Abstract The photocatalytic conversion of methane to formaldehyde under mild conditions is important for C1 chemistry and methane utilization, yet challenges such as reliance on noble metals and poor selectivity persist. Here, we report a noble-metal-free Fe-doped ZnO catalyst enriched with oxygen vacancies (OVs), where single-atom Fe and OVs synergistically lower the water dissociation barrier (0.15 vs. 0.52 eV on ZnO) to drive the proton-coupled electron transfer (PCET) process. Kinetic isotope effect experiments reveal that water dissociation is the rate-determining step, the acceleration of which is crucial for establishing a self-sustaining proton supply. In situ diffuse reflectance infrared Fourier transform spectroscopy and electron paramagnetic resonance confirm that PCET-mediated O2 reduction generates •OH, which selectively oxidize methane to formaldehyde via methanol intermediates. The optimized Fe0.05-ZnO achieves a formaldehyde yield of 29.00 μmol h−1 (89.45% selectivity), surpassing pristine ZnO by 4.12-fold while suppressing CO2 formation. This work provides mechanistic insights into proton-regulated photocatalytic alkane activation and solar-driven C1 conversion.

The research and development of new and efficient solid lubricants are crucial. Because a layered crystal structure is prone to lateral slip and is conducive to lubrication, in this study, for the first time, layered lanthanide hydroxy sulfates RE(OH)SO4 (RE = La/Sm) are evaluated as solid lubricant additives, and the tribological properties of these materials on steel/steel friction pairs in lithium-based grease under various harsh conditions are investigated systematically by SRV tester. The extreme-pressure loads of RE(OH)SO4 can reach 1000 N (equivalent to 4.69 GPa), which is twice that of molybdenum disulfide (MoS2). In addition, the RE(OH) SO4 materials exhibit excellent anti-wear performance. The microscopic analysis of the friction surface indicates that RE(OH)SO4 undergoes a tribological chemical reaction with the metal substrate during the friction process, and the resulting products adhere to the steel surface, forming a protective film. Through the in-depth analysis of the action mechanism of the friction film, the reason for the excellent synergistic effects on lubrication properties and corrosion resistance of RE(OH)SO4 has been revealed. In addition, the fluorescence properties of the lanthanide Sm may be used to assess the lifespan of the lubricating grease, thereby providing a basis for determining the correct time for the replacement of ineffective lubricating grease.

The transfer hydrogenation of polycyclic arenes is highly challenging due to the absence of lone-pair electrons in aromatic systems, which are typically essential for H-donor activation via the Meerwein-Ponndorf-Verley (MPV) pathway. This study aims to overcome such limitation by designing an integrated catalytic pair capable of independently achieving hydrogen donor dissociation and substrate activation, thereby decoupling hydrogen transfer from substrate coordination. Herein, we constructed copper-iron spinel catalyst with abundant Cu+-Fe3+ pairs via a liquid-phase reduction strategy. This catalyst showcases excellent performance in the transfer hydrogenation of diverse polycyclic arenes with isopropanol as H-donor (e.g., 100% conversion and 99% selectivity toward dihydroanthracene in anthracene hydrogenation). In-situ spectroscopic studies and theoretical calculations reveal that the synergistic Cu+-Fe3+ pairs within the spinel are crucial for cleaving hydrogen species from isopropanol. The reaction proceeds via a non-cyclic proton-transfer mechanism, thereby establishing a general strategy for activating inert arenes.

Hydrogenation of aromatic compounds under mild conditions remains challenging because of the high stability of aromatic pi systems. Here, we report a physically mixed catalyst comprising rhodium (Rh) and cobalt (Co) nanoparticles embedded in montmorillonite (MMT) that overcomes this limitation. The enhanced activity arises from dynamic interparticle cooperation: Rh nanoparticles selectively dissociate H2, and the resulting hydrogen intermediates are transferred through particle collisions to Co nanoparticles, where aromatic hydrogenation occurs. This cooperative process can be finely regulated by tuning the oxidation states of the individual metal nanoparticles, leading to catalytic performance surpassing that of corresponding Rh-Co alloy catalysts (initial rate: 45 vs 9 mu M s-1). Combined experimental and computational investigations reveal that cooperative catalysis can be quantitatively described using linear regression analysis and thereby be predicted through the rate similar to k & times; (Co2+/Co3+)/(Rh0/Rh3+). Our findings establish a data-driven statistical approach for designing high-performance bimetallic catalysts based on dynamic interparticle interactions.

