Electrocatalytic reduction of CO2 to high-value chemicals and fuels, such as formate, offers a promising route to achieve carbon neutrality and climate change mitigation. In this work, we report a counterion-induced amorphization strategy applied to anionic indium metal-organic frameworks (In-MOFs) aimed at strengthening the binding of desired intermediates for efficient CO2 electroreduction. In-TDC containing the small counterion Me2NH2+ undergoes facile cation exchange, triggering framework reconstruction into an amorphous phase (A-In(OH)x(CO3)y). The A-In(OH)x(CO3)y catalyst achieves a FEformate of 97.2% at -1.4 V vs. RHE and maintains ∼90% selectivity for 36 h, far surpassing the other anionic crystalline analogue In-TEA with the bulky counterion TEA+ as a structural "anchor" for resisting collapse. Experimental and theoretical studies indicated that the better performance of A-In(OH)x(CO3)y results from the strong orbital coupling between In p and O p of *OCHO, which not only lowers the free energy barrier for the conversion of *CO2 to *OCHO but also enhances the *OCHO binding. This work highlights counterion exchangeability as a powerful tool to unlock p-orbital activity for efficient CO2 electroreduction.

Lithium‑sulfur batteries (LSBs) offer high energy density, yet their performance is restricted by uncontrolled lithium polysulfides (LiPSs) migration and the intrinsically slow multistep conversion of sulfur species. To alleviate these issues, a Fe/Co/Ni/Cu/Mn high-entropy metal-organic framework (HE-MOF) was directly grown on MXene nanosheets to form an HE-MOF@MXene heterostructure, which was subsequently employed as a separator modifier in LSBs. The reciprocal structural regulation between HE-MOF and MXene effectively suppresses component aggregation and layer re-stacking, thereby increasing the accessible surface area of the heterostructure and promoting greater active-site exposure. Meanwhile, the two components are functionally integrated. The well-exposed high-entropy multimetal sites in HE-MOF can effectively exert their adsorption and catalytic advantages toward sulfur species with the assistance of the efficient electron/ion transport network constructed by MXene. Density functional theory calculations suggest distinct electronic structures and d-d interactions among the metal sites in HE-MOF. The resulting multimetal synergy may help accommodate the differentiated adsorption requirements of sulfur species and facilitate their subsequent conversion. Consequently, with the separator functionalized by HE-MOF@MXene, the cell achieves 1445 mAh g-1 at 0.2C. At a high rate of 5C, the cell still delivers 690 mAh g-1. Moreover, continuous operation over 1000 cycles at 3C results in an average capacity loss of merely 0.060% per cycle.

Enzyme confinement at the molecular scale reveals catalytic performance that is previously unseen at the ensemble level, but all such delicate enzyme hosts now available encounter their intrinsic issues. Here, we present a mild, one-pot emulsification-directing approach to customize colloidosomes (CSs) with pores matching enzyme size as enzyme hosts for optimizing continuous-flow biocatalysis. By means of the dissolution-induced inside-out self-assembly, uniform and enzyme-matched pores can be readily achieved. Typically, 5.8-nm pores obtained using 22-nm SiO2 nanoparticles (SiO2 NPs) as building blocks are optimal for confining Candida antarctica lipase B (CALB, ∼5 nm), conferring 98.3% activity recovery and minimal leaching of only 2.1%. The catalytic efficiency of CALB-confined colloidosomes (CALB/CSs) is dozens of times higher than that of free CALB (fCALB) in batch mode. Moreover, a 21.3-fold catalytic efficiency was achieved by integrating robust CALB/CSs with a continuous-flow platform. Meanwhile, the desired long-term stability was confirmed, with over 85% of the initial efficiency maintained after 200-h of consecutive operation. This study offers a potentially generalizable strategy that establishes a CS platform as an enzyme-confined host that is competent for continuous flow manufacturing, hoping to unlock the full potential of enzymatic reactions.

