Excessive greenhouse gas emissions from fossil fuel consumption, particularly in energy-dependent sectors, highlight the urgent need for cleaner alternatives such as hydrogen as a promising energy source. Methane decomposition (MD) is a key milestone in the production of CO_x-free fuels, while producing valuable carbon nanomaterials, and commonly used catalysts include metallic oxides and noble metals. Noble metals have attracted wide attention because of their unique electronic structures and good catalytic qualities. Hence, initially, this review systematically focuses on the performance of noble metal catalysts, including Pt, Pd, Rh, Ru, Ir, and Au in the methane decomposition process, highlighting their distinct reaction mechanisms and active site behaviors. Beyond serving as active catalytic components, special attention is placed on the promotional behavior of noble metals, which, when incorporated with transition metals, can tune electronic interactions, increase dispersion, and suppress deactivation, offering a new perspective on their dual functionality in methane decomposition catalysis. Additionally, the influence of reaction conditions, including WHSV, feed ratio, and CH₄ partial pressure, is examined to correlate reaction conditions with catalytic performance. The next objective also encompasses strategies for improving catalytic performance, such as evaluating various active sites, exploring synthesis strategies, investigating the nature of the supports, examining the presence of promoters, and utilizing plasma-assisted reduction. The final section of this review provides a roadmap for future development of high-performance, cost-effective, and durable noble metal-based catalysts for efficient methane decomposition.

Photocatalytic water splitting for hydrogen production presents a promising pathway for sustainable energy generation. Among various semiconductors, cadmium sulfide (CdS) stands out as a leading visible-light-responsive photocatalyst due to its narrow bandgap and suitable conduction band potential. However, its severe charge carrier recombination and photo-corrosion significantly hinder practical application. While previous reviews have summarized this field, they fail to encompass the latest breakthroughs in the fields of material synthesis, mechanistic understanding aided by advanced characterizations, and innovative photocatalytic applications. Especially, their performance in the context of high-value chemical synthesis has been rarely summarized. This review is therefore timely and aims to highlight recent advances in engineering CdS-based photocatalysts to optimize charge carrier utilization and achieve highly efficient photocatalytic H₂ evolution. We begin with a brief overview of the fundamental properties of CdS-based photocatalysts. Next, we discuss key strategies for performance enhancement, including morphological design, solid solution engineering, cocatalyst integration, and heterojunction construction. We then examine advanced pathways for charge carrier utilization, focusing on both pure water splitting and systems where H₂ generation is coupled with the production of value-added chemicals. Finally, we outline the current challenges and prospects for CdS-based photocatalysts in the context of sustainable H₂ production. This review provides insights into the rational design of high-performance CdS-based photocatalysts, paving the way for more efficient utilization of photogenerated charge carriers.

The direct propylene epoxidation with molecular oxygen offers an atom-economical route to propylene oxide (PO). However, the oxidative reaction conditions required at high temperatures often induce complete propylene oxidation and the reconstruction of the active centers, compromising PO selectivity. Herein, we propose a redispersion-confinement strategy to encapsulate small, low-valence Cu nanoparticles (NPs) within a silica shell, thereby achieving stable dispersion across various supports. We confirm that the formation of Cu-O-Si coordination between Cu and silica, together with cesium promotion, could stabilize the small Cu NPs and enhance the PO formation. The optimum Cs-Cu@Si/SBA-15 catalyst delivers a 3.9% propylene conversion and a 68% PO selectivity, markedly surpassing the 0.6% conversion and 42% selectivity obtained over Cs-Cu/SBA-15 without the silica shell. A significant space and chemical state confinement effect is evidenced between CuO and the silica shell, which retards the reactivity of lattice oxygen and allows the moderate activation of molecular oxygen to electrophilic oxygen species; thus, promoting the selective epoxidation of propylene. This strategy offers a general approach for molecular-level control of active-site structure and electronic states in heterogeneous catalysts.

The carbonylation of epoxides to β-lactones is an attractive route for sustainable chemical production but remains constrained by the instability of [Co(CO)₄]^- and the limited activity of current catalysts. We report a cobalt nanoparticle catalyst supported on carbon (Co NPs-C) that, with [(TPP)CrCl], delivers unprecedented performance, achieving a turnover number (TON) of 230000 and a productivity of 11000 mol/(mol-_Cr·h). Mechanistic studies reveal in-situ generation of [Co(CO)₄]^- from Co NPs, with synergistic Lewis acid activation ensuring high β-lactone selectivity. The catalyst is recyclable and scalable to > 200 g, offering a practical platform for industrial β-lactone synthesis and highlighting the promise of nanoparticle-based cobalt catalysis.