Aqueous manganese-ion batteries (AMIBs) benefit from low cost, high safety, and abundant manganese reserves, positioning them as strong candidates for next generation energy storage systems with promising development potential. Nevertheless, a series of critical issues still limit the further development of AMIBs. Manganese metal anodes suffer from severe hydrogen evolution, corrosion and dendrite growth, while Mn2+ exhibits sluggish interfacial kinetics. In addition, advanced electrode materials and high-efficiency electrolyte systems remain insufficiently explored. This review systematically summarizes recent progress in AMIBs regarding cathodes, anodes, and electrolytes. It analyzes the advantages and limitations of diverse electrode materials, with a focus on charge storage mechanisms and performance optimization strategies. The characteristics and design principles of different electrolytes are also discussed. Finally, feasible development strategies are put forward, providing a reference for the design and optimization of high-performance aqueous manganese-ion batteries.

Cumene, a key intermediate for phenol and acetone production, is synthesized via benzene alkylation with propylene over solid acid catalysts. In zeolite catalysts, the spatial distribution of Br & oslash;nsted acid sites, determined by the framework aluminum siting, plays a decisive role in catalytic performance and stability. Herein, conventional (Conv-beta), hierarchical (Hier-beta), and nanocrystalline (Nano-beta) zeolites with comparable Si/Al ratios were synthesized to reveal how the spatial distribution of Br & oslash;nsted acid sites governs catalytic performance. The results of the catalytic stability tests demonstrated a distinct lifetime trend: Nano-beta > Hier-beta > Conv-beta. Characterization by probe-molecule FTIR and Al-27 MAS NMR, demonstrated that Nano-beta not only shortens the intracrystalline diffusion path length but also alters the distribution of Al in T-sites, thereby increasing the fraction of kinetically accessible Br & oslash;nsted acid sites. This tailored aluminum distribution shifts coke formation from internal pore blockage to a superficial carbon layer, which preserves the internal porosity and maintains active sites. Our findings demonstrate that the enhanced stability of Nano-beta thus results from the synergistic effects of diffusion shortening and modified Al siting.

Photoelectrochemical glycerol oxidation for biomass valorization is critically limited by inefficient charge separation and poor product selectivity. This work presents a synergistic bulk-surface dual-modification strategy that simultaneously overcomes both challenges through a Mo-doped BiVO4 photoanode decorated with CoOOH cocatalyst (Mo:BiVO4/CoOOH). Under simulated sunlight at 1.23 V vs. RHE, the composite achieves a photo-current density of 3.50 mA & sdot;cm-2 with exceptional 68% selectivity for glyceraldehyde (GLAD), representing a 3fold improvement over pristine BiVO4 (23%). Mechanistic investigations reveal complementary functions: Mo6+ doping creates donor levels and lattice strain, establishing an intrinsic electric field;while the amorphous CoOOH layer extracts interfacial holes and forms Co3+ active sites that selectively bind and activate the primary hydroxyl group of glycerol. This surface regulation directs the reaction pathway toward GLAD while suppressing deep oxidation to C1 products. By elucidating how coordinated bulk and surface engineering controls both efficiency and selectivity, this work provides a versatile blueprint for designing advanced photoelectrocatalytic biomass conversion systems.

Zeolite Beta, discovered in 1967, features a unique three-dimensional (3D) 12-ring channel system and a highly tunable Si/Al ratio (SAR), granting exceptional stability and acidity crucial for catalysis. While conventional hydrothermal synthesis normally yields zeolite Beta with the SAR range of 10-30 using tetraethylammonium hydroxide (TEAOH) as the organic structure-directing agent (OSDA), the discovery of Al-rich natural mineral (Tschernichite) with the & lowast;BEA topology (SAR similar to 3.3) spurred efforts to synthesize low-SAR Beta zeolite for enhanced acid site density, hydrophilicity and ion-exchange capacity, enabling applications like dehydration, separation and shape-selective catalysis. However, achieving low SARs for the hydrothermal crystallization of zeolite Beta is still challenging, requiring excess Na+ which promotes impurity phases (e.g., GIS, ANA, MOR), prolongs crystallization period and reduces yield. Inspired by our recent work on the kinetic-control synthesis of high-silica NaY zeolite using aluminophosphate as the aluminum carrier, this study presents an accelerated, impurity-free synthetic route to achieve Al-rich zeolite Beta. Using the pre-synthesized aluminophosphate (e.g., AlPO-5) as a partial Al source favors the formation of a silica-rich Beta zeolite nucleus, thus effectively suppresses impurities (eliminating GIS phase in Na+-containing system) and amorphous phase (in Na+-free system), ultimately accelerating crystallization process. Based on this synthetic control, this study successfully synthesized the phase-pure Beta zeolite at SAR of 7.55 (Na+-free) and 6.58 (Na+-containing), while this strategy was extended to the Beta zeolite synthesis with other aluminophosphate, including SSZ-51 (SFO) and AlPO-18 (AEI).

