The development of highly efficient catalysts for light olefins production via alkane cracking remains a pivotal challenge due to the inherent limitations of conventional zeolites, such as excessive secondary reactions and rapid deactivation. Herein, we reported the rational design of a core-shell ZSM-5@Sn-MFI zeolite, where an Alrich ZSM-5 core was encapsulated by a Sn-doped MFI shell, to enhance catalytic performance in n-hexane cracking. Comprehensive characterization revealed that the Sn-MFI shell, incorporating framework Sn(IV) species as Lewis acid sites (LAS), modulated acidity by spatially shielding the strong Br & oslash;nsted acid sites (BAS) in the core while introducing synergistic BAS-LAS interactions. Systematic variation of the Si/Sn ratio (50-400) enabled tuning of the acid site distribution and acid strength. Catalytic performance evaluations demonstrated that the core-shell architecture effectively suppressed hydrogen transfer (the corresponding coefficient was reduced from 2.75 to 0.36) and aromatization pathways, thereby improving light olefins (C2-C4 olefins) selectivity and reducing BTX (benzene, toluene, xylene) formation. The light olefin yield over the optimal ZSM-5@Sn (200)-MFI reached 31.7 %, outperforming the values obtained over pristine ZSM-5 (15.7 %) or the physical mixture of ZSM-5/Sn(200)-MFI (2.5 %). Moreover, the core-shell catalyst shows excellent 24-h stability with minimal coke deposition, preserving pore structure and crystallinity under reaction conditions. These results demonstrate that spatial control of acid site type and accessibility via core-shell engineering is an effective route to enhance selectivity and coke resistance in alkane cracking.

A robust analytical method based on Captiva EMR-Lipid solid-phase extraction and HPLC-MS/MS was developed and validated for the simultaneous determination of 19 aromatic amine antioxidants (AAs) and two p-phenylenediamine-derived quinones (PPD-Qs) in human plasma. The optimized protocol effectively removed phospholipid interferences from complex blood matrix, significantly mitigating ion suppression and improving the recovery of hydrophobic AAs compared to conventional liquid-liquid extraction. Method validation demonstrated good accuracy (spike recoveries: 73.0-96.8%), precision (RSD < 11%), and sensitivity with method detection limits ranging from 0.81 to 21 pg/mL. The method was successfully applied to plasma samples from 20 adults, in which 11 AAs were detected at total concentrations of 240-710 pg/mL. Diphenylamine derivatives, particularly bis(4-tert-butylphenyl)amine (DBDPA) and diphenylamine (DPA), were identified as the predominant compounds, contributing over 69% of the total AA burden. No PPDs or PPD-Qs were detected, which may be attributed to their biotransformation and urinary excretion, as well as the limited sample size. This study provides a comprehensive biomonitoring tool for assessing combined human exposure to multiple AAs and establishes a foundation for further investigation into their health implications.

Hindered amine light stabilizers (HALSs) have been detected in various environmental media, yet human biomonitoring evidence remains absent. Herein, we determined 11 HALSs in paired breast milk and urine samples from nursing mothers in South China. At least one HALS was detected in 98.7% of breast milk samples and 98.7% of urine samples, with ∑HALS concentration ranges of < MDL-19.9 ng/mL (median: 2.20 ng/mL) and < MDL-23.0 ng/mL (median: 1.29 ng/mL), respectively. HALS compositions differed between breast milk and urine samples and 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine (HA 201) was the dominant compound. Most intercompound correlations were weak, suggesting compound-specific sources and toxicokinetic behaviors. In paired-sample regression analyses, breast milk concentrations of HA 201 and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (HS 508) showed weak but statistically significant positive associations with corresponding urinary concentrations. In exploratory analyses, recent home renovation, frequent plastic-packaged convenience food consumption, and greater personal care product use were associated with higher HALS levels. Under high exposure scenario, breastfeeding-mediated intakes of bis(1,2,2,6,6-pentamethyl-4-piperidyl) butyl(3,5-ditert-butyl-4-hydroxybenzyl) malonate (Tinuvin 144) in infants younger than 3 months exceeded the predicted reference dose, indicating a screening-level risk signal. This biomonitoring evidence of HALSs in human biological samples highlights the need for expanded exposure and toxicity studies.