Developing efficient Pt-based catalysts is crucial for sustainable lactic acid (LA) production via glycerol oxidation. Herein, we synthesized a series of robust PtIn/Sn-MFI catalysts with low Pt loading of 0.5 wt% for glycerol oxidation under base-free conditions. The PtIn/Sn-MFI catalysts with varying In contents exhibited a volcano-shaped trend between turnover frequency (TOF) and In/Pt molar ratio. Among all tested catalysts, the Pt_0.5In_1.0/Sn-MFI sample exhibited the highest catalytic activity (1283 h^-1), achieving 96.8% glycerol conversion with 73.5% LA selectivity, surpassing the monometallic Pt_0.5/Sn-MFI catalyst. Furthermore, the Pt_0.5In_1.0/Sn-MFI catalyst maintained excellent stability, with no significant degradation in catalytic performance even after five consecutive recycling runs. Experimental analysis and characterizations verified the formation of PtIn₂ nanoalloys, accompanied by electron transfer from In to Pt, which significantly enhanced the catalysts’ O−H bond activation ability, resulting in high activity and selectivity. Combined with kinetic studies and density functional theory calculations, we further revealed that PtIn₂ nanoalloy active sites significantly reduce the activation energy barrier for the dehydrogenation of the secondary hydroxy group in the reaction pathway. This work offers new perspectives on the rational design of cost-effective, high-efficiency catalysts for the sustainable oxidation of glycerol to LA.

CO₂ hydrogenation to ethanol represents a pivotal pathway for valuable utilization of greenhouse gas CO₂, yet conventional catalysts are still limited by active-phase instability and undesirable byproduct selectivity. Herein, we propose a dual-components catalyst system synergized by hydrophobic carbon-encapsulated Fe-based catalyst (NaFe@C) and K modified CuZnAl component (KCZA), which achieves ultra-high ethanol selectivity of 35% under optimized conditions (5 MPa and 320 °C). KCZA initiates the CO₂ activation via reverse water-gas shift reaction and supplies oxygen-containing intermediates (mainly CH_xO*, x = 0, 1, or 2). NaFe@C component is mainly responsible for the C-O activation for CH_x* formation and C-C coupling between CH_x* and CH_xO*, as well as the following hydrogenation step for ethanol synthesis. Notably, the hydrophobic carbon shell in NaFe@C plays a critical role in tailoring the oxidation behaviors of Fe-based active sites and optimizing the phase ratio of Fe₃O₄/χ-Fe₅C₂ via water management. Multiple characterization and theoretical simulation results clarify that the unique electronic property of Fe-based active sites endowed by the optimized phase ratio is beneficial to boost the ethanol synthesis performance by balancing the coverage of key intermediates and lowering the energy barrier of essential steps. This work is promising to provide guidance for the rational design of advanced catalysts for targeted transformation of CO₂ or syngas into ethanol and beyond.

Conventional thermocatalytic recycling of plastics is typically constrained by high energy input requirements, leading to marginal gains in energy efficiency and yield. We herein report an innovative strategy that combines π-π interaction-guided solvent engineering with microwave irradiation to achieve rapid glycolysis of highly crystalline waste poly(ethylene terephthalate) (PET) under mild conditions. In spite of the lack of solubility of PET, the depolymerization pathway is shifted from a solid-liquid interfacial process to a pseudo-houmogeneous reaction through judicious cosolvent selection. Furthermore, π-π interactions between the cosolvent and PET modulate the electron density and nucleophilic character of the ester bonds, facilitating their activation by Lewis acid catalysts. Complementarily, microwave irradiation enables rapid and uniform heating via the synergistic dielectric response of ethylene glycol (high dielectric loss tangent) and a bifunctional ZnO catalyst (serving as both microwave absorber and substrate catalyst). The synergistic cosolvent-microwave system lowers the apparent activation energy for PET glycolysis from 185 to 45 kJ·mol^-1, attaining 100% PET conversion and 97.5% bis(2-hydroxyethyl) terephthalate (BHET) yield at 150 °C within 20 min. This represents a 142-fold enhancement over the system devoid of cosolvent and microwave assistance. The integrated approach also exhibits excellent cycling stability, broad applicability across various catalysts, and selective PET depolymerization from mixed plastics, highlighting its potential as a sustainable platform for plastic waste valorization.

