Atomic layer deposition (ALD) typically achieves uniform, conformal coatings on battery electrodes, but can also produce island coatings under specific low-concentration growth conditions. This work proposes a discrete ALD island coating strategy for porous Li-rich layered oxide cathodes, which is achieved through a low-cycle ALD process. Utilizing N2 adsorption–desorption isotherm and synchrotron nano computed tomography (nano-CT)-based three-dimensional reconstruction for quantitative pore analysis. It is confirmed that compared to a homogeneous film, the tungsten oxide islands selectively nucleate at pore sites, reducing both pore size and pore-throat ratio of the particles, thereby facilitating electrolyte infiltration as confirmed by wetting experiments. Thus, the improved electrolyte accessibility establishes continuous ion pathways and enhances the bulk ion-transport kinetics, which is further substantiated by a series of electrochemical measurements showing that the island-coated material consistently outperforms the homogeneous-coated counterpart in rate performance across the entire temperature range. The proposed strategy offers a new design principle for optimizing electrode materials through targeted pore engineering, moving beyond conventional homogeneous surface films.

Mesoporous metal vanadates (mMVO) are promising visible-light photocatalysts for energy conversion and environmental remediation owing to their suitable band structures, broad visible-light absorption, and excellent chemical stability. However, the controlled synthesis of crystalline mMVO remains challenging, involving the complicated coassembly process and high-temperature crystallization. Herein, we develop a facile polymer-oriented solvent-mediated coassembly strategy to prepare mMVO without additional chelating agents. Using mesoporous InVO4 (mIVO) as a representative example, the ethanol/water volume ratio is used to tune solvent polarity and thereby regulate the electrostatic coassembly of protonated poly(ethylenimine) (PEI), polyoxovanadate species, and In3+ into compact inorganic-organic composites. Subsequent hydrothermal crystallization and calcination yield mIVO with a well-developed mesoporous framework. This strategy can be extended to synthesize a series of mMVO. Among the obtained samples, mIVO (1/1), synthesized at an ethanol/water volume ratio of 1/1, exhibits excellent visible-light photocatalytic degradation of methylene blue (MB), achieving a degradation efficiency of 97.8% within 40 min under irradiation with λ > 420 nm. Experimental results demonstrate that the enhanced activity originates from the synergistic effects of the accessible mesoporous structure, abundant oxygen vacancies, and efficient separation and transport of photogenerated charge carriers.

Multicomponent mesoporous metal oxides (MMOs) with modulated metal composition and porous structure are promising for numerous applications. However, the synthesis system for multicomponent MMOs commonly involves various inorganic precursors, templates, catalysts, and so forth, which is a challenge for efficient synthesis and reserved porous structure due to the complicated assembly process and high-temperature crystallization. Here, we propose a facile low-temperature solid-solid interface crystallization approach for the synthesis of multicomponent MMOs, enabling the precise regulation of metal composition, crystalline structure, and morphology. Representatively, the solid TiO2(OH)n/template composites containing characteristic hydroxy groups and Sr(OH)2 8H2O undergo in situ dehydration to form mesoporous STO/TiO2 with brick-mortar structure, consisting of crystalline SrTiO3 and amorphous TiO2, without the addition of solvent or high-temperature crystallization process. The prepared STO/TiO2 exhibits high surface area of 295-347 m2 g-1 and this method can be extended to synthesize a series of multicomponent MMOs. The mesoporous nanospherical STO/TiO2 exhibits highly selective photocatalytic oxidation, achieving up to 99% conversion of benzyl alcohol and 99% selectivity of benzaldehyde. Experimental results and density functional theory calculations demonstrate the exceptional catalytic performance benefits from the effective separation of photogenerated electron and hole pairs on unique heterojunctions, rich oxygen vacancies, and porous structures.

