Nonlinear optical (NLO) materials are the core materials in the field of modern optics and laser technology. While these materials inherently depend on noncentrosymmetric (NCS) structures for their functionality, the targeted synthesis of such acentric crystals remains a prominent scientific challenge. To address this issue, we herein proposed a bonding-type-driven strategy to realize NCS structural transformation and enhance optical properties. The newly designed [(IO3F)SO3] hybrid anion exhibits substantial polarizability anisotropy, which endows K2(IO3F)SO3 with a large birefringence of 0.103 @ 1064 nm (51.5 times K2SO4). Notably, K2(IO3F)SO3 exhibits excellent overall optical properties, particularly in the solar-blind ultraviolet region. Compared to traditional iodate-sulfates, it possesses a comparable birefringence, a shorter ultraviolet cutoff edge (230 nm), and a moderate second-harmonic generation (SHG) response (1.5 x KDP). Ultimately, this bonding-driven strategy opens a novel avenue for the design and synthesis of next-generation NCS structural materials, particularly for fluorinated complex anionic systems.

Converting CO2 and CH4 into syngas offers an effective route to reduce both greenhouse gases, supporting large-scale carbon sequestration and carbon neutrality goals. However, existing catalysts often suffer from limited conversion efficiency and short lifespans under high-temperature conditions, with the lack of durable, structurally stable materials being a key bottleneck. Herein, a robust exsolution alloy Co–Ni catalyst embedded in an inert vermiculite-derived oxide matrix was developed. The catalyst exhibited a conversion of approximately 81%/86% for CH4–CO2 conversion at 750 °C, a syngas yield (H2/CO) of 0.88, and a lifetime of 60 h. Characterization confirmed the effectiveness of the alloying strategy, attributing the performance to a confined, highly dispersed structure and alloy synergy that enhanced CH4 cracking and CO2 adsorption. In situ DRIFTS revealed that the Co–Ni interface acts as the active site for adsorbing and activating CH4 and CO2, forming the key intermediate CHxO* and thereby opening a new reaction pathway while suppressing metal agglomeration and coke formation. This strategy provides a new idea for the development of clay mineral-based exsolution alloy catalysts for high-temperature dry reforming reaction, and overcomes the typical problem of difficult balance between activity and stability.

The industrial synthesis of substitute natural gas via CO/CO2 methanation is severely hampered by the irreversible deactivation of nickel catalysts by trace sulfur impurities. Overcoming this challenge is difficult because the electronic properties that make nickel active also make it prone to strong sulfur bonding, creating a fundamental scaling relation. Here, we report a robust sulfur-tolerant catalyst constructed by atomically dispersing ruthenium into a nickel lattice, which breaks this limitation. By leveraging the electronegativity difference between Ru and Ni, we induce a directed charge transfer that functionally decouples sulfur adsorption from the catalytic turnover. Combining in situ spectroscopy and density functional theory, we reveal that electron-rich Ru single atoms act as deep thermodynamic traps for H2S but energetically inhibit its dissociation into poisoning sulfide species. This decoy effect leaves the adjacent electron-deficient Ni ensemble sites protected and free to drive the methanation reaction. Consequently, the catalyst exhibits exceptional stability in 10 ppm H2S stream conditions that rapidly deactivate monometallic counterparts during both CO and CO2 methanation. This work demonstrates a generalizable electronic immunization strategy to design durable catalysts by spatially separating toxicant adsorption sites from active centers.

Water-lean amine absorbents represent a promising technology direction for energy-efficient CO2 capture from wet flue gas. However, achieving efficient regeneration at low temperatures remains a critical challenge. In this study, four secondary amines with distinct N-substituents, i.e., 2-(ethylamino)ethanol (EAE), 2-(butylamino)ethanol (BAE), N-methylbenzylamine (NMB) and N-ethylbenzylamine (NEB), were systematically evaluated in water-lean alkoxyethanols (2-butoxyethanol (BE), 2-phenoxyethanol (PE)) with various water contents. A constant-heating-rate desorption method was proposed to determine the characteristic regeneration temperature (Tmax) at the maximum desorption rate (Rmax) in comparison to the benchmark aqueous MEA. Notably, the reduction in Tmax correlates strongly with the Taft substituent parameter (steric hindrance Es and polar effect σ⁎) and solvent parameters (ε and δa). A multiple regression analysis quantitatively established this correlation, revealing the synergistic effects of N-substituents and solvent environment on desorption performance. Remarkably, the proposed water-lean formulation (60NEB-30BE-10 W) under desorption at 353 K reduced the regeneration energy consumption by approximately 50%, while achieving a cyclic capacity 30% higher than 30 wt% MEA desorbed at 373 K. These findings demonstrate that tailoring molecular structure and solvent microenvironment enables efficient CO2 desorption driven by the potential industrial waste heat, paving the way for a more sustainable and economical carbon capture technology.