The chemical recycling of polyolefins (PE, PP) and polystyrene (PS) remains a major challenge due to their chemical stability of C-C backbones as well as the limited accessibility of polymer chains to catalytic active sites. Here, we report a solvent-free, low-temperature, and synergistic depolymerization strategy using a GaCl₃-based molten Lewis acid catalyst for the efficient conversion of PE, PP, and PS, both individually and in mixed plastics streams. The low melting point of the catalyst ensures liquid-phase mobility and efficient contact between polymer and catalysts, achieving complete PS conversion and over 60% PE/PP conversion within 30 min. In mixed plastics, a synergistic reaction pathway mediated by carbocation-type intermediates enables Friedel-Crafts alkylation between PS-derived aromatics and polyolefin-derived olefins, enhancing overall conversion (~85%) and selectivity toward mono-alkylated aromatics (up to 33.5%). Raman spectra confirmed the formation of [GaCl₄]^- and [Ga₂Cl₇]^- chlorogallate species during the reaction. This study demonstrates a novel, integrated approach for solvent-free, selective, and energy-efficient chemical recycling of mixed plastics, highlighting GaCl₃-based molten salts as versatile catalysts for circular and sustainable plastic recycling.

Co-thermal coupled in-situ hydrogenation of carbonates represents a promising strategy for producing metal oxide coupling syngas, facilitating the CO₂ conversion into value-added chemicals while reducing thermal decomposition temperatures. Nevertheless, the impact of CaCO₃ morphological modulation on hydrogenation performance and mechanisms has yet to be elucidated. Herein, we first report the morphology-controlled synthesis of CaCO₃ with distinct crystalline phases (e.g., rhombohedral calcite, spherical vaterite, and rod-shaped aragonite). This engineered morphology significantly enhances co-thermal coupled in-situ reduction, simultaneously lowering the decarboxylation temperature and promoting syngas formation. Compared with rhombohedral calcite, spherical vaterite exhibits superior CO selectivity and formation rate during reduction processes across various temperatures, reaching 96% and 0.80 mmol min^-1 at 700 °C, respectively. Notably, rod-shaped aragonite achieves an exceptional CO selectivity of 86%, surpassing both rhombohedral calcite and spherical vaterite, and the CO formation rate (0.46 mmol min^-1) is more than 2.3 times that of spherical vaterite at 550 °C. Moreover, combination of temperature programmed reduction-mass spectrometry and in-situ diffuse reflectance infrared Fourier transformed experiments reveals temperature-dependent hydrogenation mechanisms for different morphologies of CaCO₃: direct hydrogenation dominates at relatively low temperatures, while at elevated temperatures, the dual mechanism combining direct hydrogenation and reverse water-gas shift reaction (HCOO* as the key intermediate) prevails. This study presents a novel strategy demonstrating high efficiency and low carbon for sustainable carbonate hydrogenation systems, offering significant scientific merit and industrial potential.

Electrocatalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) in a near-neutral electrolyte mitigates HMF polymerization, thereby enhancing catalyst stability for long-term operation. However, the insufficient supply of active oxygen species during the electro-oxidation process often leads to the formation of partially oxidized intermediates instead of the desired product, 2,5-furandicarboxylic acid (FDCA). In this study, an atomically dispersed ruthenium-loaded copper oxide electrocatalyst (Ru/CuO) is prepared to promote the generation of hydroxide (OH^-) ions and facilitate complete HMF oxidation to FDCA. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, density functional theory calculations, and quartz crystal microbalance mass analysis revealed that CuO serves as the active site for the HMF oxidation reaction (HMFOR), whereas the introduction of Ru single atoms accelerates OH^- formation, lowers the reaction barrier for the key dehydrogenation steps in HMFOR, and enhances HMF adsorption. These features enable the Ru/CuO catalyst to deliver significantly improved low-potential oxidation performance under near-neutral conditions, reaching a 93% FDCA yield and 87.7% Faradaic efficiency at 1.15 V_RHE, along with stable operation in a flow cell. This work demonstrates efficient conversion of HMF to FDCA in a near-neutral electrolyte and proposes a rational design strategy for HMFOR catalyst operating under near-neutral conditions.

Metal organic frameworks (MOFs) are frequently employed as electrocatalysts for chemical and energy conversions, owing to their tailored structure and electronic properties. However, the stability and evolution of MOFs under electrochemical conditions remain unclear, resulting in the identification of true active sites a challenging task, thus limiting the design of high-performance electrocatalysts. Here, we follow the development of a representative Co-MOF anode in electrolyte under bias by in-situ spectroscopies, and resolve the evolution of active species for efficient electrocatalytic ammoxidation of aldehydes. A rapid dissociation of Co-MOF occurs in KOH, forming a composite electrocatalyst (e-Co) that consists of crystalline cobalt hydroxide (Co(OH)₂) and amorphous cobalt oxide (CoO_x). The active Co²⁺ sites promote the dissociative adsorption of ammonia, forming Co³⁺-NH_3-x sites to interact with aldehyde, yielding an imine intermediate and eventually generating nitrile via dehydrogenation. The evolved e-Co electrocatalyst exhibits a satisfactory yield (83%) and Faradaic efficiency (72%) for the synthesis of nitrile at an ultra-low cell voltage of 1.0 V in aqueous electrolyte under ambient air pressure. The e-Co electrocatalyst also displays a decent stability, a broad substrate scope, and a consistent catalytic performance at higher reactant concentrations, offering a sustainable solution for ammoxidation at a practical scale.