Mesoporous single-crystal metal oxides are highly attractive for heterogeneous catalysis because they combine high surface accessibility with long-range lattice coherence; however, their synthesis remains fundamentally challenging due to the thermodynamic incompatibility between crystallization and pore formation. Here we report a template-free, energy-driven facet-oriented crystallization strategy that enables the formation of mesoporous single-crystal metal oxides with tunable pore architectures and exposed high-energy facets. Polyvinylpyrrolidone functions simultaneously as a pore maintainer and surface-energy regulator, preserving mesoporosity while selectively stabilizing high-energy facets to direct single-crystal growth. The method is applicable to multiple oxides, including Co3O4, MgO, NiO, and mixed-metal systems. As a representative example, mesoporous single-crystal Co3O4 with preferentially exposed (111) facets exhibits outstanding performance in the selective oxidation of aromatic alkanes, achieving up to 99% conversion and selectivity under mild conditions. Experimental and theoretical analyses suggest that the synergy between mesoporosity and active-facet exposure enhances reactant adsorption, oxygen activation, and reaction kinetics, providing a general design principle for crystallographically defined porous catalysts.

The direct photocatalytic CO2 hydrogenation to hydrocarbons is one of the sustainable alternatives for fossil fuels production but remains challenging due to the intrinsic difficulty of C-C coupling process and ambiguous reaction mechanisms. Here, a composite photocatalyst Ag/AgCl@H '-WO3 (ACW) was constructed for conversion of CO2 and H2 to C2-C6 olefins within a hydrophobic microenvironment constructed from a fluorinated polytetrafluoroethylene (PTFE) layer. CO2 gas is enriched at the interface between the photocatalyst and PTFE due to the hydrophobic interactions. Subsequently, the linear CO2 is bent and polarized through electrostatic interactions from O = C center dot center dot center dot F, C = O center dot center dot center dot F bonds and hydrogen bond from C = O center dot center dot center dot H-O-W. The CO2 activation process facilitates the key CO2 center dot- radicals formation and then increases *CO surface coverage on the photocatalyst. Crucially, Cl- coordinated with Ag enables to shift the*CO adsorption configuration from linear (*COatop) to bridging (*CObridge), which is advantaged for C-C coupling. The yield of C2H4 and C3H6 reached 69.66 mu mol g-1 h-1 under the optimized ACW2-PTFE catalyst and reaction conditions. Moreover, the photocatalyst exhibits efficient performance for the dilute concentration CO2 (20 %) conversion to olefins. This work reveals mechanisms and strategies for the photocatalytic hydrogenation of CO2 into olefins, thus advancing solar fuel development.

The rapid recombination of photogenerated electron-hole pairs is a bottleneck constraining the improvement of photocatalytic efficiency. The construction of porous single-crystalline BiVO4 is expected to resolve this issue and provide plenty of active sites for charge carriers to promote the catalytic reaction. However, due to the fact that the synthesis process requires a delicate balance between the kinetic-driven co-assembly process and thermodynamic-driven crystallization process, it faces significant challenges. Herein, a polymer-intercalated modulation assembly strategy is proposed for synthesizing mesoporous single-crystalline BiVO4 (MSC BiVO4) with tunable pore structure. In this case, the co-assembly of the two metal precursors, acetate ions and polyethyleneimine (PEI), leads to the formation of an inorganic-organic composite via coordination and hydrogen bonding. Moreover, the "modulator" acetate ions obviously weaken the effect of PEI on the original crystal growth orientation of metal oligomers, thereby maintaining the single-crystalline structure. The dendritic PEI acts as a "porogenic agent" to develop a 3D network to intercalate into metal oligomers and form the mesoporous structure. Various characterizations and theoretical calculations verified that the excellent photocatalytic performance with 99% conversion and 99% selectivity for various aromatic alcohols of the as-prepared MSC-BiVO4-1800 is attributed to its single-crystalline properties and well-defined mesoporous structure with vanadium vacancy microenvironment.

