Scheelite and calcite share analogous surface characteristics, hindering their flotation separation, while traditional depressants suffer from excessive dosage and poor selectivity. This work fabricates a stable, high-selectivity composite depressant consisting of lanthanide Er3+ and macromolecular CMC for effective scheelite-calcite separation. At a depressant dosage of 1 mg/L and an Er3+ to CMC ratio of 1:2, this composite depressant elevated the scheelite concentrate grade to 73.12%. Potentiometric titration, density functional theory (DFT) calculations and FTIR spectroscopy were adopted to reveal the underlying mechanism. Er3+ can bind to the long carbon chains of CMC at arbitrary angles to form stable complexes. Subsequently, irregular pentahedral coordination structures are constructed via interactions between Er3+ and oxygen atoms in CO32−. These complexes tightly attach to the calcite surface and generate a hydrophilic film, thereby blocking the adsorption of collectors. This coordination flotation strategy highlights lanthanides’ unique mineral processing merits and guides novel flotation reagent development.

Dielectric materials are indispensable in modern electronics owing to their rapid polarization response and excellent thermal stability. However, their widespread application is often constrained by limited energy storage density. A promising approach to overcome this limitation in Bi0.5Na0.5TiO3 (BNT)-based systems involves introducing relaxor ferroelectric phases into the materials, which can produce pinched hysteresis loops beneficial for energy storage. In this study, the incorporation of the relaxor ferroelectric end member Sr0.7Bi0.2TiO3 into BNT-based thin films effectively reduces the ferroelectric-to-relaxor phase transition temperature and stabilizes an ergodic relaxor ferroelectric state at room temperature. This structural modification promotes low-field polarization switching and enhances high-field polarization response, while retaining comparable remnant polarization. As a result, the expanded polarization response leads to a significant improvement in energy storage density, reaching up to 49 J/cm3 in the developed thin films. This work highlights the strategic use of ergodic relaxor ferroelectrics as an effective route for enhancing energy storage performance in ferroelectric materials.

The uniform distribution and high density of ionic moieties in functional porous organic polymers are highly advantageous for carbon dioxide (CO2) capture and conversion. In this study, a series of functional poly(ionic liquid)s (FPILs) with hierarchical nanoporous structure bearing definite hydroxyl group were synthesized via ionothermal free-radical self-polymerization of hydroxyl-functionalized bis-vinylimidazolium monomer. The characterizations reflected that an improved surface area (up to 130.1 m(2) g(-1)), uniform chemical structure, and high-density ionic sites (up to 4.32 mmol g(-1)) and hydroxyl-based hydrogen bond donor (HBD) were achieved by optimizing synthetic parameters. After anion exchange to enrich active Br- anions, the resulting FPIL behaved as high-efficiency heterogeneous organocatalyst for solvent-additive-free CO2 cycloaddition at 90 degrees C and 1 MPa CO2. A high yield of 99.2 % with turnover frequency of 55.7 h(-1) over epichlorohydrin (ECH) was attained, much higher than most reported HBD-based heterogeneous catalysts, even surpassing homogeneous analogue. Furthermore, a wide range of epoxides including sterically hindered ones were transformed with high yields under atmospheric pressure. A possible synergistic effect involving Br- anions and HBDs dual active sites was proposed. This work highlights the significance of integrating hierarchical porosity, high-density and uniformly distributed active sites in the rational design of HBD-based heterogeneous organocatalysts for efficient CO2 fixation.

Catalytically converting 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) underpins renewable, bio -based plastics, yet designing metal-efficient catalysts remains challenging. Here, we combine alloy and support effects by anchoring AuPd alloy nanoparticles on 2D covalent organic frameworks (COFs). Rationalizing alloy composition and COF functionality yielded Au67Pd33/TTATP, which converted HMF → FDCA in water using atmospheric O2 mild conditions, delivering >99% FDCA yield, stable reusability, a turnover number (TON) of ∼100 at HMF/metal = 100, increasing to 518 at 600 (86.4% yield). High performance stems from alloy-support synergy that (i) partitions function (Au: HMF dehydrogenation; Pd: O2 activation) and (ii) matches adsorption-desorption (TTATP enriches HMF yet releases FDCA; alloy surfaces moderate HMF binding and avoid the strong FDCA adsorption of Pd alone), thereby enhancing metal atom efficiency.