Developing green and efficient methods for recycling waste lithium-ion batteries (LIBs) is increasingly important, and deep eutectic solvents (DESs) have emerged as a promising alternative to conventional acid leaching, but their high viscosity and the difficulty of separating multiple chemically similar metals remain challenges. Herein, we propose an inactive diluent-modified DES for the gradient extraction of transition metals from waste LIBs, in which dimethyl carbonate (DMC) is introduced to regulate the properties of the choline chloride (ChCl)-oxalic acid (OA) system. Based on our previous study, the synthesized DES is applied to leach transition metals from the OA leaching residue obtained after Li recovery. Under the optimized conditions (2 h, 70 °C, 40 g/L, 10 wt% DMC), it achieves leaching efficiencies of Co and Mn exceeding 99%, while Ni is barely leached and remains enriched in the solid residue. While Co and Mn account for more than 99% of the dissolved transition metals, demonstrating the high selectivity of the gradient separation. Mechanistic analysis reveals that the modified DES retains its structural consistency, with abundant ChCl-OA clusters dispersed in DMC, while lowering the viscosity and modulating the competitive coordination environment. OA provides protons while ChCl facilitates complexation, and both promote the redox processes that drive metal dissolution and precipitation. This approach realizes efficient and environmentally compatible stepwise metal recovery for the green, value-added utilization of retired batteries.

Manganese dioxide (MnO₂)-based catalysts have emerged as promising candidates for the complete oxidation of volatile organic compounds (VOCs). However, insufficient oxygen mobility and the limited availability of reactive oxygen species restrict their low-temperature catalytic performance. Herein, Ni-doped ε-MnO₂ nanosheet catalysts were synthesized via a redox-precipitation route under two distinct synthesis redox environments by tuning the KMnO₄/Mn2+ ratio. The redox-controlled synthesis generates distinct surface chemistries, leading to different catalytic behaviors toward aromatic and oxygenated VOCs. Comprehensive structural, spectroscopic, and redox characterizations reveal that the catalyst synthesized under Mn2+-rich conditions possesses oxygen-vacancy-rich surfaces together with enhanced oxygen mobility and MnONi redox interactions, which correlate with superior low-temperature oxidation of toluene. In contrast, the catalyst prepared under KMnO₄-rich conditions exhibits more pronounced carbonate-modified surface chemistry, which is associated with enhanced ethyl acetate oxidation. The optimized catalysts achieve T₉₀ values of 238 °C for toluene and 198 °C for ethyl acetate oxidation. Catalytic tests under an inert atmosphere further support the direct participation of catalyst oxygen species, consistent with a Mars-van Krevelen-type oxidation mechanism. Moreover, the catalyst synthesized under Mn2+-rich conditions maintains nearly complete ethyl acetate conversion for 48 h at 220 °C. These results demonstrate that controlling the synthesis redox environment provides an effective strategy to tailor surface chemistry and oxygen activation in Mn-based catalysts, offering new insights into the rational design of efficient catalysts for VOC oxidation.

Rechargeable zinc-air batteries (ZABs) require efficient electrocatalysts to boost the sluggish oxygen reduction reaction (ORR)/ oxygen evolution reaction (OER) kinetics at the air cathode. However, designing high-activity catalysts faces considerable challenges due to spatial and electronic constraints. Herein, a boron-doped hollow spherical porous carbon (HS-FeNi-BNC) anchored with Fe-B-Ni diatomic sites is prepared via a facile B-bridging strategy, realizing the regulated construction of heteroatom doping and diatomic active sites. HS-FeNi-BNC possesses abundant micropores/mesopores, uniformly dispersed FeNi diatomic centers (0.27 nm spacing) with a Fe-B-Ni bridge structure, and topological carbon defects induced by B/N co-doping. HS-FeNi-BNC exhibits exceptional trifunctional electrocatalytic performance in alkaline electrolytes, with an ORR E1/2 of 0.864 V, an OER overpotential of 308 mV and a hydrogen evolution reaction (HER) overpotential of 301 mV at 10 mA cm-2. HS-FeNi-BNC-based ZABs achieve an outstanding wide-temperature operating range of -10 °C to 60 °C, a specific capacity of 761.51 mAh g-1 and a Zn utilization efficiency of 92.9%, outperforming Pt/C + RuO2-based ZABs. Density functional theory (DFT) calculations reveal that the Fe-B-Ni bridge structure triggers p-d orbital hybridization, regulating metal site electronic structures, optimizing reaction intermediate adsorption and accelerating interfacial electron transfer. This work advances the development of high-efficiency heteroatom-modified non-noble metal multifunctional catalysts.