This study focuses on the severe hazards of nitrogen oxides (NOx) to the environment and human health, and explores the selective catalytic reduction of NO (CO-SCR) technology based on water-washed mica-derived layered double oxides (LDOs). Although CuAl-LDO has certain potential in this reaction, its activity is still limited, and there is a problem of asynchronous conversion of CO and NO. Therefore, this paper designs a Ti-doped CuAl-LDO catalyst, which is successfully synthesized by the co-precipitation combined with calcination method. Performance tests show that Ti doping significantly enhances the CO-SCR activity of the catalyst and the conversion of CO and the reduction of NO achieve good synchronization. Mechanism studies indicate that the introduction of Ti induces the formation of a Cu-O-Ti interface structure, promotes electron transfer between Cu and Ti sites, enhances the redox cycling ability, and strengthens the adsorption and dissociation processes of NO. Through pure CO atmosphere tests, In situ Fourier transform infrared spectroscopy (In situ FTIR), and density functional theory (DFT) calculations, it is further confirmed that Ti doping effectively inhibits the CO disproportionation reaction. The Cu-O-Ti interface helps to stabilize the formation of the key reaction intermediate Cu+-CO and significantly reduces the energy barrier of NO reduction. The catalyst remains stable under continuous operation at 400 °C for 30 h, and the N2 selectivity always remains above 95%. This study provides a new design idea and theoretical basis for developing efficient and stable CO-SCR catalysts through precise interface engineering strategies.

Precisely modulating the synergistic effect of N-2 reduction and H2O oxidation reactions at the molecular level for photocatalytic N-2 fixation remains a challenge. Herein, MnOx and Pt nanoparticles (NPs) were decorated onto amine-functionalized metal organic framework NM-Fe {NH2-MIL-101(Fe)}, attempting to promote photoredox reactions simultaneously. Benefiting from the synergy of redox reactions, the optimized Pt@NM-Fe/MnOx exhibits an NH3 production rate of ca. 340 mu mol g(-1) h(-1), which is 4.5 times that of NM-Fe, along with an apparent quantum efficiency (AQE) of 0.33% at 420 nm. N-15 isotope labeling experiments demonstrates that the N in the nitrogen reduction reaction (NRR) originated exclusively from N-2. The performance improvement can be attributed to the spatial synergy of N-2 reduction and H2O oxidation reactions on the Pt@NM-Fe/MnOx composite photocatalyst. More specifically, MnOx acts as the H2O oxidation site by capturing holes to generate H+, while NM-Fe serves as the N-2 reduction center by accepting electrons. MnOx captures holes to oxidize H2O into H+, while Pt NPs activate the generated H+ into *H for photocatalytic N-2 fixation. Density functional theory calculations indicate that the breakage of the O-H bond in the H2O oxidation process is synchronized with the formation of *NNH in N-2 reduction, lowering the energy barrier. The present work demonstrates a synergistic integration strategy that overcomes the kinetic mismatch between the two half-reactions through precise spatial modulation of functional sites.

ABSTRACT The design and synthesis of highly efficient electrochemical sensors are pivotal to electrochemical conversion technologies. This study successfully synthesized a composite material comprising two‐dimensional (2D) conductive MXene and nickel‐based metal–organic framework (Ni‐MOF) by stirring at room temperature. By adjusting the amounts of dimethylformamide (DMF) and MXene during synthesis, the morphology of Ni‐MOF was effectively controlled, yielding both two‐dimensional nanosheets and three‐dimensional nanoribbon structures. The optimized composite (designated 1.5M200@Ni‐MOF) exhibits enhanced conductivity, a larger specific surface area (85.54 m 2 g −1 ), and an excellent multilevel pore structure, significantly promoting electron transfer and ion diffusion. Electrochemical testing indicates that the 1.5M200@Ni‐MOF modified electrode achieves a rapid response time of 1.3 s, high sensitivity of 2238.07 μA mM −1 cm −2 , and a low detection limit of 0.081 μM in glucose detection. This composite material exhibits outstanding resistance to common interferents such as dopamine, uric acid, ascorbic acid, and NaCl. This study reveals the synergistic effect between MXene and Ni‐MOF, opening up novel avenues and possibilities for designing highly efficient electrocatalytic glucose sensing materials.

