Catalytic upcycling of waste plastics alleviates their environmental and health hazards while providing renewable carbon feedstocks for sustainable energy and chemical production1-6. Bifunctional metal-zeolite catalysts hold great promise for this process, yet suffer from insufficient efficiency, limited durability, and excessive metal usage. Here we show that encapsulating metal nanoparticles within zeolites unlocks the full potential of bifunctional catalysis for plastic hydrocracking. The H-Beta zeolite-encapsulated ruthenium catalyst (Ru@H-Beta) efficiently converts, at only 0.14 wt% Ru loading, polyethylene to gasoline-range hydrocarbons with ~90% yield in 0.5 h at 275 ºC, achieving an unprecedented liquid fuel formation rate of 61 g gcat-1 h-1 (43,700 g gmetal-1 h-1)—6‒10 times higher than conventional supported catalysts. Notably, the single-run Ru usage for Ru@H-Beta is merely 42 gRu tonLDPE-1—the minimum among the reported metal-based catalysts, underscoring its exceptionally low resource footprint. Furthermore, unlike supported catalysts that deactivate rapidly, encapsulating Ru nanoparticles in Ru@H-Beta maintain ultra-stable performance over 100 recycling runs and exhibit high activity for diverse plastics—including high-density polyethylene, polypropylene, and polystyrene (converted to gasoline fuels), as well as polyethylene terephthalate (converted to terephthalic acid), even from post-consumer wastes. Notably, encapsulation opens an unconventional bifunctional mechanistic pathway, where metal sites are used to activate H2 but not directly exposed to the polymer, thus preventing catalyst poisoning and improving hydrocarbon selectivity; the metal-activated hydrogen species migrate to the zeolite external surface and accelerate hydrocracking without favoring short chain scission. This work unlocks a straightforward and general design strategy for high-efficiency, robust metal-zeolite catalysts and prompts a fundamental rethinking of bifunctional catalysis

This review presents a comprehensive discussion of ionomers for microenvironment modulation in the electrocatalytic CO 2 RR, with a focus on elucidating their crucial roles in reaction modulation and outlining vital future research directions.

C1 molecules (e.g., CO, CO2, CH4, and CH3OH) are pivotal platforms for synthesizing fuels and chemicals from nonpetroleum resources. However, the selective activation of C-O and C-H bonds, precise control of C-C formation, and preservation of functional groups are tough challenges in catalysis. Traditional routes like Fischer-Tropsch synthesis and methanol conversion often suffer from limited selectivity or require multiple processing steps. By using a relay catalysis strategy, a series of bifunctional or multifunctional catalysts composed of metals and acidic zeolites has been developed for the selective hydrogenation of CO to hydrocarbon fuels. Recently, this methodology has also been successfully applied for the precise synthesis of high-value chemicals, such as lower olefins, aromatic hydrocarbons, and higher alcohols from not only CO but also CO2 and CH4. The core of relay catalysis is integrating sequential reactions within one multifunctional catalyst or in a single reactor and providing controllable product selectivity. This review will analyze recent advances in C1 chemistry using relay catalysis as well as tandem catalysis for the selective synthesis of hydrocarbon fuels and chemicals. We also detail the design principles of relay pathways, outlining the strengths, applications, and future potential of relay catalysis in C1 chemistry.

Photocatalytic oxidation mediated by reactive oxygen species (ROS) provides an effective platform for a wide range of important chemical transformations. However, conventional oxygen-vacancy engineering strategy, while enhancing O2 activation, often hampers subsequent ROS evolution due to overly strong adsorption, thereby limiting oxidation kinetics. Here, we demonstrate that asymmetric vacancies in ZnGa2O4, characterized by a ZnTd-Ov-GaOh configuration, can overcome this intrinsic limitation by synergistically coupling O2 activation with efficient ROS evolution. Specifically, the dynamic GaOh site preferentially promotes O2 adsorption and activation, whereas the ZnTd site interacts weakly with oxygen-derived species, facilitating ROS release and vacancy replenishment, thereby achieving an optimal balance between these critical steps. Consequently, Ag/ZnGa2O4 delivers the highest turnover number (TON) reported to date among Ag-based catalysts for the photocatalytic oxidative coupling of methane via a ROS-mediated pathway. The general effectiveness of this asymmetric-vacancy strategy is further validated in other representative photocatalytic reactions, including hydrogen peroxide production and the oxidative coupling of benzyl alcohol.

