinsic incompatibility between the hydrophilic dual-cation side chains and the hydrophobic backbone drives the formation of well-organized microphase-separated structures, enabling efficient ion transport. The optimized membrane delivers a hydroxide conductivity of 141.9 ± 2.0 mS cm−1 with a swelling ratio of 5.7 ± 0.1% at 80 °C. The crosslinked membrane preserves 90.9% of its initial conductivity after 1600 h in 2 M NaOH at 60 °C. In AEMWE, the membrane delivers 1.80 A cm−2 at 2.0 V (60 °C) and operates stably for 375 h at 0.5 A cm−2. These results demonstrate that the designed AEMs are promising candidates for efficient and stable hydrogen production.

A novel continuous-flow system coupling partial nitrification/Anammox (PN/A), partial denitrification (PD), and Anammox (Amx) biofilm reactors was developed (PN/A-PD-A) to treat mature landfill leachate (MLL). To maximize synergy, the NH4+-N removal in the PN/A reactor was regulated based on the NO2--N accumulation ratio (NAR) in the PD stage, ensuring optimal substrate stoichiometry for the final Amx polishing step. Over 174 days of operation, the system achieved a superior total nitrogen removal efficiency (TNRE) of 98.30 ± 0.14% (effluent TN: 21.80 ± 1.71 mg/L). The PN/A granular sludge, enriched with Candidatus_Kuenenia (5.87%) and Nitrosomonas (9.73%), demonstrated high adaptability to MLL characteristics and contributed to 83.51% of the TN removal. In the PD stage, the dominant genus Thauera (43.91%) facilitated efficient NAR (82.86 ± 1.61%) at a limited COD/NO3--N ratio of 2.32 ± 0.02. The Anammox biofilm (Candidatus_Kuenenia, 27.80%) in the Amx reactor contributed to 13.10% of TN removal, ensuring to meet the MLL discharge standard. Kinetic and metagenomic analyses confirmed that distinct shifts from complete to partial nitrification (and denitrification) in enzymes activity and gene abundance under chronic MLL stress underpinned the robust NO2--N accumulation in both PN/A and PD reactors. Notably, compared to conventional nitrification-denitrification process, the PN/A-PD-A system significantly reduced oxygen demand (60.18%), exogenous organic carbon consumption (91.61%), sludge yield (83.72%), and CO2 emission (94.66%), demonstrating a sustainable pathway for low-carbon nitrogen removal from high-strength wastewater.

Electrosynthesis of bulk chemicals such as active chlorine depends on the most reactive crystal facets, yet these facets are often thermodynamically disfavored during crystal growth. Here, we present a faceting strategy that integrates 3D printing with electric field inducement to reorient triclinic Ti4O7, realizing a dominant facet transition from (1 - 2 0) to high-energy (0 2 - 2) by storing and releasing strain energy to promote the preferential growth of crystal. Such transition trigger active site switching from O on pristine (1 - 2 0) facet to Ti on the reoriented (0 2 - 2) facet, greatly boosting the active chlorine generation rate to a comparable level (0.19 mg·min-1·cm-2) to benchmark dimensionally-stable anodes while suppressing parasitic water activation. A flow-by reactor reaches high active chlorine generation rates of 0.33-0.35 mg·min-1·cm-2 within 2.9-8.9 s, outperforming industrial dimensionally-stable anodes. This strain-induced faceting approach establishes a general paradigm for controllable crystal reorientation and underscores the potential of 3D printing to expand facet engineering for advanced catalytic systems.

The extensive global application of chlorpyrifos (CPF) has led to significant environmental accumulation through aquatic systems, presenting substantial risks to ecological integrity and public health. This urgency necessitates advanced detection methodologies with enhanced sensitivity and operational efficiency to ensure environmental safety. Here, we developed a novel photoelectrochemical aptamer sensor utilizing a MIL-101(Cr)&Bi2S3 heterostructure composite. This architecture synergistically integrates the broad-spectrum photon absorption capability of Bi2S3 with the hierarchical porosity and structural stability of MIL-101(Cr), achieving remarkable enhancement in both electron-hole separation efficiency and interfacial charge transfer. The sensing platform was further optimized through aptamer functionalization, which confers precise molecular recognition capabilities while maintaining optimal charge transfer dynamics at the electrode interface. Systematic evaluation demonstrated exceptional analytical performance: a linear detection range spanning four orders of magnitude (0.05-10 mu g/mL), ultralow detection limit of 0.022 ng/mL (S/N = 3). The developed methodology provides a versatile framework for adapting to other organophosphorus pesticide detection requirements through modular aptamer replacement.