Microfiltration is widely applied for surface water purification; however, the coexistence of microplastics (MPs) and organic contaminants in source waters of varied salinity and natural organic matter (NOM) may influence contaminant partitioning and fouling behavior during filtration. This study investigates how polymer type (i.e. polyethylene (PE) and polyethylene terephthalate (PET)) and aging of MPs affect their interactions with mixed contaminants, transport and partitioning of the contaminants in cake layer during microfiltration under varying salinity and NOM. PE-MP and PET-MP exhibited a stronger adsorption affinity toward bisphenol A (BPA) than atrazine (ATZ). Density functional theory calculations confirm noncovalent-dominated adsorption on PE-MP and π-π interactions governing adsorption on PET-MP. Aging alters such interactions by modifying surface physicochemical properties, leading to differential adsorption behavior compared to pristine MPs. Increasing ionic strength enhanced BPA adsorption via a salting-out effect (P < 0.05) but suppressed ATZ adsorption, while Suwannee River fulvic acid showed negligible influence due to competitive sorption. Microfiltration experiments demonstrated that polymer type, aging state, operating pressure, and water chemistry jointly regulate MP cake structure, thereby controlling contaminant transport, partitioning, and specific cake resistance. PE-MP and PET-MP held negative surface charge at zeta potentials of -18.07 and -6.39 mV in feed water, respectively. Polymer properties and aging-induced surface modifications governed the transition between interaction-driven fouling and mechanical compaction, which is increasingly important at elevated trans-membrane pressure. Moreover, hetero-aggregation between organic contaminants and MPs alleviated hydraulic resistance. These findings provide mechanistic insights for optimizing membrane processes to improve the removal of MP-associated contaminants.

The valorization of biomass waste into advanced electrode materials presents a promising pathway toward sustainable electrochemical energy storage. Herein, a silicon-doped carbon material (Si-CTS-Carbon) is synthesized from chitosan via an in situ reaction with silicon tetrachloride (SiCl4) and subsequent controlled pyrolysis. When evaluated as an anode for lithium-ion batteries (LIBs), Si-CTS-Carbon exhibits a high reversible capacity of 509.2 mAh g−1 with 99% capacity retention after 100 cycles at 0.05 A g−1. For sodium-ion battery (SIB) applications, it achieves a stable reversible capacity of 155.4 mAh g−1 under identical conditions. Structural and electrochemical analyses reveal that the robust C–O–Si covalent network effectively accommodates volume variation of silicon and enhances structural integrity during cycling. Furthermore, the hierarchically porous architecture shortens ion diffusion pathways, leading to improved Li+/Na+ transport kinetics. This work demonstrates a viable strategy for fabricating high-performance battery anodes by synergistically doping silicon into biomass-derived carbon, enabling practical biowaste valorization for energy storage.

Enhancing the dehydrogenation kinetics of both electrocatalysts and the substrate is crucial for the electrooxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to high-value 2,5-furandicarboxylic acid. Herein, we develop a dual oxyanion co-adsorption strategy by constructing a Mo-doped Ni3S2-modified Ni(OH)x electrocatalyst (denoted as Mo-Ni3S2/Ni(OH)x), enabling the simultaneous adsorption of in situ generated SO42- and MoO42- oxyanions on the Ni(OH)x surface. Experimental results and theoretical calculations demonstrate the distinct and synergistic role of co-adsorbed oxyanions in promoting HMF oxidation: (i) SO42- primarily lowers the energy barrier for Ni(OH)2 dehydrogenation, accelerating the formation of active Ni3+ species; and (ii) MoO42- predominantly interacts with hydrogen atoms of HMF, reducing the adsorption energy of HMF and facilitating its dehydrogenation kinetics. Taking advantage of this bifunctional synergy, Mo-Ni3S2/Ni(OH)x achieves a current density of 100 mA cm-2 at 1.46 V vs. RHE, 2.5 times higher than that of the Ni3S2/Ni(OH)x reference with only SO42- adsorption. This synergy also allows Mo-Ni3S2/Ni(OH)x to outperform Ni3S2/Ni(OH)x in terms of electrochemical activity during the oxidation of other nucleophiles. Remarkably, it demonstrates satisfactory practical applicability in an integrated membrane electrode assembly (MEA) electrolyzer, achieving near 100% FDCA selectivity after 20 cycles at 1.9 V. In contrast, exogenously added oxyanions show a markedly weaker promotional effect due to competitive adsorption with HMF and OH- at the active sites. This work elucidates the regulatory mechanism of similar oxyanions in a complex co-adsorption system for HMF oxidation and offers a rational strategy for designing efficient electrocatalysts for biomass valorization.