The electrocatalytic nitrogen reduction reaction (NRR) poses formidable challenges, such as competing hydrogen evolution and poor N₂ activation. Herein, we introduce a precise electronic-structure tuning modality through controlled sulfur vacancy (V_S) engineering in 1T-MoS₂. By manipulating the V_S concentration to nearly 9.38%, the optimized catalyst (MoS₂-100) achieves an outstanding NH₃ yield of 64.50 μg h^-1 mg^-1 and a Faradaic efficiency of 15.25%, superior to most electrocatalysts reported. Mechanistic studies reveal that enhanced d-σ orbital coupling between Mo and N₂ significantly promotes N₂ activation, while the distinct orbital-coupling responses of Mo-N₂ and Mo-H to V_S concentration render a potential competition-preponderance window for NRR. This work establishes a novel paradigm for decoupling the competitive reactions by utilizing their differential sensitivity of orbital coupling to vacancy engineering.

Efficient electrooxidation of ethylene glycol (EG) to glycolic acid (GA) is highly desirable for biomass valorization and EG recycling, which remains challenging owing to side reactions involving C-C bond cleavage. Herein, the bimetallic AgPd hollow nanocubes (AgPd hNCs) are successfully prepared via a solvothermal-assisted Galvanic replacement strategy. Both theoretical calculations and experimental results indicate that the electronic interplay between the Pd atom and Ag atom hinders C-C bond breaking and enhances the adsorption of critical intermediates, resulting in high selectivity toward GA production. Benefiting from these features, AgPd hNCs achieve a Faradaic efficiency of 93% toward GA formation and a 2.8-fold increase in mass activity compared to Pd black. Moreover, the strong oxygen affinity of Ag promotes the removal of CO-like intermediates from the Pd surface, resulting in superior EG oxidation stability. This study highlights a generalizable Ag-based strategy to modulate bimetallic interfaces for selective oxidation reaction of specific functional groups, contributing to the rational design of electrocatalysts for biomass upgrading.

The electrochemical reduction of CO₂ to CO offers a promising route for mitigating carbon emissions and producing sustainable feedstocks. Although noble metals like Ag exhibit high CO selectivity, their high cost and scarcity hinder scalability. Earth-abundant Zn catalysts suffer from intrinsic activity limitations, while alloying with trace Ag would modulate electronic structures for tuning its CO₂ electroreduction activity. Herein, a surface-alloyed Ag-Zn hollow-fiber penetration electrode (HPE) is constructed via an electrochemically induced reconfiguration process that transforms the initial phase-separated Ag clusters on ZnO substrate into a homogeneously dispersed Ag-Zn alloy (AgZn₃). The resulting Ag-Zn HPE achieves 91% faradaic efficiency for CO at 1.2 A cm⁻² and demonstrates long-term electrolysis over 150 hours, as well as promising cost-effectiveness for industrial applications. Combined with the penetration effect that effectively mitigates CO₂ mass transport limitations, the HPE enables high-rate CO production even at large current densities. Mechanistic investigations reveal that alloying modifies the d-band center of Zn, strengthens *COOH adsorption and facilitates *CO desorption to boost CO formation while suppressing hydrogen evolution reaction. This work provides fundamental insights into the role of surface alloying in enhancing CO₂ reduction kinetics and presents a scalable electrode architecture with significant potential for sustainable CO₂ conversion.

The pressing need to address global energy demand and climate change has positioned electrochemical CO₂ reduction into high-value chemicals as a crucial technology for carbon cycling and sustainable energy storage. However, precise control over the interfacial structure of active sites in single-atom alloy (SAA) remains a considerable challenge, significantly restricting their catalytic performance. In this study, we propose an atomic-level substitution strategy, integrating large atomic radius of Bi atoms into the Ag lattice to trigger and stabilize a 4H/fcc-Ag heterophase interfaces. Theoretical and experimental analyses reveal that the induced lattice strain stabilizes the metastable 4H phase and optimizes the geometric/electronic configuration of active sites, thereby enhancing the orbital overlap between Ag-3d and C-2p orbitals and lowering the energy barrier for *COOH formation. The optimal 4H/fcc Ag₄₉Bi₁ SAA catalyst, comprising approximately 3% 4H-Ag and 97% fcc-Ag, achieves CO Faraday efficiency (FE_CO) of 99.5%, single-pass conversion efficiency of 70%, CO yield of 45.6 mmol h⁻¹ cm⁻² and superior durability over 330 h under 200 mA cm⁻² in an alkaline flow cell. A membrane electrode assembly electrolyzer incorporating the catalyst reached a peak FE_CO of 98.6% at 150 mA cm⁻² and maintaining FE_CO >80% for 70 h under 100 mA cm⁻² without decay. When applied in a customized Zn-CO₂ battery, it delivered a peak power density of 0.86 mW cm⁻², along with 140 h cycling stability at 2 mA cm⁻². This work underscores the potential of atomic-level substitution for precise interface engineering, providing a novel strain-engineering strategy for designing high-performance SAA catalysts.

