The urgent need to mitigate accelerating CO2 emissions has driven intense interest in photocatalytic CO2 reduction (CO2RR), a process that mimics natural photosynthesis to generate carbon-neutral, value-added chemicals. While efficiency has improved, the selective production of high-value C2+ products rather than C1 compounds remains a critical challenge to economic viability. Single-atom catalysts offer promise for steering selectivity, yet how atomic-scale spatial distribution dictates reaction pathways remains poorly understood. Here, we demonstrate a programmed spatial distribution approach to induce synergistic cooperativity between neighboring Cu motifs within a UiO-67 matrix. By precisely modulating site distribution, we reveal a spatial threshold at which the framework transitions from isolated sites favoring C1 products to correlated single-atom pairs (CSAPs) that facilitate C-C bond formation. Temperature-resolved electron paramagnetic resonance spectroscopy provides compelling evidence for the distribution-dependent proximity, capturing a unique magnetic feature that emerges as torsional linker motions are suppressed. This structural configuration utilizes the inherent rotational flexibility of the linkers to dynamically optimize interatomic distances, effectively stabilizing [OC-CO]* dimer intermediates and steering the reaction toward C2 products.

Abstract Electrochemical urea synthesis through C–N coupling is a promising alternative to conventional thermochemical production, yet the activity-determining factors of alloy catalysts under realistic electrochemical conditions remain unclear. Here, we combine density functional theory, solvation-inclusive modeling, and constant-potential analysis to investigate Cu3M alloys for urea synthesis from nitrite and carbon dioxide. The Cu3M stoichiometry preserves a Cu-like adsorption environment while introducing controlled heteroatom-induced asymmetry, and the Cu3M(111) surface provides neighboring fcc and hcp threefold sites for site-resolved analysis. Among the alloys, Cu3Sn(111) exhibits the lowest C–N coupling barrier. We show that intrinsic asymmetry between neighboring triangular adsorption motifs plays a decisive role in governing urea formation, with adjacent fcc sites generally showing more favorable coupling energetics than hcp sites. To quantify this effect, we introduce a Janus descriptor that captures the geometric and electronic asymmetry of neighboring dual sites and correlates strongly with activity across the Cu3M alloy series. Constant-potential calculations further reveal that *CO2 + *NH2 coupling is selectively stabilized at negative potentials through hydrogen bonding. These findings establish an asymmetry-based framework for designing Cu-based alloy catalysts.

The photocatalytic CO2 reduction reaction (CO2RR) into high value-added chemicals using clean and renewable solar energy represents a promising strategy to address energy and environmental challenges. Metal-organic frameworks (MOFs) have garnered extensive research attention for their applications in CO2RR owing to their superior CO2 capture capabilities, photochemical properties, and structural tunability. This review explores recent advancements in the atomic-level engineering of metal active sites within MOFs for enhanced photocatalytic CO2RR, with a specific emphasis on strategies to overcome one of the well-recognized challenges, i.e., selective production of multi‑carbon (C2+) products. We systemically analyze the impact of single-atom catalysts (SACs), dual-atom catalysts (DACs), metal loading density, and spatial architecture on the selectivity and efficiency of CO2 conversion. By integrating experimental findings and theoretical insights, we elucidate structure-activity relationships and propose rational design principles for MOF-based photocatalysts with optimal metal sites targeting high-value C2+ products. This comprehensive analysis not only clarifies fundamental mechanistic aspects but also identifies current limitations and outlines promising future research trajectories for advancing solar-driven carbon chain growth.

High-capacity Mn-rich layered cathodes suffer from intrinsically unstable anionic redox chemistry. Herein, we report that structural ordering regulation via synthesis temperature effectively stabilizes this anionic redox, achieving 253 mAh g-1 capacity after 100 cycles at 0.1C and over 92% capacity retention after 200 cycles at 1C.

In aluminosilicate zeolites, the atomic-scale insights into catalytic performance are tied to Br & oslash;nsted acid sites (BASs), the primary active sites generated by the substitution of aluminum (Al) for silicon (Si) in the tetrahedral framework, with a proton (H+) compensating for the resultant charge imbalance. The profound influence of Al distribution on BAS density, spatial arrangement, and acidity is well established. Yet, the precise atomic positions of these Al atoms remain poorly resolved. Using silver (Ag) as a molecular probe, this study combines synchrotron X-ray diffraction (SXRD) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to reveal the specific locations of Al atoms in ZSM-5, a prototypical zeolite catalyst. Statistical analysis of HAADF-STEM images unambiguously identifies the crystallographic adsorption sites of Ag at T4, T6, and T8, linking their distribution directly to the predominant framework Al sites, which correlates perfectly with the predominant Al sites identified by our previous work. By mapping these Al sites, we establish an atomic-scale model for single atom catalysis within the zeolite framework. This work develops methodologies further to elucidate the structure-activity relationship of industrially relevant zeolite catalysts, providing the foundational knowledge for rationally designing zeolite catalysts with optimised active sites and enhanced performance.