The effects of surface functionalization and metal ordering on the structural, mechanical, and electrochemical properties of two-dimensional transition metal carbide MXenes remain insufficiently understood, particularly for double-metal systems. Nb2TaC2 and Ta2NbC2 monolayers, in bare and oxygen-functionalized forms, are studied using density functional theory to determine how these factors affect lithium adsorption, diffusion, and storage performance. Oxygen functionalization increases in-plane stiffness (Young's modulus up to 384.7 N/m) and stabilizes Poisson's ratios, while lithium preferentially adsorbs at metallic sites on bare MXenes and at carbon sites on O-functionalized surfaces, with adsorption energies reaching -3.70 eV. Nudged elastic band calculations show that oxygen functionalization slightly increases diffusion barriers, from 0.05 to 0.21 eV for Nb2TaC2 and from 0.06 to 0.24 eV for Ta2NbC2, while fast Li-ion mobility is maintained. Open-circuit voltage analysis indicates average voltages of 0.74 to 0.95 V with capacities up to 412 mAh/g. These results provide design guidelines for tuning surface chemistry and metal ordering in double-metal MXene anodes for Li-ion batteries.

RuO2 undergoes overoxidation at high oxidation potentials, involving the lattice oxygen oxidation mechanism (LOM) that leads to severe Ru dissolution. The current state-of-the-art strategy suppresses the kinetically favored LOM pathway by triggering conventional adsorbate desorption mechanisms, but this approach sacrifices activity for enhanced stability. To address this challenge, this work reports a Cs-doped RuO2 (Cs0.05-RuO2) catalyst. The low electronegativity of Cs enables electron transfer to Ru via Cs-O-Ru bridges, achieving high LOM activity while avoiding Ru overoxidation and thus maintaining high stability. Cs0.05-RuO2 exhibits a low overpotential of 169 mV@10 mA cm[-2] under acidic conditions. Furthermore, the Cs0.05-RuO2||Pt/C electrode pair operates stably for ∼1800 h@500 mA cm[-2] in an anion-exchange membrane water electrolysis cell. Advanced in situ spectroscopic techniques and density functional theory calculations confirm that the introduction of low-electronegativity Cs strengthens the RuO bond and suppresses the overoxidation of Ru.

The electrocatalytic nitrate (NO3[-]) reduction reaction (NO3RR) presents a sustainable and promising avenue for simultaneous ammonia (NH3) synthesis and wastewater remediation. However, conventional copper (Cu)-based catalysts are severely bottlenecked by sluggish water dissociation kinetics and a consequent deficiency in active hydrogen ([⁎]H) supply. Herein, we construct an interfacial dual-site catalyst consisting of oxygen-vacancy-rich cerium oxide nanoclusters anchored on a copper foam substrate (CeOx@Cu). Specifically, the oxygen vacancies on CeOx promote water dissociation to generate [⁎]H, which subsequently spills over to adjacent Cu sites to accelerate the nitrate hydrogenation step. This synergistic relay mechanism is comprehensively validated by density functional theory (DFT) computations and operando Fourier-transform infrared (FTIR) spectroscopy. Consequently, the as-prepared CeOx@Cu catalyst exhibits a balanced catalytic performance under neutral conditions, concurrently achieving a Faradaic efficiency (FE) of 94.6% and a corresponding NH3 yield rate of 404.08 μmol h[-1] cm[-2] (corresponding to 6.88 mg h[-1] cm[-2]) at a low potential of -0.5 V versus the reversible hydrogen electrode (vs. RHE). Furthermore, the practical viability of the catalyst is demonstrated in an assembled zinc-nitrate battery, which delivers a peak power density of 5.85 mW cm[-2] alongside robust durability. This study provides valuable insights into coordinating vacancy engineering and spillover kinetics for the rational design of high-efficiency dual-site electrocatalysts.