Constructing the active sites of a heterogeneous catalyst, controlling the accessibility of molecules to active sites and ultimately tailoring its catalytic property are of utmost significance yet highly challenging. Herein, we report two systems of atomically precise cluster catalysts for the cyclohexanone electrooxidation reaction, which correspond to 2-phenylethanethiol-protected Ni₆(SC₂H₄Ph)₁₂ and 1-dodecanethiol-protected Ni₆(SC₁₂H₂₅)₁₂. The two clusters are identified to have similar metal active cores while their distinct surrounding environments access to the metal cores are capable of discriminating between water and cyclohexanone, exhibiting substantially influences on their activity and selectivity. Our studies reveal that water molecules are preferably adsorbed onto the surface of the Ni₆(SC₁₂H₂₅)₁₂, thereby pushing the cyclohexanone molecule away from the metal core, which favors the oxygen evolution reaction on the Ni₆(SC₁₂H₂₅)₁₂ catalyst. In contrast, the cyclohexanone is adaptively pulled toward the Ni core by the 2-phenylethanethiol ligands of Ni₆(SC₂H₄Ph)₁₂, in which the C=O group of the cyclohexanone can approach, adsorb and convert over the Ni sites and 2-phenylethanethiol ligands have stronger electron interactions with Ni core facilitating the cyclohexanone oxidation reaction on the Ni₆(SC₂H₄Ph)₁₂ catalyst and hence achieving high faradaic efficiency and high yield for adipic acid. This study challenges the conventional heterogeneous catalysts without atomic-precision structure and instead couples the complementary roles of the inner and outer environments of the cluster catalysts to tailor their catalytic properties.

High-performance single-atom iridium (Ir) catalysts offer ultrahigh atomic utilization and can lower proton exchange membrane water electrolysis costs, but their improved oxygen evolution reaction (OER) activity often sacrifices stability. Here, incorporation of lanthanum (La) enables atomic dispersion of Ir on cobalt spinel (Co₃O₄) surface and shifts the Ir active-site OER pathway from the conventional adsorbate evolution mechanism to a lattice oxygen-mediated mechanism (LOM). The strongly oxophilic La sites tune the local electronic structure of Ir and accelerate interfacial water dissociation, enabling real-time replenishment of lattice oxygen consumed during LOM that a key process mitigates catalyst degradation. Consequently, Ir/CoLaO_x shows an overpotential of 215 mV at 10 mA cm^-2 in acid and sustains 200 mA cm^-2 operation for 300 h in a full proton exchange membrane water electrolysis. This work provides a mechanistic framework for dynamic oxygen replenishment to stabilize lattice-oxygen catalysis and offers a strategy for designing atomically dispersed Ir catalysts for efficient, durable acidic OER.

The electron donor-acceptor (EDA) strategy has emerged as a sustainable alternative in photochemistry, enabling the generation of radicals without any photocatalysts. However, the formation of the EDA complex often requires stoichiometric donors, resulting in excessive waste of the electron donors, and the catalytic EDA strategy remains challenging. Herein, a novel catalytic EDA complex, employing N-(4-bromophenyl)-N-phenylnaphthalen-1-amine as the catalytic electron donor and O-aryl oximes as electron acceptors, was described to achieve cyanoalkyl difunctionalization of alkenes via a radical-relay strategy under visible-light irradiation. Various versatile compounds with cyanoalkyl and 1,4-dicarbonyl groups could be easily synthesized under green and sustainable reaction conditions. The significance of this sustainable methodology was highlighted by the novel catalytic EDA complex, broad substrate scope (36 examples), green solvent, good synthetic applications, and high selectivity.