Seawater electrolysis driven by offshore renewable energy is a promising avenue for large-scale hydrogen production but faces challenges in designing robust anodes that suppress surface chlorine reactions and corrosion at high current densities. Here we report a strategy by selectively docking PW 12 -polyoxometalate (PW 12 -POM) onto Fe sites of CoFe hydroxide anode to modulate the electronic structure of adjacent Co active centers and regulate Cl⁻/OH⁻ adsorption for efficient alkaline seawater oxidation. Our CoFe-based anode achieves low overpotentials, high catalytic selectivity, and notable durability, with continuous operation at 1 A cm⁻² for over 1300 hours and at 2 A cm⁻² more than 600 hours. Theoretical calculations and ex situ/in situ analyses reveal that PW 12 -POM coordination at Fe sites stabilizes Fe, suppresses its leaching, modulates Co acidity, promotes OH⁻ adsorption, and protects metal sites from Cl⁻ corrosion.

Avoiding electron and hole recombination was always widely concerned during the design and synthesis of photocatalyst in photocatalytic water treatment, while the laws and strategies of individual hole interactions and accumulation have been rarely studied. In this study, a novel photocatalyst featuring a BiOI-modified n-n type heterojunction (TiO2@BiOI-OVs) has been introduced for efficient photocatalytic water treatment under visible light irradiation. The photocatalyst demonstrates a remarkable capability for accumulating photogenerated holes, crucial for effective water treatment processes. Upon photoexcitation, carriers swift traverse through the TiO2@BiOI-OVs structure via the n-n heterojunction transfer pathway, propelled by a directional interfacial electric field. This mechanism significantly curtails carrier recombination rates, as evidenced by the notably shortage average radiative lifetime of recombination on TiO2@BiOI-OVs (14.114 ns) compared to TiO2 (43.412 ns). Furthermore, the introduction of oxygen vacancies within TiO2@BiOI-OVs serve as electron traps, proficiently capturing photogenerated electrons. This action aids in the separation of charge carriers and fosters the accumulation holes endowed with potent oxidation capabilities. Density functional theory calculations demonstrated the formation of heterojunction effectively reduces the band gap of TiO2@BiOI-VOs and improves its responsiveness to visible light. Consequently, the kinetic constants for the photodegradation of tetracycline hydrochloride by TiO2@BiOI-OVs (0.0791 min-1) were observed 5.8 times higher than those exhibited by pristine TiO2. The photogenerated holes was mainly responsible for the TCH removal by radical quenching experiments and EPR measurements analyses. This investigation unveils a compelling strategy for systematic design of BiOI-modified n-n type heterojunction photocatalysts tailored for environmental remediation applications.