Electrochemical CO2 reduction to valuable multi‑carbon fuels offers a compelling route toward carbon neutrality, yet the selective conversion remains challenging because it requires the coordinated regulation of CO2 activation, key intermediate hydrogenation, CC coupling, and the competing hydrogen evolution reaction. Herein, we propose a dual electronic regulation strategy by coupling graphene-derived carbon interfaces and oxygen vacancies into Cu2O to construct a G/Vo-Cu2O catalyst for selective CO2 reduction reaction (CO2RR) toward ethylene. Experimental characterizations and theoretical calculations reveal that the carbon interface promotes interfacial charge transfer, enhances CO2 adsorption/activation, improves reaction kinetics, and suppresses excessive hydrogen evolution, while oxygen vacancies create localized electron-rich centers that facilitate *CO hydrogenation toward the key *CHO intermediate. Benefiting from this complementary regulation, G/Vo-Cu2O balances the formation and stabilization of *CO and *CHO intermediates, thereby favoring the thermodynamically downhill *CO*CHO coupling pathway over conventional *CO*CO or *CHO*CHO dimerization. In situ Fourier-transform infrared spectroscopy further confirms the enhanced generation of *CHO and *COCHO intermediates during CO2RR. As a result, the optimized G/Vo-Cu2O catalyst achieves a C2H4 Faradaic efficiency of 62.4 ± 4.4% at -1.2 V versus reversible hydrogen electrode, accompanied by suppressed H2 and CO formation. This work highlights the importance of interface-defect dual electronic regulation in steering CO2RR selectivity and provides mechanistic insights for designing Cu-based catalysts toward efficient C2+ production.

Lithium recovery from salt-lake brines offers a potential route to alleviate strategic lithium shortages driven by surging global demand. Solar evaporation-assisted lithium adsorption (SELA) has been developed to enhance this process by harnessing solar energy to promote endothermic adsorption and interfacial ion enrichment. However, conventional SELA architectures are fundamentally constrained by sluggish mass transfer and interfacial salt scaling in floating configurations that rely on passive capillary transport. Herein, we report a SELA hanging system that overcomes these physical limitations by establishing a gravity-driven thin-film convection regime. The system integrates a carbon fiber cloth-based photothermal layer with a core-shell polyacrylonitrile/titanium-based lithium-ion sieve@cellulose acetate adsorption layer, suspended between a higher-level supply tank and a lower-level collection tank. This hanging configuration creates a "pre-activated ionic environment", referring to the heated, concentrated, and high-flux brine generated by solar evaporation before entering the adsorption layer, which provides a thermally activated and mass-transfer-enhanced feed for subsequent Li[+] capture. Under 1-sun irradiation (1 kW m[-2]), the SELA hanging system delivers a Li[+] adsorption capacity of 27.6 mg g[-1] for 6 h, a 206.7% enhancement relative to dark conditions. When tested in simulated brine, the hanging architecture maintained exceptional stability with no visible scaling, whereas the floating model suffered a 19.9% performance decay. This work establishes a scaling-resistant and energy-efficient strategy for lithium recovery from salt-lake brines resources.

Quantitative measurement of silica nanoparticles (NPs) in liquid, particularly below 20 nm, remains fundamentally constrained by background artifacts and detection limits that are poorly understood. Here, we identify and systematically resolve a commonly underrecognized limitation in liquid-to-aerosol nanoparticle metrology: interference from dissolved non-volatile residues (NVRs) that generate artifact aerosol modes and easily interfere with NP measurements. Through mechanistic analysis of droplet formation, NVR-derived size scaling, transport losses, and charge efficiency, we establish a quantitative framework that defines the measurable concentration and size limits of aerosolization-based nanoparticle characterization. By integrating droplet-size control (via impactor coupling and electrospray tuning) with liquid-phase purification, NVR-derived artifacts are largely suppressed, enabling clear resolution of target nanoparticle peaks down single-digit nanometer range. Unified correlation equations for silica and gold NPs are developed to account for transport losses and sample feeding rate, defining practical concentration limits. An aerosolization-CPC method that avoids particle loss in DMA classification was further evaluated. Finally, the aerosolization-based method with effective NVR control is validated in membrane filtration tests where bimodal 10/20 nm silica peaks are resolved for membrane retention quantification. This work establishes a transferable metrological framework that extends liquid-phase nanoparticle quantification beyond current limitations, providing operating guidelines for reliable sub-50 nm measurements using aerosolization-based techniques.