A novel MOF-derived catalyst, C-CeMnO, was developed and employed for catalytic ozonation to degrade atrazine (ATZ). By leveraging bimetallic synergy and defect engineering during pyrolysis, a high density of oxygen vacancies (OVs) and low-coordinated Ce/Mn sites was generated. These features yielded Lewis acid site density of 186.32 mu mol.g(-1), markedly enhancing O-3 adsorption and activation. Excellent degradation of ATZ was achieved using C-CeMnO, reaching a removal efficiency as high as 91.9% while maintaining high cycling stability. Mechanistic investigations revealed that the interfacial Ce and Mn redox cycles, coupled with an OV-filling mechanism, synergistically accelerated O-3 activation to generate center dot OH, O-1(2), and O-2 center dot(-). Furthermore, toxicity assessment demonstrated that the C-CeMnO/O-3 system mitigated the ecological risk of ATZ through favorable pathways such as dechlorination-hydroxylation and stepwise dealkylation. This work highlighted the pivotal role of synergistic interactions between OVs and coordinatively unsaturated bimetallic centers, providing important guidance for the development of efficient and stable heterogeneous ozonation catalysts.

Abstract Deep purification of C 2 H 4 from CO 2 /C 2 H 2 /C 2 H 4 /C 2 H 6 mixtures requires balancing impurity rejection, recovery, capacity, and mass transfer. Here, we report an ionic‐liquid‐cation‐exchanged mordenite (MOR) adsorbent for stepwise C 2 H 4 purification. Liquid‐phase exchange of 1‐butyl‐3‐methylimidazolium cations (BMIm + ) preserved the MOR framework while regulating molecular access. The optimized BMIm‐MOR‐1 increased the IAST selectivities of CO 2 /C 2 H 4 , C 2 H 2 /C 2 H 4 , and C 2 H 4 /C 2 H 6 from 4.2, 1.4, and 39 for parent MOR to 10.2, 23.9, and 66, respectively. Dynamic breakthrough tests verified BMIm‐MOR‐1 across binary, ternary, and quaternary streams. For binary CO 2 /C 2 H 4 and C 2 H 2 /C 2 H 4 mixtures, BMIm‐MOR‐1 delivered C 2 H 4 recoveries of 76.4% and 88.0%, respectively, at C / C 0 < 0.01. For ethylene‐rich ternary CO 2 /C 2 H 2 /C 2 H 4 , BMIm‐MOR‐1 produced high‐purity C 2 H 4 with a productivity of 68.1 L kg −1 and higher C 2 H 4 recovery than its counterpart. For quaternary CO 2 /C 2 H 2 /C 2 H 4 /C 2 H 6 , a BMIm‐MOR‐1/MOR tandem scheme is proposed. BMIm‐MOR‐1 removes CO 2 /C 2 H 2 impurities before MOR fractionates the remaining C 2 H 4 /C 2 H 6 stream, increasing practical C 2 H 4 recovery from 57.4% to 64.5%.

The reversible electric-field-induced transition from ergodic relaxors to ferroelectric phase is a highly desirable feature for enhancing the functionality of (Bi,Na)TiO3 (BNT)-based materials. However, in oriented films, substrate-induced strain can significantly affect electric-field-induced structural transformations. The mechanistic interplay between strain and phase transition-crucial for real-world device applications-remains inadequately understood and represents a significant gap in the current understanding of ferroelectric materials. In this study, the electric-field-driven relaxor-to-ferroelectric transition is systematically investigated in textured BNT-based ergodic relaxor thin films. The transition is found to occur within a narrow range of applied electric fields, characterized by double-S-shaped polarization-electric-field (P-E) loops accompanied by four distinct current peaks at relatively low fields. As the electric field increases, ferroelectric behavior becomes dominant. Moreover, (001) texturing not only reduces the required driving electric field for the phase transition but also enhances the ferroelectric performance while suppressing frequency dispersion. These results offer important insights into the unique phase transition mechanisms of ergodic relaxor thin films and suggest potential pathways for optimizing their functional properties.