Open-shell organic radicals, characterized by their unique spin states, typically exhibit exceptional photothermal conversion efficiency. However, the development of open-shell organic radical materials with stability and high photothermal properties remains a challenge. Among these radicals, the stable and commercialized 4-OHTEMPO radical molecule has garnered considerable attention in various organic synthesis reactions owing to its unique redox advantages, but it shows less application comparing with the other open-shell organic radicals in photo-thermal conversion. In this study, 4-OH-TEMPO exhibits favorable photothermal properties upon combination with Cu2 + , thus it is capable of enhancing the reaction rate of HMF oxidation to DFF by a factor of 10 under LED (400 nm). Under illumination of LED, leading to the complete conversion of HMF and the generation of DFF with a yield of 99.7 % within 30 min. Mechanism study shows that the photothermal effect facilitates the kinetic process of the reaction, and accelerated conversion of 4-OH-TEMPO to the oxidatively active species 4OH-TEMPO+ under light-induced action further increased the reaction rate. This research proffers novel insights and references for 4-OH-TEMPO mediated organic synthesis reactions and the design of free-radical photothermal materials.

This study addresses the key challenges of low charge separation efficiency and insufficient redox capacity in the photocatalytic degradation of organic pollutants. By employing non-metal ion doping techniques and heterojunction engineering, we designed and fabricated direct heterojunction composite photocatalysts to enhance their performance in the degradation of organic pollutant under UV-visible light. First, oxygen-doped g-C3N4 (O-g-C3N4) was synthesized via simple calcination and hydrothermal methods. Subsequently, α-Fe2O3 was deposited onto the surface of O-g-C3N4 using an in-situ precipitation method, successfully leading to the preparation of the α-Fe2O3/O-g-C3N4 (FO/OCN) direct Z scheme heterojunction photocatalytic composite. The mechanism underlying the enhanced photocatalytic degradation performance of this composite material was investigated using a variety of advanced characterization techniques. The results indicate that oxygen doping broadens the light absorption range and raises the energy level of g-C3N4, aligns the band structures of O-g-C3N4 and α-Fe2O3, establishes a direct Z-type charge transfer pathway, promotes the separation of photo-generated electron-hole pairs at the interface, and improves the photocatalytic performance. Under simulated light irradiation, the degradation rate constant of the optimal FO/OCN (FO/OCN-15%) heterojunction for methyl orange (MO) was 13.05, 6.98, and 2.72 times higher than that of pure α-Fe2O3, g-C3N4, and O-g-C3N4, respectively, and it exhibited excellent cycling stability. Free radical trapping experiments and electron paramagnetic resonance (EPR) analysis indicate that superoxide radicals (•O2-) and hydroxyl radicals (•OH) are the primary reactive species. Finally, the mechanism of the heterojunction was further discussed through the analysis of the work function. Finally, the mechanism of the heterojunction was further discussed through the analysis of the work function. This work provides a novel design strategy for the application of highly efficient g-C3N4-based photocatalytic systems in environmental remediation.

Efficient conversion of dilute CO2 into valuable products remains a significant challenge due to the low CO2 concentrations (5-10%) in industrial flue gases, which are accompanied by inert gases and impurities. This results in low partial pressures, limited mass transfer, and dominant side reactions, undermining the efficiency and selectivity of CO2 reduction reactions (CO2RR). To address this, we present a synergistic mechanochemistry-facet engineering strategy for efficient and selective CO2RR under ambient conditions using diluted CO2 streams. By combining ultrasonic cavitation with mechanical stirring and exposing Cu2O (111) facets, the system achieves a CO yield of 1865.6 & micro;mol gcat-1 , CO selectivity of 96.4%, and CO2 conversion efficiency of 13.9% within one hour. These results surpass most previously reported systems for CO2 reduction using low-concentration CO2 streams. Mechanochemical activation enhances mass transfer and accelerates reaction kinetics, while facet engineering optimizes CO2 adsorption and facilitates intermediate conversion. Density functional theory (DFT) calculations further reveal facet-dependent adsorption configurations and mechanochemical CO2RR pathways, clarifying the origins of the improved activity and selectivity. This approach provides a scalable solution for CO2 conversion in low-concentration CO2 environments, holding practical value in advancing industrial flue gas treatment and carbon capture and utilization (CCU) technologies.