This study developed a lattice-matching engineering strategy to construct atomic-level coherent interfaces in hexagonal WO3/TiO2 S-scheme heterojunctions to boost photoelectrocatalytic glycerol (Gly) valorization. Through precise annealing control, hexagonal WO3/TiO2 achieved an ultra-low lattice mismatch (m) of 0.027%, significantly lower than the 2.30% mismatch of its monoclinic counterparts, thus inducing a strong built-in electric field (3.71 eV) and optimized S-scheme charge transfer. These features resulted in 90% suppressed carrier recombination, 2.64-fold extended carrier lifetime, and enhanced secondary hydroxyl adsorption affinity (1.854 eV), collectively steering Gly oxidation toward high-value dihydroxyacetone with 35% selectivity (1.9-fold higher than that of monoclinic systems). The heterojunction also delivered a 21% Gly conversion rate (40% higher than its monoclinic counterparts), while maintaining > 85% total C3-product selectivity and stability over 40 h. This study identified the atomic-scale interface coherence as a critical factor for synchronizing charge dynamics and surface reactions in biomass upgrading.

Suppressing CO2 formation while preserving high selectivity toward light olefins remains a central challenge in the Fischer-Tropsch to olefins (FTO) process. Herein, we propose a strategy to regulate iron carbide phases by impregnating Fe species onto layered double hydroxides (LDHs) containing auxiliary elements (Ca or Mn) within their inorganic layers. These incorporated metal ions significantly influence the reduction and carburization behavior of iron species, thereby directing the evolution of distinct iron carbide phases. Specifically, CaAl-LDH leads to a mixed Fe5C2/Fe2C phase, whereas MnAl-LDH predominantly yields Fe5C2. Consequently, the Ca-promoted catalyst exhibits superior catalytic performance, achieving 79.1% CO conversion, 47.9% selectivity toward C-2-C-4 olefins, and a significantly suppressed CO2 selectivity of only 4.5%, clearly outperforming its Mn-based counterpart. In situ DRIFTS analysis reveals a cooperative catalytic mechanism involving Fe5C2 and Fe2C phases. This dual-site pathway directed carbon toward chain propagation rather than oxidation, thereby effectively suppressing CO2 formation. Our findings demonstrate that tuning iron carbide ensembles via engineering the support offers an effective route toward carbon-efficient FTO catalysis.

The inherently ordered configuration of metal cations and hydroxyl groups in layered double hydroxides (LDHs) facilitates a spatially precise distribution of Lewis acid and Brønsted base sites with adjustable moderate strength, providing an optimal platform for cooperative transfer hydrogenation. A series of LDHs were synthesized through coprecipitation and assessed for their efficacy in cinnamaldehyde transfer hydrogenation using in situ infrared spectroscopy, isotope labeling, chemisorption, and density functional theory calculations. Isotope labeling verified the presence of distinct hydrogen species originating from dual active centers, while infrared spectroscopy demonstrated that surface Lewis acid sites activate the carbonyl group and Brønsted base sites promote hydride transfer, with the periodic LDHs lattice ensuring their orderly spatial cooperation. These findings establish an acid–base synergistic mechanism for transfer hydrogenation in iron-based LDHs. This study underscores the potential of leveraging the intrinsic structural order of LDHs to develop sustainable, non-noble metal catalysts for the selective hydrogenation of α,β-unsaturated aldehydes in environmentally friendly fine chemical synthesis.