Photothermal carbon dioxide (CO2) hydrogenation offers an effective avenue to produce solar fuel like methane (CH4) by using the entire sunlight spectrum. However, its application is severely hindered by the sluggish kinetics, leading to the low solar-to-chemical (STC) energy conversion efficiency. Herein, we demonstrated a strategy to boost the photothermal CO2 conversion by directly integrating a high loading (>10 wt.%) of Ni-NiO species into silicalite-1. The highly dispersive Ni species effectively harvested the full solar spectrum to reach a remarkable photothermal effect. Simultaneously, the NiO and Ni sites facilitate CO2 and H-2 activation, respectively, reducing the energy barrier. The surrounding silicalite-1 matrix functions as a thermally insulation shell and exerts a confinement effect to enrich the key intermediate CO. Thereby, under atmospheric conditions, an unprecedented CO2 conversion rate of 92.7 mol m(-2) h(-1) (2.7 mol g(cat)(-1) h(-1) and 23.0 mol g(Ni)(-1) h(-1)) was obtained to achieve a remarkable STC of 9.1%.

Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive-and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework via an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h-1 without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. In situ spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.

Double perovskites offer a chemically flexible platform for coupling cation order, oxygen non-stoichiometry, and transition-metal electronic structure, but these descriptors are often evaluated separately. This study develops a linked structure–property–performance framework for Ba₂FeIrO₆-δ (BFIO) and evaluates how synthesis-controlled B-site order and oxygen-vacancy content relate to oxygen-evolution electrocatalysis. A 72-condition design matrix is analyzed using multivariable ordinary least squares with HC3 heteroskedasticity-robust inference, nonlinear and interaction terms, pathway decomposition, Huber M-estimation, median regression, residual diagnostics, bootstrap confidence intervals, and five-fold cross-validation. Synthesis variables explain substantial variation in B-site order (adjusted R²=0.966) and oxygen non-stoichiometry (adjusted R²=0.932). B-site order is positively associated with conductivity (β=5.712, p<0.001) and inversely associated with charge-transfer resistance (β=-96.095, p<0.001). In the full overpotential model, greater order remains associated with lower η10 (β=-74.809, p<0.001), while higher Rct is associated with higher η10 (β=0.418, p<0.001); the model explains 97.2% of adjusted response variance and retains similar predictive error under five-fold cross-validation. The vacancy linear term is negative, whereas the quadratic term is imprecisely estimated, indicating that the location of any vacancy optimum requires direct experimental validation. Durability is independently associated with order, vacancy state, microstrain, and oxygen post-annealing. Across robust and median-regression estimators, the principal coefficient directions are stable. The results support a quantitative design strategy centered on high B-site order, low interfacial resistance, controlled defect chemistry, and explicit uncertainty reporting rather than single-descriptor optimization.

Solar-driven carbon dioxide (CO2) reduction can sustainably produce chemicals and fuels but is often limited by rapid charge recombination and slow CO2-to-product kinetics, typically necessitating homogeneous photosensitizers and cocatalysts. Here, we reported an integrated photocatalyst, TF-COF-CONH-Au25-Co, constructed by immobilizing atomically precise Au25 nanoclusters (NCs) on a covalent organic framework (COF) incorporating [Co(bpy)3]2+ complex (Co-N6 coordination). Under visible-light illumination, this hybrid catalyzes CO2 conversion to syngas without external photosensitizers or cocatalysts, delivering a CO formation rate of 2,321.9 μmol·g-1·h-1 (turnover number of 171.9 and turnover frequency of 7.2 h-1). The Au25 NCs enhance light responsiveness and charge transfer efficiency, thereby enriching long-lived photogenerated electrons, while concurrently modulating the electronic state of Co sites to reduce the energy barrier for CO2 reduction. This study illustrates a molecular-level strategy to synergistically integrate metal NCs, COFs, and [Co(bpy)3]2+, showing a promising platform for high-performance photocatalytic CO2 conversion.

Efficient removal of trace acetylene (C2H2) from ethylene (C2H4) is crucial for polymer production, yet remains challenging for physisorption separation owing to their molecular similarity. Herein, we synthesized a series of LTL zeolites with varied Si/Al ratios via an acid co-hydrolysis route. The optimal adsorbent LTL(2.3) with a low Si/Al ratio of 2.3 exhibited both high C2H2 uptake (2.79 mmol g-1) and C2H2/C2H4 (1/99, v/v) selectivity of 26.84 at 1 bar and 298 K, as well as superior dynamic separation efficiency. Structural refinement based on high-resolution powder X-ray diffraction (PXRD) patterns illustrates that reducing Si/Al ratio provides more K+ cation that serves as the strong C2H2 binding sites, thereby promoting the C2H2/C2H4 separation. Moreover, the optimal LTL zeolite also demonstrates favorable separation efficiency towards other gas mixtures (e.g., CO2/N2, CO2/CH4, C2H4/C2H6, and C3H6/C3H8), showing the promising potential as a versatile adsorbent for gas separation and purification.