Developing bifunctional electrocatalysts for energy-efficient urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is critical for sustainable hydrogen production and wastewater remediation, yet hindered by sluggish kinetics and insufficient active sites. Herein, we propose demonstrate that lanthanum (La) doping effectively activates nickel selenide (NiSe) by inducing lattice expansion—substituting smaller Ni²⁺ (0.69 Å) with larger La³⁺ ion (1.16 Å)—thereby modulating its electronic structure. The optimized La-NiSe-2 catalyst exhibits markedly enhanced UOR and HER performance: it achieves a UOR current density of 213 mA cm^-2 at 1.6 V vs. RHE (twice that of pristine NiSe) and requires only 135 mV overpotential for HER at -10 mA cm^-2, with a Tafel slope of 78 mV dec^-1. Operando electrochemical impedance spectroscopy and density functional theory calculations reveal that La incorporation enhances charge transfer and strengthens urea adsorption. This work highlights rare-earth-mediated electronic modulation as a viable strategy for designing high-performance bifunctional catalysts for urea-assisted energy and environmental applications.

Electrochemical CO₂ reduction reaction (CO₂RR) is a potential strategy for mitigating severe greenhouse effect. Despite its potential, CO₂RR encounters critical challenges to convert low CO₂ concentrations in practical scenarios, due to the CO₂ mass transfer limitations. Herein, we prepared a reduced 2-aminoterephthalic acid modified bismuth coordination compound (Re-BiBDC-NH₂) for CO₂RR in low CO₂ concentrations. Retained amino groups after in situ reduction induce abundant unsaturated coordination sites, enhancing CO₂ adsorption and enabling localized concentration enhancement even under low CO₂ supply concentrations. As such, the optimized Re-BiBDC-NH₂ achieves a Faradaic efficiency for formate (FE_formate) of > 80% at a wide potential range of 700 mV, FE_formate of >75% across 15%-100% CO₂ concentrations. Furthermore, in a flow cell at a current density of 300 mA cm^-2 and across a wide pH range (pH = 1.7, 7, and 14), the Re-BiBDC-NH₂ catalyst achieved FE_formate > 95%, with a single-pass carbon efficiency (SPCE) reaching 71.6% in acidic electrolyte (pH = 1.7). In situ spectroscopies and Density functional theory calculations reveal that dynamically frustrated Lewis pairs formed by amino groups and defects concentrate CO₂, and stabilize *OCHO intermediates to reduce energy barriers, thereby not only enhancing the CO₂RR performance but also allowing reaction to operate under low CO₂ concentrations. This work presents a promising ligand-defect synergistic catalyst for low-concentration CO₂RR, offering insights for bridging catalyst research and practical CO₂ conversion.

High-entropy oxides (HEOs) have emerged as promising electrocatalysts for the oxygen evolution reaction (OER) due to their unique tunable electronic structures and multi-site synergistic effects. Triggering the lattice oxygen oxidation mechanism (LOM) is considered an effective strategy to overcome the intrinsic limitations of the conventional adsorbate evolution mechanism (AEM). However, promoting the shift from AEM to LOM requires highly oxidized metal centers. Herein, we report on the rational design and synthesis of a (FeNiMoMnCr)₃O₄/NF HEO catalyst, wherein the introduction of high-valent Cr species serves as an electronic modulator to facilitate lattice-oxygen activity. The resulting catalyst exhibits a low overpotential of 248 mV at 100 mA cm^-2 in 1 mol L^-1 KOH and demonstrates excellent operational durability over 100 hours under high current densities. Comprehensive investigations, including pH-dependent electrochemical measurements, radical trapping experiments, and density functional theory calculations, reveal that the incorporation of Cr induces the in-situ formation of oxygen vacancies, thereby activating lattice-oxygen participation in the OER. This activation breaks the conventional linear scaling relationships associated with AEM, leading to enhanced reaction kinetics. This study provides mechanistic insights into how high-valent metals regulate electronic structure and lattice oxygen reactivity in HEOs, offering a feasible design strategy for advanced OER electrocatalysts based on the LOM pathway.

Interfacial hydrogen bond connectivity (HBC) of electrical double layer (EDL) has been identified as a critical factor for many electrocatalytic reactions, However, there is a lack of systematic investigation on the correlation between HBC and oxygen evolution reaction (OER) kinetics, and the advanced strategies to rationally manipulate HBC. Herein, we proposed an interfacial charge manipulation (ICM) methodology to engineer HBC and enhance OER kinetic of various electrocatalysts including Ni3FeN and the benchmark oxides (RuO₂, Ni(OH)₂, Co(OH)₂, FeNi LDH, and FeCo LDH). With Ni₃FeN as a model catalyst, we systematically studied the influence of different anion chemisorption (NO₃^-, SO₄^2-, and PO₄^3-) on HBC and establishing a positive correlation between OER activity and the charge of anions. Electrochemical tests show that the modified Ni₃FeN catalysts with NO₃^-, SO₄^2-, and PO₄^3- exhibit 1.1-, 1.4-, and 2.3-fold activity enhancements at 1.5-1.6 V vs. RHE relative to the raw Ni₃FeN, respectively. The in-situ spectroscopy and AIMD reveal that high anion charges increase four-hydrogen-bonded water populations, strengthening HBC to promote proton transfer across the EDL during deprotonations step and lower energy obstacle of the rate-determining step. This work has offered a new paradigm to regulate the interfacial HBC at molecular scale for promoting OER.

