Low-temperature conditions have long hindered the removal of organic pollutants from water in cold regions. In this study, a photothermal catalyst was prepared by embedding polyoxometalates into metal-organic frameworks using electrospinning and high-temperature pyrolysis methods. Furthermore, a synergistic advanced oxidation technology combining visible light irradiation and peroxymonosulfate (PMS) activation was developed to effectively remove organic pollutants from low-temperature water. The introduction of polyoxometalates and morphological regulation significantly inhibited metal active sites agglomeration, and increased absorption of incident light and photothermal conversion efficiency. The resulting local high temperatures on the surface of catalyst effectively facilitated PMS activation, enabling an ibuprofen removal efficiency of 92.3% at 10 degrees C. By decoupling the mechanisms of different reaction systems, it was revealed that the photothermal conversion effect under visible light is the dominant factor in PMS activation, accounting for up to 54.4% of the overall process. The quenching experiments, electron paramagnetic resonance analysis, and electrochemical tests jointly confirmed that the degradation process involves both direct electron transfer and non-radical pathways dominated by 1O2. Furthermore, density functional theory calculations demonstrated that the charge separation and transfer facilitated by polyoxometalates as electron acceptors, combined with the photoexcited plasmon resonance effect, synergistically enhanced the catalytic efficiency under low-temperature conditions. This catalytic system has demonstrated strong resistance to interference and practical effectiveness through repeated utilisation, real-water experiments, and outdoor low-temperature photocatalytic applications. This study offers novel insights and a promising strategy for the efficient elimination of refractory pollutants in cold environments.

Selective oxidation of cellulose to C1/C2/C3 acids, such as glycolic acid (GA), lactic acid (LA), and formic acid (FA), represents an attractive route for biomass utilization. Aerobic oxidation of cellulose proceeds via multiple pathways, including hydrolysis to glucose by Brønsted (B) acids, subsequent oxidation to various acids, Lewis (L) acid-catalyzed isomerization to fructose, and L/B acid co-catalyzed [4+2] retro-aldol condensation to glycolaldehyde and erythrose, for which multifunctional catalysts are essential to control product distribution. Herein, polyoxometalates (POMs), H3PMo12O40, were solidified by introducing L-acidic Ag+ cation via mechanochemical synthesis. During this process, metallic Ag0 was generated in situ and anchored on the surface of reduced POMs through Ag0–O–MoVI interaction in the presence of ethanol. Experimental and theoretical studies revealed that the interaction of Ag0-O-MoVI, together with the coexistence of mixed-valence Ag+/Ag0 and MoVI/MoV, induced the changes and splitting of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies, modulated acid content and distribution, and established electron transfer mediator (ETM) and electron donor couples. As a result, cellulose conversion rate over Ag0(1.40 wt%)/Ag0.75H3.25PMoVI11MoVO40 (abbreviated as Ag0(1.40)/Ag0.75H3.25PMo) increased by 2.1 and 1.5 times compared with H3PMo12O40 and AgH2PMo12O40 powders, respectively. Mechanistic studies suggested that Ag/Mo dual active sites in Ag0/AgnH3−nPMo12O40 acted as adsorption sites for glucose, likely facilitating the formation of a pentagonal-ring intermediate that promoted [4+2] retro-aldol condensation rather than isomerization to fructose, thereby enhancing GA production. Furthermore, turning the Ag+ content in Ag0(1.40)/Ag0.75H3.25PMo and Ag0(1.28 wt%)/Ag2.75H0.83PMoVI11.43MoV0.52O40 (abbreviated as Ag0(1.28)/Ag2.75H0.83PMo) enabled tunable selectivity toward GA (51.7%) and LA (15.9%) or GA (29.1%) and LA (35.6%), respectively. In addition, Ag0/Ag+H3PMo12 exhibited a uniform and tough nanospherical morphology, which acted as a micro-ball mill to facilitate a synergistic physicochemical process of nanoscale shearing and strong interfacial adsorption, effectively disrupting hydrogen bonds in cellulose and enhancing its conversion. Overall, this work presents an efficient strategy to design dual-active POM nanohybrids for coupled acidic-redox transformations.

A zinc-mediated catalyst-free cross-electrophile coupling of gem-difluoroenol sulfonates with N-(acyloxy)phthalimides is developed. It efficiently affords diverse α,α-difluoroketones with broad radical compatibility, good gram-scale scalability, and functional group tolerance, enabling access to complex amino acid and glycosyl derivatives.