Recently, Metal-organic framework (MOF)-derived diatomic catalysts (DACs) have emerged as novel optimal candidates for advanced oxidation processes (AOPs). Currently, several reviews have summarized MOF-derived DACs and their applications in AOPs. However, novel perspectives yet to be reported and in-depth discussions grounded in current research status remain underexplored. This review tries to provide some real-time patches to the existing insights into synthesis, characterization, and mechanism research. First, the dynamic process of catalyst synthesis was examined through a time-scale lens, focusing on the incorporation of targeted metal. Critical conditions during precursor pyrolysis and the evolution of support configuration were systematically summarized. Subsequently, conventional characterization techniques were reviewed, highlighting potential risks of data misinterpretation and proposing optimization strategies for characterization paradigms based on information necessity. The current application and practical implementation challenges of in-situ characterization technologies were also discussed. Furthermore, the persulfate-mediated water purification mechanism of MOF-derived DACs was elucidated, emphasizing the regulatory effects of secondary metal atom introduction on oxidant capture pathways and the enhancement in pollutant decomposition driven by metal-support-pollutant synergies. Finally, challenges in the design and practical implementation of MOF-derived DACs are proposed. This review is expected to accelerate the development of MOF-derived DACs, enabling their brilliant performance in water purification.

The energy-efficient separation of propylene (C3H6) and propane (C3H8) is severely hindered by their closely similar physicochemical properties and by the susceptibility of many adsorbents to moisture-induced performance degradation. Herein, we report a "template-to-pore modifier" strategy to systematically regulate the intracrystalline pore environment of a pure-silica STT zeolite. By controlling the partial thermal decomposition of the occluded organic template, N,N,N-trimethyl-1-adamantammonium hydroxide, we generate template-derived confined carbon species as confined pore-environment modifiers. These species tune the effective pore aperture to enhance diffusion-assisted discrimination for closely sized molecules while simultaneously creating an in situ hydrophobic shield. Unlike pristine pure-silica STT, which exhibits negligible discrimination between the two hydrocarbons, the optimized sample STT-550(1.4) delivers a C3H6 uptake of 1.59 mmol g-1 and a C3H6/C3H8 IAST selectivity of 11.0 at 298 K. Dynamic breakthrough experiments further confirm efficient separation, together with strong humidity tolerance and cyclic stability under realistic conditions. Beyond C3 separation, this strategy also improves CO2-related separations, providing a practical and potentially general strategy for converting template-derived confined carbon species into functional confined pore-environment modifiers for energy-efficient gas separations.

Photocatalytic aerobic oxidation of methane (CH4) to methanol (CH3OH) offers an alternative to the current energy-intensive route for CH4 utilization, while suffering from the activity-selectivity trade-off due to the uncontrolled generation of reactive oxygen species (ROS). Herein, we perform the photocatalytic CH4 aerobic oxidation in the presence of H2 over a PdCu NPs-modified ZnO catalyst, which exhibits a CH3OH yield of 13.5 mmol gcat -1 h-1 and a selectivity of 71.1%, surpassing many previously reported results. The introduction of H2 enables more ROS production simultaneously from photoelectron-induced O2 reduction and in situ-produced H2O2, facilitating the conversion of CH4. Compared to Pd, the PdCu cocatalyst favors the generation of more center dot OOH radicals in the ROS. More importantly, it is proposed that intermediate CH3OOH can be converted to CH3OH by H2-derived Pd-H species, which could also scavenge the excessive center dot OH radicals and holes, thus promoting the productivity of CH3OH and suppressing overoxidation. This work provides a strategy to regulate ROS formation for efficient CH4 oxidation into CH3OH under mild conditions.