The practical implementation of electrocatalytic nitrate reduction reaction (NO3RR) for ammonia synthesis is critically hindered by its inherent sensitivity to temperature fluctuations, which leads to unpredictable selectivity shifts among NO3RR, nitrite reduction reaction (NO2RR), and the hydrogen evolution reaction (HER). Using Cu2O as a model catalyst, the temperature-dependent competition among different pathways within the 10-40 degrees C range was elucidated. An atomically dispersed Co-doped Cu2O catalyst (Co-Cu2O) was then designed to function as a thermal-adaptive platform. Mechanistic studies reveal that the atomically dispersed Co sites not only enhance the intrinsic hydrogenation capability but also dynamically stabilize key N-H intermediates (*NOH, *NH2, and *NH3) against temperature variations. This synergistic effect stabilizes the reaction pathway toward NH3, enabling robust and selective ammonia production under thermal perturbations. As a result, the Co-Cu2O catalyst maintains a Faradaic efficiency (FE) for NH3 above 90 % across the entire 10-40 degrees C temperature window and achieves a remarkable NH3 production rate of 53.79 mg h-1 mgcat-1 at 40 degrees C. This work provides fundamental insights into temperature-mediated catalysis and establishes an effective design strategy for wide-temperature electrocatalysts.

Although NaX zeolites show great potential for CO2 capture due to abundant cationic sites, their practical application is limited by weak cation-CO2 interactions and strong framework hydrophilicity. Herein, transition metal ions (Cu2 +, Fe3+, Zn2+) were introduced to modify NaX zeolites via in-situ hydrothermal synthesis, aiming to synergistically enhance CO2 adsorption performance by regulating pore structure and framework charge distribution. Dynamic breakthrough tests indicate that Fe-NaX exhibits the optimal comprehensive performance. Under dry 30/70 CO2/N2 feed, Fe-NaX achieves the highest CO2 uptake of 4.435 mmol·g−1 and selectivity of 41.24. At 15/85 feed, the uptake reaches 3.426 mmol·g−1 with selectivity of 52.05. Under humid conditions, Fe-NaX maintains superior uptake, selectivity, and delayed breakthrough. Structural characterizations confirm that metal incorporation narrows and homogenizes pore size, enhances micropore spatial confinement, and significantly reduces the distance between CO2 and adsorption sites. Furthermore, Fe3+ incorporation increases moderate-strength chemisorption sites. Density functional theory (DFT) calculations verify Fe-NaX possesses the strongest adsorption energy (-0.58 eV). Grand Canonical Monte Carlo (GCMC) simulations reveal at the atomic scale that the strong local electric field induced by the high charge density of Fe3+ significantly enhances electrostatic interactions. This study demonstrates that physical confinement restricts CO2 molecules within the strong local electric field via homogenized pores, ensuring highly efficient CO2 polarization; concurrently, strong electrostatic interactions endow the confined pores with specific CO2 recognition capability, ultimately realizing a synergistic enhancement in capacity and selectivity, providing a theoretical basis for efficient CO2 adsorbents.

Electrocatalytic nitrate reduction reaction (NO3RR) offers sustainable ammonia synthesis from industrial flue gases, yet SO2-induced sulfur poisoning hinders catalyst activity. Herein, we engineer Cu-doped BiFeO3 (Cu-BFO) with optimized oxygen vacancies, demonstrating NH3 Faradaic efficiency (FE) of 92.1 +/- 0.27% and NH3 yield rate of 36.2 +/- 1.86 mg mg(cat)(-1) h(-1) at -0.6 V vs.RHE. In-situ analysis and Density Functional Theory (DFT) calculations confirm NO3RR pathway and mechanism. Within the SO32-/NO3- ratio range from 0.1 to 1, the NH3 FE kept higher than 79.3% and 88.8% for NO3RR and NO2RR, respectively. The Cu-BFO maintains 64-h stability and > 80% FE at -0.6 V vs.RHE under 0.05 M SO32- conditions. Electrolyte refreshment recovers slightly attenuated activity. Catalyst reconstruction induces phase separation, re-exposing Cu sites and regenerating NO3RR activity. This work provides insights into catalytic interface design for high SO2 resistance through defect engineering. This paper deepens the understanding of SO2 poisoning mechanism and regeneration methods during electrocatalytic nitrate reduction.