A series of Mo/V-containing polyoxometalates(POMs),H3+nPMo12-nVnO40(n=0-5,8),were evaluated for their peroxidase(POD)-and sarcosine oxidase(SOX)-like activities.Mechanistic studies revealed that the POD-like activity originated from the redox properties of the Mo/V POMs,with protons participating via a proton-coupled electron transfer(PCET)process to activate H2O2 and generate·OH through a Fenton-like pathway.Among them,(NH4)5H6PMo4V8O40(abbreviated as HPMo4V8)exhibited the highest POD-like activity,with Km and vmax values of 5.814 μmol·L-1 and 8.065 μmol·L-1·min-1,respectively,for the H2O2-mediated oxidation of 3,3',5,5'-tetramethylbenzidine(TMB).Furthermore,HPMo4V8 displayed excellent SOX-like activity,catalyzing the aerobic oxidation of sarcosine(Sar)to produce H2O2,glycine,and formaldehyde.By coupling these two enzyme-like activities,a cascade colorimetric platform(HPMo4V8/Sar/TMB)was established for Sar detection.The H2O2 generated from Sar oxidation was quantified via TMB color changes,enabling indirect determination of Sar concentration.Under optimal conditions(pH=3,25 μmol·L-1 HPMo4V8,15 mL·min-1 O2,25 ℃),a good linear relationship between absorbance at 652 nm and Sar concentration was obtained in the range from 10.0 to 30.0 μmol·L-1,with a detection limit(LOD)of 9.123 μmol·L-1.This bifunctional POM-based nanozyme offers a simple,stable,and cost-effective alternative to natural enzymes,allowing qualitative and quantitative colorimetric detection of Sar by UV-Vis spectroscopy or naked-eye observation.The novel technique used new POM materials to successfully apply in Sar and H2O2 detection in urine without complex pretreatment instead of natural enzymes with great potentials.

The selective upgrading of biomass-derived platform molecules under mild conditions remains a significant challenge in advancing the substitution of fossil resources and promoting cleaner production. 5-Hydroxymethylfurfural (5-HMF), a versatile chemical intermediate derived from carbohydrate-rich biomass, has emerged as a critical platform compound bridging renewable feedstocks and value-added products in sustainable chemistry. We report a novel electron-transfer mediator (ETM)-assisted strategy for efficient aerobic oxidation of 5-HMF to 2,5-diformylfuran (DFF) under ambient pressure, achieved by anchoring (NH4)5H6PMo4V8O40 (NPMoV) on mesoporous g-C3N4 (mpg-C3N4) via hydrogen bonding. These NPMoV(n)/mpg-C3N4(n = 10, 20, 25, 30, 35 %, POM loading amount) showed high activity in activating oxygen to oxidize 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF) under atmospheric pressure of O2. NPMoV(30)/mpg-C3N4 achieves 90.6 % DFF yield at 97.6 % conversion. This superior performance originates from its unique structure of BrØnsted acidic, redox, basic sites in one, as well as strong absorption of 5-HMF. Meanwhile, the direct interaction between polyanion and mpg-C3N4 enables faster electron transfer in hybrids than in NPMoV. Here mpg-C3N4 acts as an ETM, accelerating electron transfer between NPMoV and O2 while suppressing overoxidation via spatial confinement of DFF. Meanwhile, the multifunctional sites in NPMoV(30)/mpg-C3N4 allow the fructose and glucose to be converted to DFF undergoing acidic/basic catalyzing isomerization, dehydration over acidic sites, and oxidation by redox sites. The strong interaction between NPMoV and mpg-C3N4 permitted no leaching of active sites of NPMoV confirming its high stability and recyclability. This work integrates technical and economic analyses to propose a scalable strategy for the high-value utilization of biomass platform compounds.