ABSTRACT Among various CO 2 utilization strategies, methanol synthesis via hydrogenation has been extensively studied due to its technological maturity and broad downstream applications. However, the development of catalysts that simultaneously provide high activity, selectivity, and cost‐effectiveness remains challenging. This work investigates cadmium‐based catalysts for CO 2 hydrogenation to methanol, examining the influence of support composition, crystal phase, and metal promotion on catalytic performance. It was found that Cu‐promoted cadmium sites supported on TiO 2 with a mixed‐phase of anatase and rutile markedly enhanced catalytic performance. Under optimized conditions (5 MPa and 290°C), the CdCu/TiO 2 catalyst achieved a methanol selectivity of 82% at a CO 2 conversion of 15% or a methanol selectivity of 78% at a CO 2 conversion of 18% at different space velocities. Our characterization demonstrates that the loading of cadmium onto mixed‐phase TiO 2 provides weak basic sites that favor CO 2 adsorption and activation. The combination with a trace of Cu facilitates the reduction of cadmium, thus promoting the hydrogenation reactivity. The synergistic interaction among Cd, Cu, and the mixed‐phase TiO 2 collectively promotes methanol formation. This study demonstrates a cost‐effective and alternative catalyst for CO 2 hydrogenation and offers insights into structure–activity relationships for catalyst design.

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. (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Supported subnanometric metal clusters have attracted widespread interest in heterogeneous catalysis owing to their high atom exposure and increased density of low-coordinated metals. However, these reactive metals are often in a highly charged state due to the strong metal-support interaction, leading to limited chemoselectivity toward multifunctional substrates and poor resistance to poisoning. This study demonstrates that the site-specific doping of trace selenium (Se) can sustain the metallic state of fully exposed palladium (Pd) nanoclusters, enabling chemoselective hydrogenation of halonitrobenzenes to haloanilines, an important yet highly challenging transformation. The precision Se-doped Pd nanoclusters outperform many reported noble-metal catalysts, achieving >99% selectivity at full conversion and a turnover frequency of 15,593 h-1, together with excellent poison resistance and reusability. Mechanistic investigations reveal a semiquantitative correlation between the Pd0/Pdδ+ ratio and haloaniline selectivity. Trace Se doping enriches electron density on Pd sites, enhancing H2 activation while suppressing undesired hydrodehalogenation by modulating the adsorption and activation of haloanilines. This work not only establishes a versatile strategy to precisely tune the metallic state of metal clusters via Se doping but also provides insights for designing efficient catalysts that overcome support-induced electronic perturbations.

The oxyhalogenation of methane to mono-halogenated methane CH3X (X = Cl, Br, or I) is one of the most feasible routes for the utilization of methane, but the current catalysts still suffer from limited product yield due to the overoxidation of CH4 into CO and CO2 at high conversion levels. Herein, we demonstrate a CeO2 nanorod catalyst with the surface fabricated by atomically dispersed Pd and Mn for efficient methane oxychlorination (MOC). The optimum Pd-Mn/CeO2 catalyst offers an MOC performance with a CH3Cl selectivity of 72

Fe-based catalysts have been extensively investigated for CO2 hydrogenation to light olefins, but achieving precise control over the active phase remains a challenge. In this work, a series of Fe-based catalysts with varying particle sizes were synthesized using carbon nanotubes (CNTs) as supports via controlled preparation methods, enabling the regulation of the product distribution in CO2 hydrogenation to light olefins. The characterization results demonstrated that the size of Fe particles in the catalyst plays a critical role in the formation of the Fe3O4 active site for reverse water gas shift (RWGS) and the Fe5C2 active site for C-C coupling activity. Fe particles with a diameter of 15.8 nm exhibit an optimal Fe3O4 to Fe5C2 ratio, achieving the excellent CO2 conversion and light olefin selectivity in the CO2 hydrogenation to light olefins. Furthermore, a relationship between Fe particle size and the relative content of active Fe species was established. This work provides a highly promising approach for predicting and controlling the concentration of active phases through direct regulation of metal particle size.