Phosphomolybdic heteropolyacids (HPAs) are promising catalysts for selective oxidation due to their integration of acid and redox properties. Herein, we investigated partial oxidation of methacrolein (MAL) to methacrylic acid (MAA) on modified phosphomolybdic HPA through GC-MS and in situ IR detections in combination with DFT calculations. Consequentially, the reaction networks including main and side reaction were proposed by confirmation of product components. It was believed that the presence of protons on catalyst surface affect not only MAL adsorption and MAA desorption but also C-H bond activation of aldehyde group. In addition, the oxidation selectivity in catalytic pathways can be controllably modulated by substitution of Mo with other coordinating atom (M = W, V, Nb, Ta, As, and Sb). As a result, it can be explained that the V-substituted phosphomolybdic HPA exhibited excellent catalytic activity and selectivity in MAL oxidation to MAA. These findings will provide guidance and basis for design and optimization of HPA catalyst.

Developing high-performance and durable electrocatalysts for alkaline seawater electrolysis is critical for advancing practical hydrogen production. Yet it is severely hindered by chloride-induced side reactions that intrinsically limit catalytic efficiency. Therefore, we construct a core-shell structured catalyst Co3(PO4)2@Cr2O3-CoP (denoted as Co-Pi@Cr2O3-CoP) for alkaline seawater electrolysis, exhibiting excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance, the overpotential requiring only 266 mV for HER and 433 mV for OER at a high current density current density of 1000 mA cm−2, respectively. In situ Raman reveals that the Co-Pi layer undergoes in situ reconstruction into CoOOH active phase and releases PO43− ions during OER. Quantitative UV–vis spectroscopy reveals that Co-Pi@Cr2O3-CoP reduces active chlorine (ClO−) generation by 78% relative to bare CoP after prolonged OER in alkaline seawater, confirming that PO43− significantly suppresses chlorine oxidation through electrostatic repulsion. Meanwhile, Cr2O3 can enrich OH− due to its Lewis acidity, thus resulting in exceptional performance of Co-Pi@Cr2O3-CoP towards alkaline seawater electrolysis. An anion-exchange membrane electrolyzer employing Co-Pi@Cr2O3-CoP as dual-functional electrodes demonstrates outstanding durability, for 400 h at 100 mA cm−2 in alkaline seawater. This work provides a promising pathway towards scalable and sustainable seawater-based hydrogen production with high activity and excellent chlorine corrosion resistance.

The synthesis of methyl methacrylate (MMA) from coal-derived methyl propionate (MP) and formaldehyde (FA) via aldol condensation is a process with high atom economy and low energy consumption. The key challenge lies in designing and preparing efficient and stable catalysts. Herein, a series of Cs/Zr/SiO2 bifunctional catalysts with tailored acid–base properties were synthesized by a two-step impregnation method and systematically characterized by N2 adsorption–desorption, TEM, XRD, XPS, TPD and Py-IR. The dispersion of Zr species was controlled by using ligand compounds, thereby prompting the dispersion of the Cs active sites. The weak acid and base sites, originating from the active Si–O–Zr and Si–O–Cs linkages, were linearly correlated with MP conversion and MMA selectivity. As a result, the 10Cs/2Zr/SiO2 catalyst exhibited optimal performance, achieving 43.5% MP conversion with 91.8% MMA selectivity. In-situ DRIFTS analysis demonstrated that FA was activated on Zr-associated Lewis acid sites while MP was deprotonated on basic Si–O–Cs sites, and this synergy facilitated an efficient condensation process. Kinetic analysis of the 10Cs/2Zr/SiO2 catalyst revealed reaction orders of 1.01 for MP and 1.15 for FA, with an activation energy (125.0 kJ·mol-1) significantly lower than that of the 10Cs/SiO2 catalyst (149.5 kJ·mol-1). Furthermore, deactivation studies indicated that the decline in catalytic activity was primarily due to the deposition of amorphous carbon, which can be removed by thermal treatment. Overall, this work elucidates a fundamental understanding of the structure–activity relationships and provides a mechanistic insight for rational design of high-performance acid–base catalysts for MMA production.