Fe-based metal organic frameworks (Fe-MOFs) are promising for peroxymonosulfate (PMS) activation, yet their performance is limited by sluggish Fe3+/Fe2+ cycling and inefficient interfacial charge transfer. Herein, a heterointerface-engineered catalyst, PMoV2(30)/NH2-MIL-101(Fe), is constructed by integrating H5PMo10V2O40 (PMoV2) clusters into an amino-functionalized MIL-101(Fe) framework to modulate interfacial electronic structure. Structural characterization confirms that the framework is preserved, while the Fe local coordination environment and interfacial charge distribution are effectively reconstructed. Benefiting from the synergistic coupling between electron-donating amino groups and redox-active PMoV2 species, the catalyst exhibits markedly enhanced PMS activation, achieving complete bisphenol A removal within 30 min with a rate constant 15.5 times higher than that of MIL-101(Fe). Mechanistic investigations reveal a non-radical pathway dominated by singlet oxygen (1O2), enabling selective oxidation. The coupled Fe3+/Fe2+ and V5+/V4+ redox cycles accelerate interfacial electron transfer, while density functional theory calculations indicate strengthened PMS adsorption and a reduced energy barrier for 1O2 generation. The catalyst also demonstrates high stability, broad pH applicability, and negligible metal leaching. This work highlights an effective strategy for regulating interfacial electronic structure toward selective PMS activation.

Stimuli-responsive materials integrating photochromism and luminescence switching are widely utilized in anticounterfeiting, data encryption, optical storage, green printing, and sensing. Here, a series of photoresponsive composite films with tunable multicolor luminescence were fabricated by doping lanthanideu2013polyoxotungstates into an agarose matrix via a combined solu2013gel and casting method. Characterization via X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and elemental mapping confirmed the successful fabrication and uniform doping of the films. Spectroscopic analyses revealed that the dopant content effectively tuned the optical transmittance and emission intensity of the films. Crucially, the films exhibited reversible photochromism and synchronous luminescence switching upon alternating ultraviolet irradiation and oxygen exposure. This switching behavior was repeatable for a minimum of 10 cycles with minimal fatigue, underscoring their potential as multifunctional, stimuli-responsive smart optical materials.

Revealing the mechanism of photocatalytic organic transformation in aqueous solutions is crucial for photocatalytic processes, yet precisely regulating complex interfacial electron transfer and the microenvironment of reaction molecules remains challenging. Inspired by cellular structures and natural metalloproteins, we construct a ZIF-67@CoS/CdS nanoreactor mimicking organelle architecture. This system enables directional charge transport and hydrogen-bond microenvironment regulation, allowing efficient co-production of H2 and pyruvic acid under light irradiation. Characterizations and calculations reveal that the interfacial electric field accelerates charge migration, while the catalyst reduces the energy barriers for water dissociation and hydrogen formation by modulating hydrogen bonds. The optimized catalyst delivers a molar-level H2 activity of 1457.1 mmol m-2 (5 h, 1,000 cm2) under sunlight, with a pyruvic acid selectivity of 91.2%. In this work, we propose a design strategy for an organelle-mimetic nanoreactor for scalable sunlight-driven H2 production and selective pyruvic acid synthesis.

Photothermal (PT) synergistic catalysis for the conversion of CO2 to methanol (MeOH) represents a promising strategy for CO2 utilization. However, the development of Cu-ZnO catalysts exhibiting high thermal stability and photocatalytic activity remains a critical challenge for efficient CO2 conversion via the PT catalysis. To address these issues, Pd single atoms are successfully anchored onto the Cu-ZnO surface of the Z-scheme heterostructure (designated as Pd1/Cu-ZnO), resulting in three distinct asymmetric coordination environments: Pd-O-Cu, Pd-Cu, and Pd-O-Zn. The non-uniform charge distribution at the Pd-Cu site on Pd1/Cu-ZnO enhances the adsorption and dissociation of H2, while the Pd-O-Zn site simultaneously optimizes the CO2 adsorption configuration, thereby promoting significant elongation of the C=O bond. The band structures of semiconductors (CuO and ZnO) are modulated by Pd single atoms, which simultaneously enhances the localized surface plasmon resonance (LSPR) effect for Cu0, thereby improving Pd1/Cu-ZnO light response. The MeOH yield achieved with Pd1/Cu-ZnO as the catalyst is 1.45 times greater in the PT catalytic reaction compared to the thermal catalytic reaction, reaching 332.1 mmol·g-1Cu·h-1, while the selectivity increased from 50.1% to 87.2%, highlighting the exceptional performance of the single atom asymmetric sites. This study underscores the crucial role of single atoms in PT synergistic catalysis, demonstrating their superior potential for enhancing CO2 utilization under mild conditions and improving atomic economy.