Electrocatalytic CO2 reduction reaction (CO2RR) has achieved remarkable selectivity toward C1 and C2 products; however, the direct electrosynthesis of long-chain (C4+) and structurally complex molecules remains challenging. Coupling CO2 electrolysis with downstream biological, thermal, electrochemical, or organic transformations offers a practical route to produce long-chain and structurally complex compounds, thereby expanding the product spectrum to include fuels, fine chemicals, polymers, and functional materials. In this mini review, we systematically summarize recent progress in four representative cascade configurations: electro–biological, electro–thermal, electro–electro, and electro–organic systems. For each configuration, we discuss the underlying principles, analyze the key coupling challenges, and summarize the corresponding optimization strategies along with representative studies. We further compare the technological features, product scope, and scalability limitations of these cascade systems in terms of reaction condition compatibility, multiphase interface engineering, energy efficiency, and system integration. Finally, we outline future research priorities aimed at accelerating the translation of CO2 cascade technologies from laboratory-scale proof-of-concept studies to industrially relevant platforms.

Among various CO2 utilization strategies, methanol synthesis via hydrogenation has been extensively studied due to its technological maturity and broad downstream applications. However, the development of catalysts that simultaneously provide high activity, selectivity, and cost-effectiveness remains challenging. This work investigates cadmium-based catalysts for CO2 hydrogenation to methanol, examining the influence of support composition, crystal phase, and metal promotion on catalytic performance. It was found that Cu-promoted cadmium sites supported on TiO2 with a mixed-phase of anatase and rutile markedly enhanced catalytic performance. Under optimized conditions (5 MPa and 290°C), the CdCu/TiO2 catalyst achieved a methanol selectivity of 82% at a CO2 conversion of 15% or a methanol selectivity of 78% at a CO2 conversion of 18% at different space velocities. Our characterization demonstrates that the loading of cadmium onto mixed-phase TiO2 provides weak basic sites that favor CO2 adsorption and activation. The combination with a trace of Cu facilitates the reduction of cadmium, thus promoting the hydrogenation reactivity. The synergistic interaction among Cd, Cu, and the mixed-phase TiO2 collectively promotes methanol formation. This study demonstrates a cost-effective and alternative catalyst for CO2 hydrogenation and offers insights into structure-activity relationships for catalyst design.

The electrocatalytic CO2 reduction reaction (CO2RR) in aqueous electrolytes is a cornerstone technology for achieving a carbon-neutral society. Beyond the direct CO2RR, the sequential reduction of CO2 to CO followed by the CO reduction reaction (CORR) offers an alternative pathway. Water plays a pivotal and complex multi-scale role in CO2RR/CORR systems. Its influence spans multiple scales, including micro-scale water-mediated reaction kinetics, meso-scale regulation of the local aqueous microenvironment, and macro-scale optimization of operational conditions. Factors at these different scales are interconnected and mutually interactive, ultimately determining the overall reaction performance. Therefore, this review establishes a comprehensive multi-scale framework for water regulation in both the CO2RR and the CORR. We systematically elucidate the roles of water, survey advanced regulation strategies, and discuss state-of-the-art in situ characterization and simulation techniques. Finally, we identify key challenges and provide a forward-looking perspective, emphasizing that as this technology matures towards large-scale applications, such synergistic, multi-scale regulation becomes increasingly critical. This work aims to offer a clear roadmap for designing high-performance, stable, and large-scale CO2RR/CORR systems and accelerating their practical implementation.

Decomposing ammonia to produce hydrogen is a promising approach to address challenges in hydrogen storage and transport. While Ru-based catalysts have demonstrated high activity, their long-term stability under industrial conditions remains a critical hurdle. Here, we develop a reductive synthesis strategy to fabricate rod-shaped ceria (CeO2-RodRed) featuring high-density oxygen vacancy clusters, where Ru clusters are effectively anchored via robust Ru-O-Ce3+ linkages formed at 450 °C under N2 atmosphere. The resulting Ru/CeO2-RodRed-450N2 catalyst achieves an impressive 99.0% NH3 conversion at 450 °C, approaching the thermodynamic equilibrium (99.6%), and shows exceptional stability over 1000 h of operation. Integrated experimental characterization and density functional theory calculations reveal that the abundant Ce3+ species and oxygen vacancy clusters create an electron-rich surface with high electron conductivity, which facilitates hydrogen spillover from Ru clusters onto CeO2 to form dynamic Ce-OH groups. The reversible formation and dehydrogenation of these hydroxyl groups accelerate H2 release while suppressing hydrogen poisoning of Ru active sites. By continuously removing adsorbed H atoms via spillover, this mechanism promotes N-N coupling and lowers the energy barrier for the rate-limiting N2 desorption step. This work offers a general strategy for designing highly efficient and stable ammonia decomposition catalysts through rational construction of interfacial active sites.