Synthetic antioxidants (AOs) can accumulate in municipal sludge during wastewater treatment, yet current occurrence-based assessments remain largely focused on hindered phenolic antioxidants (HPAs), potentially overlooking other AO classes and transformation products (TPs) with distinct hazard characteristics. Here, we conducted a nationwide assessment of four major AO classes comprising 60 AOs and TPs in municipal sludge across China by integrating occurrence and hazard information. Forty-seven compounds were detected nationwide, including 17 compounds reported in sludge for the first time (e.g., AO 3052, PANA/PBNA, AO 168=O, and DLTP). HPAs overwhelmingly dominated AO occurrence, accounting for 94.0% of total AO concentrations nationwide, with BHT and DBP as the major contributors. In contrast, hazard-informed prioritization revealed that aromatic amine antioxidants (AAs) and their TPs, particularly 6PPD, DPA, and 6PPD-quinone, disproportionately dominated hazard profiles despite their substantially lower abundance. The high rankings of TPs further suggest an important role of environmental transformation in shaping AO-related hazards in sludge. These findings reveal a pronounced mismatch between abundance and hazard profiles across AO classes, suggesting that concentration-driven monitoring strategies may overlook lower-abundance but highly hazardous contaminants in municipal sludge.

Vulcanization accelerators (VAs) are essential additives widely used in rubber production, especially for tire rubber. However, their environmental occurrence, migration, and risk in sediments on a large geographical scale remain poorly understood. In this study, we conducted the first large-scale geographical investigation of eight VA classes in sediments from multiple hydrologically connected water bodies spanning urban rivers, estuaries, coastal areas, the deep sea, and the open ocean. Five of the eight classes of VAs were detected across the studied areas, demonstrating the ubiquity of these anthropogenic chemicals. Thiazoles were the predominant class, followed by thioureas and guanidines. A total of 34 of the 43 traditional and emerging VAs were detected, with most nonthiazole VAs being reported in sediments for the first time. Total sedimentary VA concentrations declined along a gradient: urban river (median: 188 ng/g) > estuary (81.8 ng/g) > coast (53.5 ng/g) > deep sea (12.0 ng/g) > open ocean (7.49 ng/g). Riverine export fluxes indicate a significant input of these anthropogenic chemicals via particle-mediated transport from terrestrial sources into the coastal ocean. We developed a novel framework that combines multidimensional substance hazards and environmental occurrence indices to prioritize the identified chemicals and assess the risks of surface-deposited VAs in aquatic environments. Fourteen VAs posed medium to high risks in urban rivers and were identified as high-priority VAs of concern. These findings underscore the urgent need for regular monitoring and risk assessment of these ubiquitous but understudied rubber chemicals.

Fluorinated lithium (Li) salts are essential constituents of Li-ion battery (LIB) electrolytes, yet their environmental emissions during the rapidly expanding recycling of retired LIBs remain unexplored. Herein, we established a targeted screening list of 11 commonly used fluorinated Li salts and reported their first identification in dust and recycled black mass (BM; a powder-like primary form of crushed spent LIBs after pyrolysis) from a typical spent LIB recycling plant in China. Nine and seven fluorinated Li salts were detected in the dust and BM samples, respectively, with lithium hexafluorophosphate as the dominant compound, followed by lithium bis(fluorosulfonyl)imide and lithium bis(trifluoromethanesulfonyl)imide. Total concentrations of fluorinated Li salts (∑F-Li salts) exhibited high levels ranging from 581 to 47,500 ng/g (median: 12,100 ng/g) in ambient dust, with significantly higher levels in LIB dismantling areas than in nondismantling areas. By contrast, ∑F-Li salts in BM samples were much lower (<LOD-1800 ng/g; median: 17.8 ng/g), indicating that fugitive emissions to the environment or the transformation/decomposition of fluorinated Li salts occurred during high-temperature pyrolysis. Our findings demonstrate that spent LIB recycling contributes to substantial emissions of fluorinated Li salts into the surrounding environment, highlighting the need for further evaluation of their environmental impacts.