Abstract Defect engineering of metal-oxide interfaces offers a powerful approach for regulating catalytic hydrogenation, yet its role in the deep hydrogenation of polycyclic aromatic hydrocarbons remains elusive. Herein, we synthesize a series of two-dimensional WOx nanosheets with tunable oxygen vacancy concentrations through a glucose-assisted hydrothermal strategy and construct defect-engineered Pt/D1-WOx catalysts for PAHs hydrogenation. The Ov-rich Pt/D1-WOx catalyst exhibits remarkably enhanced deep hydrogenation performance toward decalin formation compared with defect-free Pt/WO3, achieving a nearly 2.5-fold increase in TOFNA (162.7 gNA gPt–1 h–1). Experimental measurements and theoretical calculations reveal that Ov fundamentally reconstructs the Pt-WOx interfacial microenvironment by strengthening electronic metal-support interactions and stabilizing interfacial Ptδ+–O–W5+ configurations. Meanwhile, Ov adjacent to Pt functions as a hydrogen reservoirs that facilitate hydrogen spillover and maintain high local hydrogen chemical potential around interfacial active sites, which is critical for continuous aromatic ring hydrogenation. The cooperative interplay among interfacial electronic modulation, hydrogen spillover, and substrate activation establishes a hydrogen-enriched catalytic interface for efficient PAHs deep hydrogenation. These findings provide mechanistic insights into defect-regulated metal-oxide interfacial catalysis in aromatic hydrogenation.

Zeolitic imidazolate frameworks (ZIFs) are widely used as precursors for producing atomically dispersed catalysts, but structural collapse and metal sintering during pyrolysis often limit the accessibility to active sites. Herein, a pre-passivation strategy is proposed to enable the synthesis of an axial Co-N-5 configuration through the controlled pyrolysis of ZIF-67. This mild thermal treatment effectively prevents structural collapse and metal aggregation. Experimental and theoretical analyses demonstrate that this strategy enables highly dispersed metal sites, while axial N coordination effectively modulates the acid-base properties of the material. The large number of acid-base sites facilitates the cooperative activation of ethylene oxide and fatty alcohols, thereby lowering the energy barrier for the rate determining ring opening step. Moreover, the shape selectivity within the microporous framework modulates the adsorption of the key CH3OCH2CH2O* intermediate. This synergistic acid-base catalysis endows Co-N-5 /NC with enhanced ethoxylation performance and narrow product distribution. The Co-N-5 /NC catalyst achieves 93.90% alcohol conversion at 180 degrees C with a selectivity coefficient (Cs) of 12.56 in the ethoxylation reaction, outperforming most reported catalysts. This work provides insights into Co-N-5 active sites that are important in acid-base catalysis.

Interfacial engineering is central to heterogeneous catalytic hydrogenation. However, achieving the precise control of bimetallic interfaces in supported bifunctional catalysts remains a critical issue. Herein, we present a strategic atom-replacement approach in which Cu acts as a spatial mediator and anchoring site, enabling Pt to be selectively deposited onto CuWOx nanoislands, thereby forming well-defined high-density Pt-WOx active sites for the selective hydrogenolysis of glycerol. The characterization results demonstrate that Cu species modulate the electronic states of the Pt-WOx centers, while the cooperative interaction between Pt and Cu enhances the hydrogen spillover across the Pt-WOx interface. This synergy promotes the formation of 1,3-propanediol (1,3-PDO) by optimizing the reaction pathway. Consequently, the Pt-WOx/gamma-Al2O3 catalyst achieved 65% selectivity to 1,3-PDO with a space-time yield of 0.302 g1,3-PDO & centerdot;gcat-1 & centerdot;h-1 at a high glycerol concentration (30.0 wt%), outperforming all previously reported Al2O3-based systems. This work not only provides a new approach for nanoisland synthesis, but also offers valuable insights into interfacial control in heterogeneous catalysis. (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