Renewable energy has made significant strides, with the cost of clean electricity plummeting, making the use of renewable electricity for electrocatalytic CO2 reduction to synthesize high-value chemicals and fuels more economically attractive. Notably, certain non-copper-based electrocatalysts have shown remarkable selectivity for C2+ products at low overpotentials, even enabling the production of multi-carbon molecules that are undetectable on copper-based electrodes. This breakthrough opens up new avenues for research into non-copper catalysts. This article offers a thorough review of the latest research progress in employing non-copper-based catalysts for CO2 conversion, focusing on the generation of C2+ products in aqueous media. It explores the complex mechanisms of carbon-carbon coupling and provides a critical assessment of future directions for improving catalyst design, modulating interface microenvironments, and optimizing reaction systems for non-copper-based catalysts in CO2 reduction reactions (CO2RR).

Developing low-iridium electrocatalysts combined with high efficiency and longevity for oxygen evolution reaction (OER) in proton exchange membrane (PEM) water electrolysis remains challenging in the hydrogen economy. Here, an anodic electro-oxidation approach is reported to fabricate iridium (Ir) dope MnO2 gas diffusion electrodes, which exhibited remarkable stability of over 1650 h at 100 mA cm-2 with a record-high stability number of 2.9 x 108 by considering Ir leaching. The optimized catalyst with a low Ir loading of approximate to 0.3 mg cm-2 achieved stable operation at 1.0 A cm-2 in the PEM electrolyzer. The investigation reveals that the generation of high-valence Ir within MnO2 optimizes oxygen desorption and thereby boosts activity. Furthermore, MnO2 provides a platform that enables the oxidation and deposition of leached ions, initiating a self-healing mechanism that extends the operational lifetime of catalyst. This paves an effective way toward addressing the dissolution issues encountered by OER catalysts in acidic electrolytes.

The global shift toward a low-carbon society has accelerated the development of electrocatalytic CO2 reduction reaction (CO2RR) technology, which shows great potential in simultaneously addressing environmental pollution and energy crises. In the CO2RR system, microenvironment modulation can effectively enhance catalytic activity, product selectivity, operational stability, and energy efficiency. The introduction of ionomers into catalyst layers enables precise control of the microenvironment at the catalyst surface through their unique structural properties, significantly improving CO2RR performance. In this review, we first provide a concise overview of the key components and main influencing factors of the reaction microenvironment and the structures together with the functional mechanisms of commonly used ionomers. We then systematically discuss how various ionomers modulate the microenvironment, including their effects on CO2 mass transport, stabilization and diffusion of intermediates, ion species and concentrations at the surface (affecting the pH, K+ distribution and interfacial electric field), surface morphology and hydrophobicity of catalysts, and structures of interfacial water. Finally, we present a comprehensive summary that identifies current practical challenges of ionomer applications from multiple perspectives while proposing feasible solutions and outlining future research directions for this field.

Renewable energy has made significant strides, with the cost of clean electricity plummeting, making the use of renewable electricity for electrocatalytic CO 2 reduction to synthesize high‐value chemicals and fuels more economically attractive. Notably, certain non‐copper‐based electrocatalysts have shown remarkable selectivity for C 2+ products at low overpotentials, even enabling the production of multi‐carbon molecules that are undetectable on copper‐based electrodes. This breakthrough opens up new avenues for research into non‐copper catalysts. This article offers a thorough review of the latest research progress in employing non‐copper‐based catalysts for CO 2 conversion, focusing on the generation of C 2+ products in aqueous media. It explores the complex mechanisms of carbon‐carbon coupling and provides a critical assessment of future directions for improving catalyst design, modulating interface microenvironments, and optimizing reaction systems for non‐copper‐based catalysts in CO 2 reduction reactions (CO 2 RR).