Efficient selective absorption of maleic anhydride (MAH) from n-butane oxidation off-gas is beneficial for energy savings in downstream processing. This process demands absorbents with both moderate polarity and hydrophobicity, which are two typically mutually exclusive properties. Herein, we propose a composite absorbent to address this trade-off and employ a multi-scale framework to elucidate the thermodynamic and structural mechanisms governing solute-solvent interactions. The optimal formulations that enhance MAH absorption capacity while maintaining low absorbent loss and minimal water absorption were identified through process simulations coupled with multi-objective optimization. The di-n-butyl phthalate (DBP)-sulfolane (SLF) composite system exhibits outstanding absorption performance, achieving a 38.5% reduction in absorbent consumption and over 20% decreases in both total operating costs and total annualized costs compared with pure DBP. Overall, this study highlights the synergistic potential of composite absorbents in enabling efficient and economical separation processes.

While the electrochemical CO2 reduction reaction (ECRR) to value-added multicarbon (C2+) products holds great promise for achieving carbon neutrality, it is hindered by sluggish CC coupling kinetics and severe competition from the hydrogen evolution reaction (HER). Herein, a tandem catalysis strategy featuring the dual optimization of the local CO microenvironment and the electronic structure of Cu is developed by rationally coupling Al-modified Cu2O octahedra with the Ag NPs@Ag-MOF composite. In this architecture, the Ag NPs@Ag-MOF module serves as an excellent CO-generator that efficiently supplies CO to adjacent Cu sites while suppressing HER. Building on this foundation, the tandem catalyst (Cu2O (Al)-Ag NPs@Ag-MOF) achieves a significant C2+ selectivity with a Faradaic efficiency (FE) of 55.18% and sustains stability for 70 h. Notably, the FE toward ethanol (FEC2H5OH) of Cu2O (Al)-Ag NPs@Ag-MOF is up to 49.39%, higher than pristine Cu2O (12.25%), firmly highlighting the efficacy of this dual-optimized tandem design. In situ Raman and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, along with density functional theory (DFT) calculations demonstrate that the tandem system continuously supplies *CO to adjacent Cu sites, where CC coupling yields the *OCCOH. Concurrently, Al modification dynamically optimizes the surface electronic structure of Cu to lower the CC coupling energy barrier, and further reveals the underlying mechanism by which it favors the formation of C2H5OH over C2H4. Ultimately, an integrated ECRR||methanol oxidation reaction (MOR) electrolyzer is assembled, achieving simultaneous generation of value-added chemicals with a 450 mV voltage reduction (22.28% energy savings) compared to oxygen evolution reaction systems.

The rapid growth of lithium-ion battery (LIB) recycling has raised concerns about the release of new fluorinated contaminants. Here we provide the first field evidence that spent LIB recycling is a source of emerging fluorinated organophosphorus esters (FOPEs) in the indoor environments of recycling facilities. Seven fluorinated organophosphonate, phosphite, and phosphate esters, commonly used as flame-retardant electrolyte additives, were targeted for analysis in indoor dust samples (n = 66) collected from an industrial-scale spent LIB recycling plant in China. Using a targeted UPLC-MS/MS method, all seven FOPEs were detected, with total concentrations ranging from 23.4 to 4780 ng/g (median, 738 ng/g; mean, 917 ng/g). Tris(2,2,2-trifluoroethyl) phosphite was the dominant congener, contributing 50.4% of the total FOPEs, followed by tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite and bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl) phosphonate. Correlation analysis suggested shared LIB-related sources and possible phosphite-to-phosphate transformations during battery aging or recycling. Screening-level property predictions further indicated notable persistence, mobility, and bioaccumulation potentials for several highly fluorinated congeners. These findings point to an emerging class of fluorinated contaminants associated with battery circularity with potential implications for the surrounding environment.