To enhance the energy conversion efficiency of biomass‑gasification‑based multi‑generation systems, this paper proposes a CaO‑sorption‑enhanced biomass‑gasification‑driven integrated system comprising a solid oxide fuel cell (SOFC), a gas turbine, an organic Rankine cycle, and a multi‑effect flash seawater desalination unit. The addition of CaO increases the hydrogen content in the syngas, providing high‑quality fuel for downstream processes, while significantly reducing the exergy destruction in the biomass gasification stage, reduces the carbon footprint. After modeling and validating the system, its performance was evaluated from energy, exergy, and economic perspectives. The results show that the introduction of CaO reduces the exergy destruction in the gasification unit and the SOFC unit by 23.07 % and 21.38 %, respectively. With the objectives of maximizing net power output and exergy efficiency while minimizing the levelized cost of electricity (LCOE), a five‑dimensional decision‑variable space (HDPE content, gasification temperature, SOFC temperature, SOFC pressure, and CaO/syngas ratio) and a three‑dimensional objective space were first correlated using an SSA‑BP neural network model. Subsequently, NSGA‑II was employed for multi‑objective optimization, and the TOPSIS entropy‑weight method was applied to identify the optimal operating point. Under these optimal conditions, the system achieves a net power output of 2018.2 kW, an exergy efficiency of 62.4 %, and an LCOE of 0.0942 $/kWh. Furthermore, a comprehensive economic analysis was conducted to examine the fluctuation in the economic performance of the multi‑generation system due to electricity price variations across different regions, providing guidance for suitable application scenarios and future industrialization of the system.

A Rh(III)-catalyzed selective mono- and dual C-H bond functionalization reaction of N-aryl benzamidines with iodonium ylides has been developed. Notably, this process enables unprecedented site-selective C-H activation solely on the N-aryl ring of N-arylbenzamidine scaffolds. The reaction shows remarkable selectivity depending on the reaction time and stoichiometry of iodonium ylides, providing a facile divergent route to access both mono- and dual functionalized N-aryl benzamidine derivatives. This synthetic protocol exhibits wide substrate compatibility, is feasible for gram-scale preparation, and allows for further structural modification.

Producing 5-hydroxymethylfurfural (5-HMF) through cellulose degradation using highly efficient catalytic reactions represents a promising yet challenging strategy to address the need for fossil resource replacement. In this study, amphiphilic triple-heteropolyacid (HPA), Ce (DS)2H4AlW12O40 (abbreviated as Ce (DS)AlW12, where DS is a representative dodecyl sulfonate surfactant) was designed and fabricated via the linkage of Ce3+ to anionic surfactant and polyanion. This versatile catalyst could assemble into nano-micelles in aqueous media, where heteropolyanions can locate on the surface of the micellar sphere, isolatedly as uniformed active sites, i.e. single-cluster, which was linked with Ce (DS)+ inside the sphere to form a hydrophobic core being determined by characterization and Molecular Dynamic (MD) simulations. During the catalyzing reactions, the DS groups adsorb cellulose, the fully exposed polyanions and Ce3+ provide double-active centers of Br & Oslash;nsted (B) and Lewis (L) acids in single-molecular model, and the hydrophobic cores extract and protect the product. These advantages enabled Ce (DS)AlW12 to catalyze the conversion of cellulose into 5-HMF with a high selectivity for 63.7 % at 150 degrees C for 2 h in water. This work bridges the gap between heterogeneous, hierarchically assembled structures, and uniformly dispersed catalysis, providing an effective strategy for designing amphiphilic triple-HPA single-cluster catalysts to enable efficient 5-HMF production in aqueous systems. Furthermore, Ce (DS)AlW12 exhibited versatile functionality in the cascade conversion of cellulose in the biphasic system, notably achieving an 83.8 % yield of 5-HMF at 150 degrees C within 2 h.

Color-to-color switching electrochromic polymers with a high contrast ratio and the additional ability to store energy are attractive for applications in smart display devices and energy recycling and reuse. However, developing materials that combine both optimized electrochromic and energy storage performances remains a significant challenge. To address the integration of polymer color switching and energy storage, the synthesis of a donor-acceptor-donor (D-A-D) triarylamine (TAA)-based diamine monomer with the benzothiadiazole unit as the acceptor unit and using heteroatom as ion adsorption sites is here detailed. The electroactive polyimide enabling energy storage with a visual display of the state of charge (SoC) is subsequently prepared by polycondensation of the diamine monomer with 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride. The final polyimide film electrode exhibits 90% optical contrast, provides a capacitance of 304.5 F g-1 at a current density of 1 A g-1, and enables SoC monitoring through multiple color changes. Besides, we further demonstrate here that symmetric quasi-solid-state electrochromic supercapacitors constructed with a polyimide film as functional layers also exhibit excellent optical contrasts above 60% and high capacitance for energy recovery and reuse in practical applications. Additionally, the ion adsorption energy and the density of states of polyimide are calculated using density functional theory to gain insight into the energy storage mechanism. Overall, we demonstrate and rationalize here the effectiveness in color switching, energy storage, and integrated SoC displaying of triarylamine-based monomers that use electron-withdrawing conjugated heterocycles as bridges along with the corresponding polyimides.