ABSTRACT Selective conversion of biomass‐derived glycerol into high‐value chemicals is challenged by poor selectivity and mass‐transfer limitations. Here, a BiOI/Au/TiO 2 photoanode is developed, where plasmonic Au mediators facilitate a transition from Type‐II to Z‐scheme charge transfer. This heterojunction preserves strongly oxidative holes on the TiO 2 surface, as confirmed by femtosecond transient absorption spectroscopy and spatially resolved MnO x photodeposition. In situ characterizations and density functional theory (DFT) reveal that this hole‐rich interface strengthens specific primary hydroxyl (pri‐OH) adsorption, lowering the rate‐determining dehydrogenation barrier to ∼0.6 eV. It also promotes rapid glyceraldehyde (GLAD) desorption, suppressing over‐oxidation. In a static H‐cell, the photoanode achieves 87% GLAD selectivity with a glycerol conversion rate of 341.25 mmol·m −2 ·h −1 . To overcome diffusion limitations, computational fluid dynamics (CFD) simulations were employed to design a continuous‐flow reactor for the 100 cm 2 large‐area photoanode. The flow system prevents product accumulation, boosting GLAD selectivity from 48% (H‐cell) to 77% for the large‐area electrode, with enhanced glycerol conversion (60.34%) and stable 120 h operation. This work provides a laboratory scale‐up by integrating nanoscale reprogramming with macroscale reactor engineering.

The predominance of micropores in low-permeability coal seams inherently restricts water injection due to capillary effects, impeding permeability enhancement. An advanced anionic surfactant and alkaline hydrophobic SiO2 (AS-AH SiO2) nanofluid was developed to reduce pore resistance, change the dominant pore type and increase coal sample porosity. Seepage experiments were performed on coal samples treated with AS-AH SiO2 nanofluids at varying mass concentrations. Nuclear Magnetic Resonance (NMR) and contact angle measurements were used to assess coal wettability and liquid-phase retention removal. Fourier-transform infrared (FTIR) spectroscopy was employed to investigate changes in oxygen-containing/hydroxyl functional groups. Low-temperature liquid nitrogen adsorption experiments analyzed porosity, while scanning electron microscopy (SEM) observed structural alterations. Results indicate that permeabilities of all nanofluid-treated coal samples increased, reaching a stable value within the 0.1-0.15 % mass concentration range. Contact angles on coal surfaces rose from <90 degrees (raw coal) to >90 degrees (AS-AH SiO2-treated), while oxygen-containing/hydroxyl functional groups decreased, collectively indicating a transition from hydrophilic to hydrophobic surfaces. This finding was corroborated by NMR results, revealing substantial liquid release from mesopores in treated samples. Porosity analyses via Barrett-Joyner-Halenda (BJH) and Brunauer-Emmett-Teller (BET) methods demonstrated increased pore volumes and specific surface areas in treated coal. Furthermore, density functional theory (DFT) analysis demonstrated a transition in the dominant pore size distribution of coal samples, evolving from micropore-dominated to mesopore-dominated systems. SEM imaging revealed fragmentation of raw coal blocks into smaller particles, generating extensive mesopores. In summary, AS-AH SiO2 nanofluids could effectively reduce pore resistance and enhance coal porosity optimally at 0.1-0.15 % mass concentration. These findings present a novel material for permeability enhancement during coalbed liquid injection.

Copper exchanged SSZ-13 zeolites are effective catalysts for the photothermal conversion of methane to methanol at low temperatures. Further progress is limited by the difficulty in controlling the structure and dynamic evolution of confined Cu x O y active sites. Here we show that framework incorporated Zn in SSZ-13 enables continuous photothermal catalytic methane oxidation, while Zn itself remaining redox inactive. Combined spectroscopic analyses and theoretical calculations reveal that Cu species are confined within the zeolite cages as Cu 2 O 2 and Cu 3 O 3 clusters. Framework Zn induces interfacial charge transfer from Cu to the Zn modified framework, preferentially stabilizing larger Cu 3 O 3 motifs within the eight membered ring cages and markedly lowering the energy barriers for C-H bond activation. Light does not directly initiate methane activation. Instead, it regulates thermal catalysis by modulating the electronic structure and population of Cu x O y species, thereby promoting the formation of key reactive intermediates (•OH, •O 2 − , and •CH 3 ). As a result, Cu/Zn-SSZ-13 delivers a methanol yield of 466.8 µmol g − 1 h − 1 with 79.1% selectivity and maintains stable performance over 100 h, corresponding to a 1.6-fold improvement over conventional Cu/SSZ-13 under purely thermal conditions. This work establishes a framework enabled photothermal strategy for rationally regulating confined metal-oxo species in zeolite catalysts.