Vanadium-phosphorus oxides (VPO) represent a family of complex mixed-metal oxides with structurally diverse crystalline phases, among which (VO)2P2O7 serves as the predominant active phase in the selective oxidation of n-butane to maleic anhydride (MA) and in ammonia oxidation. The catalytic activity, selectivity, and long-term stability are critically governed by crystal structure features, such as phase composition, lattice defects, and structural dynamics under reaction conditions. Based on this, this review systematically summarizes the crystallographic evolution of VPO catalysts, encompassing their historical development, synthesis methods, and structural characterization. Emphasis is placed on the relationship between the crystal structure and catalytic performance, especially in the context of n-butane oxidation. The mechanisms of phase transformation among different VPO crystalline forms are thoroughly discussed, offering insight into how structural evolution affects the catalytic behavior. Additionally, this review highlights advanced strategies for modulating the phase composition and enhancing the stability of VPO catalysts, including doping, redox treatments, and morphology control, which collectively contribute to the design of "tailored" catalysts that balance high conversion rates with excellent selectivity. Finally, future research directions are proposed, including in situ and operando studies, multiscale modeling, and advanced synthetic techniques, to drive the development of next-generation VPO catalysts for efficient and sustainable selective oxidation applications.

Per- and polyfluoroalkyl substances (PFAS), a class of synthetic fluorine-containing organic compounds, pose a serious threat to the ecological environment and human health due to their persistence, bioaccumulation, and extensive toxicity. Non-targeted screening (NTS) is a key method for identifying and determining unknown PFAS, which is crucial to the understanding of their exposure pathway and health risks. Hence, this review focuses on NTS techniques for PFAS in the environment. Firstly, high-resolution mass spectrometry and ion mobility innovations enabling novel PFAS/isomer identification are evaluated. Afterwards, pretreatment optimization (e.g., solid-phase extraction and emerging adsorbents) is summarized by analyzing the advantages of each method and the challenges posed by the limited datasets, while also outlining their applicable scenarios. Analytical challenges from structural complexity (short-chain substitutes and ether-based fluorine-modulated polymers) and matrix effects are discussed. Lastly, practical implications for environmental health and the future development potential of NTS technologies for PFAS are presented. Overall, this review proposes a science-based framework for monitoring and regulatory prioritization, with the expectation of supporting PFAS management and mitigation.

Bisphenol S (BPS) analogues are increasingly used as alternatives to bisphenol A (BPA), but their occurrence, phase behavior, and exposure implications in e-waste recycling environments remain poorly characterized. Here, we conducted an integrated investigation of BPS analogues (BPSs) in indoor dust and paired gas- and particle-phase air samples from e-waste dismantling workshops in South China, to characterize their occurrence profiles, gas-particle partitioning, endocrine-disruption screening, and occupational exposure risks. BPS and 11 analogues were detected in dust, while BPS and 10 analogues were detected in indoor air. ∑12BPSs ranged from 48.1 to 2120 ng/g in dust and 135-1790 pg/m³ in air. DBSP and BPS dominated dust, whereas DBSP dominated the particulate phase and DPS dominated the gaseous phase. Notably, DPS was the only compound detected in all gas-phase samples, indicating distinct phase preference. Gas-particle partitioning coefficients correlated significantly with predicted subcooled liquid vapor pressures and octanol-air partition coefficients (p < 0.01). EDC-Predictor screening indicated endocrine-related interaction potential for several analogues, particularly DBSP and DPS. Estimated daily intakes via dust ingestion and inhalation reached 3.32 ng/kg bw/day under the high-end scenario, higher than the recently revised BPA TDI in a screening-level comparison. These findings reveal that overlooked BPS substitutes, particularly DBSP and DPS, act as phase-specific contributors to occupational exposure in e-waste workshops.