The electrocatalytic nitrate reduction reaction (NO3-RR) to ammonia is a promising approach for converting nitrate pollutants to ammonia under mild conditions. Metal phthalocyanine-based conjugated polymers, with their well-defined structures and tunable functionality, are emerging as efficient two-dimensional (2D) catalysts for this reaction. Herein, we report a 2D-conjugated nickel phthalocyanine polymer (NiPcP) that demonstrates high efficiency and selectivity in the NO3-RR. The material features high-density, well-defined Ni-N4 sites and the nitrogen-bridged tetra-isoindole structures create a hydrophobic microenvironment and electron-rich Ni centers, which facilitate nitrate adsorption and electron transfer and suppress the hydrogen evolution reaction (HER). As a result, the NiPcP achieves a maximum faradaic efficiency of 99.7% and an NH3 yield rate of 14.2 g h-1 gcat-1, maintaining over 80% efficiency across a broad potential window (from -0.5 to -0.9 V vs. RHE) and a wide nitrate concentration range (from 10.0 mmol L-1 to 2.0 mol L-1). It is the first noble metal-free Ni-based catalyst that exhibits such a high FE in such a broad potential window and wide nitrate concentration range simultaneously. This work offers an effective molecular design strategy for developing metal-organic electrocatalysts for sustainable ammonia synthesis and nitrate pollution remediation.

In this study, an in situ oxidation method was employed to surface-treat FeSiBNbCu nanocrystalline powders, aiming to create a uniform core–shell structure of Fe3O4@epoxy resin coating. This approach enabled the successful fabrication of FeSiBNbCu nanocrystalline soft magnetic powder cores (NSMCs) with outstanding comprehensive performance. The Fe3O4 coating formed on the magnetic powder surface can effectively reduce the magnetic core loss and improve the high-frequency soft magnetic properties. Meanwhile, the growth mechanism and phase composition of the Fe3O4 insulating layer were investigated using XPS, FTIR, XRD, and SEM–EDS. The influence of oxidation temperature on the properties of FeSiBNbCu@Fe3O4 NSMCs was systematically examined. Following in situ oxidation reaction at 120 °C for 2 h, a thin and dense Fe3O4 coating was formed on the surface of the FeSiBNbCu nanocrystalline powders. The resulting NSMCs exhibit a stable effective permeability of 18.0 between 10 kHz and 10 MHz. The core loss (Pcv) is 2877.1 mW/cm3 at 1MHz and 50 mT, which is approximately 14.7

Selective oxidation of aromatic alkanes is a key reaction to produce high-value chemicals in the chemical industry. However, the strong C–H bonds and inert chemical properties of aromatic alkanes render the oxidation process difficult, thereby making the development of promising and sustainable catalysts highly desirable. Herein, a resin-assisted coordination co-assembly strategy is developed to synthesize heterometal-doped mesoporous Co3O4 with abundant oxygen vacancies, enabling precise control over both composition and pore structure. The site-specific Mn doping at octahedral sites of mesoporous Co3O4 promotes the formation of oxygen vacancy with enhanced activity. Density functional theory calculations further demonstrate that Mn doping in mesoporous Co3O4 reduces the oxygen vacancy formation energy, induces the electronic structure modifications and introduces the defect energy levels, finally promoting the efficient catalytic oxidation of a series of aromatic alkanes. Representatively, Mn-doped mesoporous Co3O4 exhibits remarkably outstanding catalytic activity, achieving 37