Ionic liquids (ILs) can modulate protein phase behavior, including crystallization and aggregation. However, crystallization outcomes are often difficult to predict because nucleation is stochastic and strongly affected by specific ion effects. Here, we examine the crystallization pathway of lysozyme in ethylammonium nitrate (EAN) using a multi-modal small-angle X-ray scattering (SAXS) strategy that integrates high-throughput 96-well screening, in situ capillary thermal treatment, and time-resolved kinetic monitoring. To address batch-to-batch variability in these soft-matter samples, we implemented a standardized workflow for extracting complementary SAXS descriptors, including a fixed-window pseudo-Rg descriptor of low-q scattering evolution and a crystallinity index based on Bragg-feature intensity. The SAXS data are consistent with a two-step nucleation-like pathway in which EAN-induced association precedes the appearance of long-range crystalline order, while thermal treatment disrupts metastable clusters without restoring a simple native monomeric state. Machine-learning models were used as within-system interpolation and screening-prioritization tools for the measured lysozyme-EAN composition grid. Linear models failed to reproduce the non-linear trends, whereas ensemble methods reproduced the main features of the measured crystallization region. Feature-importance analysis identified EAN concentration as the dominant control variable (approximately 70% contribution). Together, these results provide a SAXS-based descriptor-extraction and data-analysis workflow for mapping composition-dependent crystallization behavior in the lysozyme-EAN system.

Hybrid nanogenerators that combine piezoelectric and triboelectric mechanisms provide an effective strategy for harvesting mechanical energy from aquatic environments, where device durability and biofouling resistance remain significant challenges. In this work, we report a flexible hybrid nanogenerator based on electrospun poly(vinylidene fluoride) (PVDF) nanofibers incorporated with aluminium nitride (AlN) nanoparticles and encapsulated with hydrophobic Ecoflex for stable underwater operation. The incorporation of AlN acts as an efficient nucleating agent that enhances the electroactive β-phase formation and crystallinity of PVDF nanofibers without external poling. Systematic variation of AlN loading shows that 1 wt% AlN yields the highest crystallinity and β-phase content. Structural and electromechanical characterisations confirm improved dipole alignment and mechanical flexibility of the nanofiber mats, establishing a clear structure-property-performance relationship between nanocomposite design, piezoelectric polarisation, and electrical output. The hybrid nanogenerator integrates the PVDF/AlN piezoelectric layer with a Kapton-based triboelectric unit and is encapsulated with compliant Ecoflex to ensure waterproofing and mechanical stability. Under periodic finger tapping in air, the device produces an open-circuit voltage of 58 V and a short-circuit current of 6 μA, outperforming individual piezoelectric nanogenerator (PENG) and triboelectric nanogenerator (TENG) components. When operated as a cantilever under flowing water, the device generates 85 V and 20 μA at a flow velocity of 2 m/s, delivering a maximum instantaneous power of 0.2 mW and a power density of 0.066 W m[-2] at a load resistance of 1 MΩ. The nanogenerator powers 30 blue light-emitting diodes (LEDs) and demonstrates hydrophobicity; the encapsulated device exhibited reduced bacterial adhesion from Staphylococcus aureus and Pseudomonas aeruginosa, indicating improved interfacial stability and suitability for long-term underwater operation. These results demonstrate a scalable and robust nanogenerator architecture for durable underwater energy harvesting and marine sensing.

Zinc ions play an important role in environmental monitoring and zinc-based energy storage devices. However, simultaneously achieving specific fluorescent detection of Zn[2+] and suppressing dendritic growth on zinc anodes using a single material remains a formidable challenge. In this investigation, we designed and synthesized a series of aromatic polyacylhydrazones featuring nitrogen and oxygen coordination sites for Zn[2+] specific detection and anode protective coating. Among the three polyacylhydrazones, the representative PIH-T exhibits specific Zn[2+] detection through the chelation-enhanced fluorescence effect (CHEF) with exceptional fluorescence stability. Even in the presence of 13 common cations and 10 anions, PIH-T selectively distinguishes Zn[2+] with the detection limit of 0.16 μM and the binding stoichiometry of 2:1. More importantly, PIH-T as a protective coating on zinc anodes effectively regulates Zn[2+] deposition, substantially suppressing dendrite formation, which enables a threefold increase in the cycle life for zinc-ion hybrid supercapacitors (ZHSCs). The serial electrochemical characterization and SEM morphological analysis reveal that, compared with Bare Zn, the PIH-T coating layer enables a uniform, dense zinc surface with no observable dendrites, maintaining the structural integrity and chemical stability even after prolonged cycling. In brief, the single PIH-T not only enables sensitive and selective Zn[2+] detection but also demonstrates great potential as a protective coating layer on zinc anodes in ZHSCs.