BACKGROUND:Surface-enhanced Raman spectroscopy (SERS) substrates have undergone extensive development over the years, yet the challenge of significantly enhancing their sensitivity persists. Most existing substrates face considerable difficulties in obtaining the strongest electromagnetic coupling to maximize SERS signal intensity, i.e., it is hard to achieve optimal structural parameters such as the gap width and particle size, and to fabricate surfaces that are free from contamination such as surfactants. Therefore, there is a pressing need for a substrate optimization approach that allows for in-situ monitoring and real-time dynamic adjustments to precisely achieve the ideal substrate characteristics for superior performance. RESULTS:In this study, a highly sensitive porous copper-gold (Cu-Au) SERS substrate was fabricated using the galvanic replacement reaction (GRR), coupled with in-situ SERS monitoring to optimize substrate preparation. The Cu-Au nanoparticles formed and grew on sacrificial templates while noble metal ions were reduced by the sacrificial metal during GRR. The substrate preparation process revealed that the optimal preparation time was 200 ± 20 s. The SERS performance with crystal violet (CV) as a probe molecule demonstrated the substrate's remarkable sensitivity with detecting concentrations as low as 10-16 M, which surpasses most literature reports. The optimized SERS substrate was further tested for detecting malachite green (MG), yielding an ultra-high enhancement factor (EF) of 8.96 × 1014. The entire optimization process did not involve the addition of aggregation or surfactant agents, ensuring a clean substrate surface. SIGNIFICANCE AND NOVELTY:This study is a further proof of the significance of the in-situ optimization of SERS substrates via GRR which allows real-time adjustment of nanoparticle size and gap width to enhance sensitivity. This approach has enabled us to develop substrates with exceptional sensitivity and reproducibility. These significant contributions may open up new avenues for the facile fabrication of ultrasensitive SERS substrates.

A photoelectrochemical (PEC) biosensor composed entirely of carbon nanomaterials was synthesized to detect carbohydrate antigen 19-9 (CA 19-9). The biosensor platform integrated graphitic carbon nitride (GCN), known for its light sensitivity, polythiophene (PTh), an organic conductive and optically active material, and 1-pyrenebutyric acid N-hydroxysuccinimide (PBASE), which functions both as a biolinker to conjugate CA 19-9 antibody and antigen and as an electron mediator to facilitate electron transfer from GCN to PTh. The formation of a Schottky heterojunction between PTh and GCN reduced the bandgap of GCN from 2.66 to 1.96 eV, which enhanced transfer of photogenerated electrons for cathodic photocurrent generation. The improvement of charge transfer due to heterojunction formation and π-π stacking between GCN and the pyrene group of PBASE is confirmed by cyclic voltammetry (CV), electron impedance spectroscopy (EIS), and chronoamperometry (CA) findings. The highest current of 1.31 μA is observed for combination of 5 wt% PTh with a GCN/PBASE ratio of 1:0.5. Besides evaluating the electron mobility of GCN/PBASE/PTh, CV, EIS, and CA were also used to evaluate the sensor performance. Optimization studies revealed that 0.6 μg of CA 19-9 antibody and 1 h of antigen-antibody immobilization time significantly improved the biosensor response. The GCN/PBASE/PTh biosensor demonstrated high sensitivity to CA 19-9 antigen across a concentration of 50-1000 U/ml and a detection limit as low as 0.052 U/ml. The reported working range is within the limits required for diagnostic testing of patients with hepatic and heart problems as well as for post-treatment monitoring of colorectal and pancreatic cancer patients.

The excessive use of chlortetracycline (CTC) has the potential to adversely affect ecosystems and threat human health by inducing antibiotic-resistant infections, necessitating a rapid, sensitive and accurate detection method for CTC. Here, an electrochemical sensor based on molecularly imprinted polymer (MIP) has been developed that utilized poly o-phenylenediamine (poly-o-PD) film to specificity detect CTC, which preparation process was lowcost, time-saving and simple. It combines the recognition capabilities of MIP with the outstanding electrochemical performance of electrode modification materials, namely tungsten disulfide (WS2) and carboxylated multi-walled carbon nanotubes (MWCNTs-COOH). And, in order to verified the optimal ratio of CTC (template) and o-PD (monomer), the density functional theory is performed by Vienna Ab Initio Simulation Package (VASP) within the generalized gradient approximation to calculate the interaction energy of CTC-o-PD. The sensor detects CTC by analyzing the current changes of the redox-active probes in response to the binding of CTC to the imprinted sites on the modified electrode surface. The sensor reveals a high affinity toward CTC binding, enabling the detection of CTC concentrations within the range of 0.5 - 425.0 mu M, with a detection limit of 18.5 nM (S/N = 3). Meanwhile, the sensor harnesses the advantages of screen-printed electrode (SPE) such as miniaturization, suitability for large-scale production, and cost-effectiveness, to further enhance the practicality. The sensor described herein has been successfully used for specific quantitative detection of CTC in actual water, demonstrating its practical applicability.