Replacing fossil resources with cellulose presents a promising strategy to reduce dependence on and consumption of nonrenewable resources. Selective conversion of cellulose to levulinic acid (LeA) is one of the attractive depolymerization routes for producing a broad range of value-added chemicals, thereby offering opportunities to enhance both environmental sustainability and economic viability. To achieve high selectivity in LeA production, solid Pickering interfacial catalysts (PICs) were designed by embedding Brønsted (B) acidic/redox heteropolyacids (HPAs) H5PMo10V2O40 (HPMoV) inside the surface-functionalized ZrO2 nanoparticles as HPMoV(n)@ZrO2(C8/C5NH2) (n represents loading amount of HPMoV, n = 15, 20, 25, 30 and 35 wt

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.

Electrochromic (EC) materials based on ion insertion/desertion mechanisms provide a possibility for energy storage. Solution-processable energy storage EC polyamides have great potential for use in smart displays and EC supercapacitors. A suitable monomer structure design is particularly important for enhancing the electrochemical properties of polyamides. The symmetrical donor-acceptor-donor structure triarylamine (TAA) diamine monomer was prepared by the Ullmann reaction, and the corresponding polyamide (named BDPA-CA) was prepared by polycondensation reaction. The propeller-shaped skeleton of the TAA unit effectively increases the internal volume and endows the BDPA-CA with the property of solution processing. The introduction of electron-withdrawing benzothiadiazole groups into the main chain enhances the optical contrast of BDPA-CA during electrochemical oxidation. Moreover, the energy storage mechanism of BDPA-CA is elucidated via density functional theory calculations. The exposed sulfur (S) and oxygen (O) atoms in BDPA-CA can serve as active sites for lithium ion (Li+) binding, and the nitrogen (N) atom at the center of the TAA moiety is a perchlorateion (ClO4-) binding active site, which suggests that the full interaction of the dual active sites can increase the capacitance value of the BDPA-CA film electrodes.

The full utilization of lignocellulose involves two distinct catalytic routes: i) oxidative depolymerization of lignin and ii) acid/alkaline hydrolysis of hemicellulose and cellulose. To improve efficiency and reduce costs, constructing a single-cluster catalyst represents a desirable yet challenging strategy. Herein, triple-functional molecular polyoxometalates (POMs), NLLnH6-nV2Mo18O62 (n = 1-6) were fabricated using N-lauroyl-L-lysine (NLL) and H6V2Mo18O62 as precursors. Besides its amphiphilicity to form nano-micelles with polyanion uniformly dispersed outside and NLL inside, NLL also provided basic sites to H+/redox POMs to compensate the loss of acidity and enabled spatial separation of antagonistic acid/base sites within a single POM molecule. Density Functional Theory, Molecular Dynamics simulations and experiments were employed to analyze these processes. The adsorption of -OH in 2-phenoxy-1-phenylethanol (pp-ol) was achieved by interacting with polyanion and extra with NH and C = O groups in NLL. These synergistic effects resulted in concentrating and confining pp-ol and reactive oxygen species around polyanion, which turnover frequency increased by 0.066 h-1 compared to homogeneous H6V2Mo18O62. Full conversion of various soft and hard lignocellulose was achieved using NLLH5V2Mo18O62 catalyst under gradually increasing temperature. During the conversion process, the lignin was oxidized mainly through (3-O-4 bond cleavage without addition of NaOH, and the degradations of hemicellulose and cellulose were realized through acidic hydrolysis. The characteristics of this triple POMs allowed it to show higher activity than homogeneous H 6 V 2 Mo 18 O 62 and previous BetH5V2Mo18O62 (Bet, i.e. betaine), which pro- vided an alternative to developing new surfactant-type POMs in biomass conversion. The temperature-controlled properties in NLLH5V2Mo18O62 allowed easy separation and regeneration.