Carbon-supported Pd catalysts are pivotal in alkynol hydrogenation for fine chemicals and pharmaceuticals. Heteroatom doping and porous structures of supports can modulate the metal electronic structure and improve mass transfer, respectively, thereby influencing catalytic activity. However, precise control over doping configurations and porous support construction remains challenging. Herein, we present molecular engineering based on the three-component polymerization of ascorbic acid, ethylenediamine, and glyoxal to design mesoporous co-doped carbon with adjustable N and O composition. The strategy enables a high degree of control over mesoporous structures and phenolic and pyridinic N configurations, thereby facilitating the anchoring of Pd nanoparticles. Density functional theory calculations reveal that the interplay between lone-pair electrons of phenolic O and pyridinic N induces local strain and charge polarization, activating Pd clusters and lowering the hydrogenation barrier. The optimized supported Pd catalyst delivers an exceptional turnover frequency of 47 890 h-1 and 95% selectivity in the semi-hydrogenation of 2-methyl-3-butyn-2-ol.

Previous studies focused on transition metals-based catalysts as homogeneous and heterogeneous active sites for the degradation of pollutants by peroxymonosulfate (PMS). However, leaking or residual metals can pose secondary hazards to the environment and human health. This research demonstrated that carbonate (CO3 2-) and bicarbonate (HCO3-) could recognized as an eco-friendly homogeneous catalyst to activate PMS to degrade pollutants. Norfloxacin (NOR) was completely degraded by the HCO3-/PMS system in 30 min at 2 mM HCO3-and 5 mg/L NOR, which was significantly better than other anions. Both the electrochemical properties of contaminants and the active species produced during the degradation of pollutants played important roles in the degradation of pollutants. The pollutants with low redox potentials, high EHOMO, and low energy gaps (Delta E = ELUMO-EHOMO) were more susceptible to be attacked. The HCO3-/PMS system was capable of resisting the influence of water matrix and effectively removing pollutants in actual hospital wastewater. The effective breaking of the O-O bond of PMS by HCO3-and CO32-was verified by Density Functional Theory (DFT) calculations, which encouraged the production of SO4 center dot- for NOR degradation. Crucially, the addition of oxygen significantly increases the electron paramagnetic resonance (EPR) peak intensity of single-linear oxygen (1O2) in the HCO3-/PMS system, thus rapidly increasing the rate of PMS activation for degradation of NOR. These results illuminated the role of bicarbonate in AOPs utilizing PMS and uncovered the underlying mechanism of PMS activation by HCO3-.

Photocatalytic oxygen reduction reaction (ORR) represents a clean and sustainable strategy for hydrogen peroxidation (H2O2) production, yet it faces challenges including charge transfer and activation of O-2. The introduced of alkali metal doping and cyano group defects into C3N4 will improve the charge carrier separation efficiency and optimize the ORR pathway, thus facilitating H2O2 production over C3N4. In this study, we prepared K-doped and cyanide-modified carbon nitride (Kx-CN) using a simple potassium salt-assisted thermal copolymerization strategy. The H2O2 formation rate of K-5-CN reached at 876.7 mu M g(-1) h(-1), about 5.5 times that of the original C3N4. Moreover, the photocatalytic ORR pathway was modulated by an external magnetic field, which further increased the H2O2 yield to 2208.2 mu M g(-1) h(-1). Meanwhile, the regulation of furfural oxidation products was achieved through the application of magnetic fields. This work highlights the significant role of the external magnetic field in exciton dissociation and ORR pathway regulation, providing a new idea for the efficient H2O2 production.

Pd-based catalysts are considered promising for the formic acid oxidation reaction (FAOR), whereas the toxic effect of poisoning intermediates greatly affects the stability and activity of the catalysts. Herein, a dual-force-driven self-assembly strategy is developed to synthesize mesoporous palladium-boron (meso-Pd-B) alloy using cationic polymer polyethyleneimine (PEI) as a pore-forming agent. In this strategy, PEI can interact with the Pd metal precursor via electrostatic and coordination interactions and self-assemble into stable organic-inorganic composites. Dimethylamine borane as a reducing agent together with boric acid enables the alloying of Pd with B, and the Pd-B alloy with mesoporous structure is obtained driven by dual forces. The strategy can be generalized to synthesize other mesoporous metal-B alloys (e.g., Pt-B, Ag-B, Ir-B, Ru-B, and Rh-B). The resultant meso-Pd-B alloy exhibits remarkable catalytic performance (1310 mA mg-1) in FAOR. Combined experimental results and density functional theory calculations indicate that the enhanced activity can be attributed to the electronic effect resulting from the alloying of Pd and B, which weakens the binding strength of toxic substances on the surface of the Pd catalyst. And the favorable mesoporous structure allows the catalyst to expose more catalytic active sites and accelerates the substance transfer efficiency.