Guanidine units have garnered significant attention in the study of ultraviolet (UV) nonlinear optical (NLO) materials due to their excellent microscopic optical properties, making them ideal systems for developing novel optical devices. A novel guanidinium-templated UV NLO crystal, [C(NH2)3]SbCl4 (GSC), was successfully synthesized via an aqueous solution method. GSC crystallizes in the orthorhombic chiral space group P212121, featuring a seesaw shaped [SbCl4]- anion. Remarkably, GSC exhibits a moderate second harmonic generation (SHG) response of 1.1 × KDP at 1064 nm and a large refractive index difference of 0.2 at 546 nm. This NLO effect originates from the synergistic interaction between the [C(NH2)3]+ unit and the stereochemically active [SbCl4]- unit. This work provides a candidate for the guanidine family of NLO materials.

Atomically dispersed Zn-N-C frameworks hold great promise for high-efficiency energy storage but remain challenging to fabricate controllably. Here we present an integrated "microchannel-synthesis + carbon-bath pyrolysis" strategy that enables rapid precursor formation and precise structural conversion without inert-gas protection. Adjusting the pyrolysis temperature influences the Zn-N coordination environment and carbon microstructure: Zn-N-C-800 exhibits higher N content, atomically dispersed Zn species in Zn-N-4-type coordination environments as evidenced by XAFS/XPS, and an enlarged interlayer spacing (similar to 0.36 nm). These features facilitate ion transport and surface-controlled pseudocapacitive storage, delivering reversible capacities of approximately 700 and 186 mAh g(-1) in Li+ and Na+ systems, respectively, with excellent rate capability and cycling stability. This work elucidates the structure-activity relationship of Zn-N-C materials and provides a scalable framework for designing MOF-derived electrodes with tunable atomic coordination and enhanced electrochemical kinetics.

The low carrier separation efficiency and high interfacial charge transfer resistance in photocatalysts hinder their practical application. While layered double hydroxides (LDHs) and MXene offer unique layered structures and tunable electronic properties, LDHs suffer from low carrier mobility and rapid charge recombination, and MXene tends to oxidize and restack. To address these interfacial challenges, a surfactant-directed assembly strategy using anionic sodium dodecyl benzene sulfonate (SDBS) and cationic hexadecyl trimethyl ammonium bromide (CTAB) is developed to construct an LDHs(SDBS)@MXene(CTAB) Schottky heterojunction. This approach inhibits layer aggregation and creates a strong built-in electric field via interfacial dipole engineering, enabling unidirectional and rapid electron transfer from LDHs(SDBS) to MXene(CTAB) and extending charge separation lifetime. The optimized interface also promotes the generation of reactive species (center dot OH and 1O2). Under visible light, the composite exhibits a several-fold increase in the degradation rate of sulfamethoxazole (SMX), enhanced mineralization, and excellent cycling stability compared to individual components. Photoelectrochemical tests, EPR, and DFT calculations confirm the critical role of the surfactant-induced interface in charge separation and transfer. Toxicity assessment shows reduced ecological risk of degradation intermediates. This work provides a new strategy for designing high-performance Schottky-junction photocatalysts and offers insights for efficient antibiotic wastewater treatment.

Biomass waste conversion to energy storage devices has gained significant attention. Here, we report a silicon-doped carbon material (Si─WH─Carbon) rich in C─O─Si bonds, synthesized from walnut shells (WH) and SiCl4 via an in situ doping strategy. This sustainable approach yields a dual-functional material. As a lithium-ion battery anode, Si─WH─Carbon delivers a high discharge capacity of 604.8 mAh·g-1 at 0.05 A·g-1 over 100 cycles, which is higher than 460.3 mAh·g-1 for the undoped carbon, owing to C─O─Si bonds that buffer silicon's volume expansion. Additionally, in supercapacitor applications, the material achieves a specific capacitance of 322.9 F·g-1 at 0.5 A·g-1. Silicon doping introduces polar Si─O─C groups that enhance wettability and promote efficient electrolyte-electrode contact, thereby improving charge transfer efficiency. This work offers a novel, cost-effective strategy for developing biomass-derived carbon materials with superior dual energy storage capabilities.