A dual-site synergistic catalytic mechanism is proposed to optimize the OHad binding energy (OHBE) by constructing ultrafine Ru nanoclusters modified with highly oxygenophilic WO_2.72 clusters in nitrogen-doped carbon carriers, which can optimize the adsorptions of OH_ad and active hydrogen species, respectively, resulting in a marked increase in hydrogen oxidation reaction (HOR) activity. The constructed Ru-WO_2.72-NC shows a HOR mass activity about 8 times that of Pt-C, and the corresponding alkaline exchange membrane fuel cells demonstrate rather higher peak power densities than Ru-NC with 1.193 W cm^-2 and more than 1 W cm^-2 in H₂ fuel and CO/H₂ mixtures, respectively. The excellent alkaline HOR performance of Ru-WO_2.72-NC is attributed to the adsorption of OH_ad species by WO_2.72 clusters, which synergizes with the adsorption and dissociation of hydrogen on Ru to facilitate the Volmer step. The success in constructing dual-site synergistic catalysis of Ru-WO_2.72-NC anode provides valuable insight and new guidelines for designing and studying high-activity alkaline HOR catalysts.

Rechargeable zinc-air batteries (ZABs) suffer from poor reversibility of Zn anode due to dendrite formation and parasitic side reactions, severely limiting their practical deployment. Here we report an interfacial engineering strategy that integrates three Bi components: metallic Bi⁰, atomic Bi-N_x sites, and Bi₂O₃ nanocrystals, anchored within a nitrogen-doped mesoporous carbon framework. This triphasic Bi interphase delivers collective synergistic effects by: (1) homogenizing Zn²⁺ nucleation, (2) accelerating Zn plating/stripping kinetics, and (3) suppressing hydrogen evolution and interfacial corrosion. Density functional theory calculations confirm that the Bi₂O₃/Bi heterointerface exhibits strong zincophilicity, markedly lowering the nucleation energy barrier and enabling uniform Zn deposition. Benefiting from these collective interfacial effects, symmetric cells with s-Bi₂O₃/Bi-NC@Zn anodes sustain dendrite-free cycling for over 520 h at 10 mA cm^-2, with negligible polarization growth. When assembled into ZABs, the engineered anodes deliver an ultrahigh power density of 829.3 mW cm^-2 and an extended lifetime of 1650 h at 5 mA cm^-2 with 80% voltage efficiency. This work establishes a triphasic Bi-based interfacial design as a powerful strategy to achieve highly reversible Zn anodes and offers a generalizable approach for advancing metal-based batteries.

Fine-tuning the interfacial electronic interaction and surface reactivity of S-scheme heterojunctions is critical for advancing their photocatalytic performance. This study employs density functional theory calculations to systematically investigate the effects of transition metal (TM = Cr, Mn, Fe, Co, and Ni) doping at distinct sites of a CdS/ZnO S-scheme heterojunction: the surface (TM_s), the interface (TM_i), and co-doping at both sites (TM_s+i). The results demonstrate that all doping configurations concurrently enhance both interfacial electron transfer and the hydrogen evolution reaction dynamics. The augmentation of electron transfer across the interface is primarily driven by TM doping at the interface, which reduces the work function of CdS and enlarges the Fermi level discrepancy with ZnO, leading to an enhancement trend of TM_s+i > TM_i > TM_s. Conversely, the optimization of hydrogen adsorption free energy (ΔG_H*) is chiefly governed by surface TM doping, which downshifts the p-band center of S atoms and weakens the S-H bond, resulting in an improvement trend of TM_s+i > TM_s > TM_i. Remarkably, the co-doping configuration exhibits a pronounced synergistic effect, outperforming any single-site doping in optimizing both properties. Furthermore, a clear periodic trend is identified: the promotional effect of TM doping, from Cr to Ni, progressively diminishes for both charge separation and surface reaction, which is linked to the increasing work function and S p-band center. This work highlights the significant potential of a multi-site doping strategy for the synergistic engineering of charge transfer and surface reactions in S-scheme heterojunctions, offering valuable theoretical insights for the precise design of high-efficiency photocatalysts.