Developing electrolytes that can stably operate at high voltages is a pivotal challenge in enhancing the energy density of sodium-ion batteries (SIBs). This paper proposes a rational design strategy based on density functional theory calculations of the frontier molecular orbitals and electrostatic potential. Specifically, the highest occupied molecular orbital level of solvent molecules is regulated by introducing strongly electron-withdrawing fluorine atoms, producing a bifunctional electrolyte with weakened solvation and high oxidation stability. The weak coordination characteristics of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFETFE) are combined with the interface film-forming ability of fluorinated ethylene carbonate (FEC), synergistically optimizing the solvation structure of Na+ and the electrode/electrolyte interface. Theoretical calculations and spectroscopic analysis show that the weak coordination solvent allows more PF6 - to enter the primary solvation sheath of Na+, forming a structure rich in ionic aggregates, thus accelerating Na+ transport. Meanwhile, the formation of a stable and inorganic-rich interface film on the cathode surface effectively inhibits oxidative decomposition at high voltages. Consequently, the cathode exhibits high long-cycle stability at a high cut-off voltage of 4.3 V (vs. Na+/ Na), with a capacity retention rate of 87.6% after 2000 cycles at room temperature. This work provides a novel paradigm for designing advanced electrolytes suitable for high-voltage/high-energy-density SIBs.

Development of cost-effective catalyst for selective hydrogenation of methyl acrylate is still highly desired to boost the industrial production of coal-based methyl methacrylate. Herein, we investigated the promotional effect of boron (B) component in the catalytic performance of Ni/γ-Al2O3 catalyst on selective methyl acrylate (MA) hydrogenation to methyl propionate (MP). Series of Ni-B/γ-Al2O3 prepared through incipient-wetness impregnation method were evaluated in a fixed-bed reactor, and their physicochemical properties were systematically characterized using BET, XRD, TEM, H2-TPR and XPS. It was noticed that incorporation of only 1% (mass) B can significantly enhance the reduction and dispersion of Ni species and their electron density and effectively suppress NiAl2O4 formation. Excessive B loadings would lead to the aggregation of B2O3 and decrease of catalytic activity. Under the optimal reaction conditions, the 5Ni-1B/γ-Al2O3 catalyst sample achieved 99.9% MA conversion and 100% MP selectivity and exhibited stable performance for over 100 h time-on-stream. In situ DRIFTS measurements further verified the accelerated C=C hydrogenation into C—C after the loading of B component.

Development of highly efficient, selective, and stable single-atom catalyst (SAC) is an important research hotspot in the field of hydrogenation, due to the atomic utilization of active component. In this study, an effective single-atom nickel catalyst with a specific coordination structure of Ni─N4 was constructed using Ni-containing ZIF-8 as precursor for efficient hydrogenation of methyl acrylate to methyl propionate in the fixed-bed reactor. Multiple characterization techniques including HAADF-STEM, H2-TPR, XRD, and XAFS were utilized to systematically analyze the structure and physicochemical properties of as-prepared catalyst series. The effects of catalyst preparation and hydrogenation conditions on the catalytic performance were evaluated and further optimized. As a result, the turn of frequency (TOF) could reach up to 200.8 h-1 for methyl propionate production, with catalytic selectivity of 100%. In situ IR experiments were performed to monitor the hydrogenation mechanism on the catalyst surface, as well as kinetic studies for confirmation of reaction order and activation barrier. This study will provide a new strategy for the design and of non-noble metal SAC for the hydrogenation of methyl acrylate.