Spin polarization manipulation has been exploited as an effective strategy to regulate the catalytic efficiency, especially for the reactions that involve spin state transition. Chiral structure construction provides an interesting pathway to realize spin polarization through a chiral-induced spin selectivity (CISS) effect without complicated materials design and external magnetic field application. Most of the CISS-related studies have been carried out at room temperature, with the effect of the temperature often overlooked. Herein, chiral BiOBr was synthesized, and the CISS effect could be applied for boosting photocatalytic HBrO production, which is attributed to the suppressed recombination of photogenerated carriers. More importantly, the CISS effect was demonstrated to be temperature dependent and could be strengthened at an elevated temperature. The elaborate mechanism study also shows that electrons with a specific spin orientation would facilitate electron transfer to O2 for promoting the subsequent reactions. This work offers solid evidence for the temperature dependency of the CISS effect and could benefit the exploration of more untapped paradigms for photocatalysis through spin polarization.

Continuous flow reactors have seldom been employed in investigations concerning 5-hydroxymethylfurfural (HMF) oxidation reactions. The root cause lies in the fact that, at atmospheric pressure, the solution exhibits a rather low oxygen content. In this research, we present a Ru-loaded manganese oxide octahedral molecular sieve (OMS-2) catalyst. Remarkably, this catalyst has exhibited the ability to achieve a 100 % conversion rate of HMF and attain a 94.5 % yield of FDCA under ambient air conditions within a continuous flow reactor. This can be mainly attributed to the superior oxygen adsorption and activation capacity of 0.05Ru-OMS-2. Thanks to this, it exhibits good performance even under hypoxic conditions. The combined results of EPR and XPS clearly showed that the Ru in the catalyst not only boosts the adsorption and transformation of O2 but also weakens the Mn-O bond in the carrier, thus enhancing the activity of lattice oxygen.

Solid polymer electrolytes (SPEs) with excellent ionic conductivity and a wide electrochemical stability window are critical for high-energy lithium metal batteries (LMBs). However, the widespread application of polymer electrolytes is severely limited by inadequate room-temperature ionic conductivity, sluggish interfacial charge transport, and uncontrolled reactions at the electrode/electrolyte interface. Herein, we present a uniform polymerized 1,3-dioxolane (PDOL) composite solid polymer electrolyte (PDOL-S/F-nano LiF CSE) that satisfies these requirements through the in situ catalytic polymerization effect of nano LiF on the polymerization of 1,3-dioxolane-based electrolytes. The synergistic catalytic effect of well-dispersed nano LiF and lithium tetrafluoroborate (LiBF4) enhances the polymerization of DOL monomers, achieving a conversion rate of up to 83.19% and extending its electrochemical window. Furthermore, the well-dispersed nano LiF forms a stable LiF-rich CEI and SEI, providing exceptional interfacial stability. Based on the PDOL-S/F-nano LiF CSE, the symmetric lithium cell exhibits an ultra-low overpotential of 10 mV at 0.1 mA cm-2 and 0.1 mAh cm-2 and maintains steady cycling for over 1500 h at 0.2 mA cm-2 and 0.2 mAh cm-2. The Li parallel to LiCoO2 LMB using the PDOL-S/F-nano LiF CSE also delivers a brilliant rate capability and long cycling stability over 200 cycles at 4.4 V (capacity retention of 82.6%). This study provides solutions to the ongoing pain point issues of SPEs and facilitates practical applications of solid-state LMBs.