Metal-organic frameworks (MOFs) offer an ideal platform for constructing heterostructures to catalyze organic pollutant degradation. However, sluggish charge transfer dynamics within the bulk and at interfacial regions limit removal efficiency. Herein, we engineered a full-space electric field in BiOBr-nanosheet-coated mixed-valence MIL-88A(Fe^II/Fe^III) (m-MIL-88A@BiOBr) heterostructures via charge polarization to overcome this limitation. Specifically, this full-space electric field originates from the synergistic interplay of a bulk electric field (BEF) and an interfacial electric field (IEF), collectively driving the directional flow of photogenerated electrons. Simultaneously, mixed-valent Fe^II/Fe^III metalloclusters establish electron-transfer chains, enhancing charge mobility and IEF intensity. The optimized m-MIL-88A@BiOBr-3 catalyst exhibited exceptional photocatalytic degradation rate constant of 0.023 min⁻¹ for carbamazepine (CBZ) removal, surpassing pristine MIL-88A and BiOBr by factors of 6.99 and 2.15, respectively. Notably, m-MIL-88A@BiOBr-3 demonstrates broad environmental applicability, efficiently mineralizing structurally diverse pollutants (tetracycline, azo dyes, etc.). This work provides critical insights for regulating charge transport in MOF-based heterojunctions.

Solar-driven photocatalytic CO₂ conversion offers a sustainable solution for greenhouse gas mitigation and renewable energy storage. While metal phthalocyanines (MPc) exhibit excellent CO₂ reduction capabilities, their practical application in dispersed photocatalytic systems faces limitations of the stacking of MPc molecules that reduces active site accessibility, and inefficient electron transfer limited by diffusive mass transport. To address these challenges, we developed a bioinspired dye-sensitized RuP-TiO₂-FePc nanosheets (NSs) hybrid system, where ultrathin FePc NSs obtained by liquid-phase ultrasonic exfoliation enhance active site exposure and mass transfer, while TiO₂ serves as a mediator to facilitate electron transfer between the photosensitizer and FePc NSs. Time-resolved spectroscopic studies demonstrate that TiO₂ plays a dual role: it spatially organizes functional components to enable surface electron transfer by shortening intermolecular distances, while also functioning as a semiconductor bridge to facilitate charge transport. This synergistic design achieves a remarkable CO production rate of 27.3 mmol g^-1 h^-1 (> 98% selectivity) and exceptional stability (TON_CO = 1363 over 100 h), outperforming many noble-metal-based systems. Our work demonstrates a robust strategy for optimizing bulk catalysts through 2D exfoliation and controlled heterogenization, offering a versatile platform for efficient and durable artificial photosynthesis.

Covalent organic frameworks (COFs) offer a modular platform for photocatalytic hydrogen evolution (PHE), where linkage topology and channel architecture dictate charge separation and mass transport. However, the role of linkage isomerism in coupling pore microenvironments with photocatalytic function remains unclear. We synthesized COF-PQ and COF-DPPQ via in-situ Povarov cyclization of pyrene-based imine direction distinct intermediates, creating frameworks with identical building blocks but distinct donor-acceptor arrangements and pore microenvironments that underpin their contrasting catalytic behaviors. This structural divergence drives profound functional differences: COF-DPPQ achieves a PHE rate of 37.82 mmol g^-1 h^-1, nearly 100-fold higher than COF-PQ. Mechanistically, COF-DPPQ exhibits lower electron effective mass (0.574 vs. 1.046), stronger donor-acceptor polarization (~0.95 |e| vs. ~0.24 |e|), prolonged carrier lifetimes (37.28 vs. 1.26 ps), and superior proton adsorption and diffusion (2.2-fold capacity; 0.916 × 10^-3 vs. 0.660 × 10^-3 cm² s^-1). These results identify linkage topology as an effective lever to regulate exciton dynamics and mass transport, guiding the design of next-generation COF photocatalysts.

Combining organic photosensitive center with dinuclear-metal catalytic center through covalent bonds to synthesize supramolecular catalysts for photocatalytic hydrogen evolution is a cost-efficient approach to convert solar to hydrogen energy, while it has been rarely explored. Herein, we constructed a self-photosensitizing pyrene-decorated dinuclear cobalt(II) molecular photocatalyst [Co₂(pyrene-L)₂] via covalent bonds, which can accelerate photogenerated electron transfer from pyrene center to dinuclear cobalt(II) center, achieving efficiently photocatalytic hydrogen evolution in the absence of any noble metal photosensitizers. The photocatalytic activity of Co₂(pyrene-L)₂ is more than 3-fold over that of the physically mixed sample. Moreover, owing to the synergistic effect of dinuclear cobalt(II) centers, the activity of Co₂(pyrene-L)₂ is 10-fold higher than that of mononuclear counterpart (Co(pyrene-L)₂). As the first example of self-photosensitizing pyrene-decorated dinuclear metal molecular catalyst, it not only features multi-functions of photosensitivity, photoreduction and photooxidation, but also possesses synergistic dinuclear metal centers to improve catalytic activity, which gives new insights for researchers in designing high-performance photocatalysts for hydrogen evolution.