The versatile architecture of covalent organic frameworks (COFs) provides a powerful platform for tailoring their functions. Herein, we demonstrate the molecular engineering of 2D ionic COF nanosheets (iCONs) to reach a family of organic polymeric catalysts with tunable acidity. These solid acidic iCONs are synthesized through Schiff base condensation of the ionic monomer triaminoguanidinium chloride and the aromatic aldehydes with different surface groups. Compared with that in the monomer, the Cl- in iCON matrix tends to be near the framework H atom, generating a new Bronsted acid site with much short Cl-similar to H+ distance that resembles HCl. As a result, these iCONs are highly active in the typical acid reactions of aldol condensation and dehydration of fructose into 5-hydroxymethylfurfural (HMF). The shorter Cl- similar to H+ distance, the better acid catalytic activity. The catalyst DHPA-TG(Cl) reaches a high HMF yield of above 97 % within a short reaction time of 15 min, providing the turnover frequency (TOF) as high as 155.2 h(-1). Facile recycling and stable reusability are also observed. The free energy profiles of these iCONs catalyzing fructose conversion to HMF confirm the function of Cl-similar to H+ units in lowering the energy barrier of the rate-determining step for the water release in the HMF synthesis.

Conventional approaches for treating microplastics are often characterized as incomplete and insufficient, rendering it challenging to elucidate the aging processes and mechanisms of microplastics. We employed irradiation technology to establish a highly potent oxidation system that achieves complete aging of polypropylene microplastics within a short timeframe. The results demonstrate that gamma ray exhibits remarkably strong microplastics degradation capability, with a mass loss reaching 70.58 %. Moreover, distinct aging mechanisms were observed under varying irradiation conditions, confirming that the aging process of microplastics is influenced by the oxidative capacity of the system. As the oxidative strength changes, the generation and transformation sequence of oxygen-containing functional groups also varies. Specifically, gamma ray initially forms ether bonds, followed by the generation of carbonyl and hydroxyl groups; in contrast, electron beam induces hydroxyl formation primarily through C-H bond cleavage before the emergence of other functional groups. The experiments further identified carbonyl groups as the principal sites for adsorption and transformation during the aging and adsorption processes. Because gamma ray preferentially produces carbonyl functionalities, it significantly enhances both the adsorption performance and the aging degree of polypropylene microplastics. Our findings provide new insights and foundation for understanding the aging and adsorption behaviors of microplastics.

Semiconductor photocatalysis has rendered a potential route for aerobic methane (CH4) conversion to valued-added oxygenates under mild conditions, whereas suffering from low reaction efficiency caused by the high inertness of CH4 molecules and the fast recombination of photogenerated charge carriers. Herein, Cu doped ZnO nanoplates with polar surface exposure are employed as an efficient photocatalyst for CH4 oxidation in the presence of O2, which exhibit the liquid C1 oxygenates yield of 4742.2 mu mol g-1 h-1 with a selectivity of 99.6%, outperforming the counterparts with nonpolar surface exposure or without Cu doping. The detailed investigation elucidates that the activity enhancement is largely contributed by the intensified internal electric field, improving the separation of charge carriers and thus supplying sufficient electrons to drive surface redox reactions. More active/adsorption sites are also favorable to be created on Cu doped polar surface of ZnO, facilitating CH4 conversion. Besides, the generation of OH radicals is proposed to follow a pathway of O2 -> OOH -> H2O2 ->OH, wherein the doped Cu plays a significant role for O2 reduction and H2O2 dissociation to OH, thereby enabling efficient CH4 activation. This work offers new strategies for designing efficient photocatalysts to boost CH4 oxidation under mild conditions.

Parameters of ignition chamber (IC) in a jet control compression ignition (JCCI) and methanol-fueled engine significantly influence combustion performance and indicated thermal efficiency (ITE). This study employs numerical simulations to investigate airflow and spray interactions, influencing IC performance in a Turbulent Jet Ignition (TJI) - High Pressure Direct Injection (HPDI) methanol engine. Different IC nozzle structure, namely Modified Outlet Position (MOP) and Fixed Outlet Position (FOP) modes, are compared. Results indicate that FOP mode enhances IC stability by generating divergent velocity vectors through swirling holes, effectively balancing airflow momentum and establishing reliable pathways. Moreover, proper alignment between spray angle and airflow pathways proves crucial, and optimal spray angles enrich the mixture near the spark, thus improving ignition quality and lowering emissions. Additionally, increasing the swirl ratio (SR) in the main chamber (MC) from 0 to 3 enhances airflow momentum into the IC, raising the IC-MC pressure difference by 67.5 %, and enhancing sensitivity to nozzle structure variations. Although it leads to slightly increased THC emissions, optimized airflow structures, high turbulence intensity, and aligned spray angles further elevate the pressure difference by 57.5 %, enhance the ITE by 0.5 %, and reduce carbon emissions by 0.49 %. The findings offer critical theoretical insights for optimizing IC performance in methanol engines.