Ni 2+ single atoms on PHI photocatalyze the selective semi-hydrogenation of alkynes, using water as the proton source.

The severely sluggish kinetics of the hydrogen oxidation reaction (HOR) in alkaline media constitute a major bottleneck hindering the commercialization of anion-exchange membrane fuel cells (AEMFCs). While platinum group metals (PGMs) remain the benchmark, their high cost and scarcity drive the urgent need for efficient, durable, and affordable alternatives. Nickel (Ni), with its favorable intrinsic hydrogen binding energy (HBE) and natural abundance, has emerged as the leading PGM-free candidate. However, the rational design of highperformance Ni-based catalysts is still challenging, often hampered by fragmented approaches that treat underlying mechanisms, materials engineering, and device integration in isolation. In this review, we propose a unified "intermediate-interface-infrastructure" paradigm to bridge these gaps. Firstly, we dissect the kinetic roles and interplay of key reaction "Intermediates", including adsorbed hydrogen (Had), hydroxyl (OHad), and the interfacial water network, as the fundamental pillar. We then elucidate how the strategic engineering of the catalyst "Interface" through alloying, heteroatom doping, heterostructuring, and metal-support effects can synergistically optimize the binding energetics and conversion kinetics of these intermediates. Finally, we contextualize these catalysts within the practical "Infrastructure" of AEMFC operation, critically discussing the stability and real-world device performance metrics. By integrating these three interconnected pillars, our proposed framework not only clarifies the structure-property-performance relationships but also provides a coherent roadmap for developing the advanced Ni-based anode catalysts capable of meeting the demanding performance and durability targets for next-generation AEMFCs.

The simultaneous and selective production of syngas and value-added chemicals from biomass-derived feedstocks is fundamentally restricted by sluggish multi-electron-proton transfer and the lack of precisely defined active sites capable of stabilizing reactive intermediates. Here, we report a sulfur-mediated coordination reconstruction strategy that transforms metastable rhenium species on two-dimensional chromium boride into uniformly dispersed Re-S4 single atoms. The electronic environment of Re-S4 optimizes the d-band center, stabilizing the key intermediate glyceraldehyde for selective C-C bond cleavage. In this work, the synergistic combination of atomic-scale engineering and reactant kinetics modulation yields a total syngas rate of 34.08 mmol g-1 h-1 with a wide-ranging tunable H2/CO ratio (0.1 to 14.4), alongside a lactic acid yield of 90.8%. The system's robustness is further validated via large-scale outdoor sunlight-tracking tests, demonstrating its potential as a scalable, sustainable biorefinery technology for the concurrent production of gas-phase fuels and liquid-phase platform chemicals.

Developing earth-abundant electrocatalysts that rival the commercial platinum/carbon catalyst for the hydrogen evolution reaction (HER) remains a central challenge in renewable-energy conversion. Here, we reveal an electrochemically induced, in situ phase transformation in a Ru-MgO catalyst that leads to true active material during operation. Under acidic HER conditions, nominal 20 wt.% Ru nanoparticles supported on polar MgO(111) nanocrystals undergo a topotactic hydrolysis to Ru-Mg(OH)2(001), generating an ordered hydroxide layer that serves as a highly conductive proton-hopping network. After activation, the catalyst delivers performance comparable to commercial Pt/C under identical conditions, matching the current density of -1.1 V and surpassing it by approximately 10% at -2.3 V. Operando synchrotron X-ray diffraction combined with ex situ characterization techniques directly captures this transformation, while density-functional theory calculations reveal that water-assisted Grotthuss proton transfer across the hydroxide requires only a 0.10 eV energy barrier. These findings establish electrochemically driven oxide-to-hydroxide conversion as a new design principle for creating low-Pt or Pt-free HER electrocatalysts with intrinsically fast proton transport.

Abstract Photocatalytic reduction of O 2 to H 2 O 2 is generally regarded to proceed through the *O 2 hydrogenation pathway (*O 2 → *OOH), which inevitably encounters a high energy barrier proton extraction process via cleavage of the H-O bond in H 2 O. Designing a K and Cs co-modified polymeric carbon nitride (CN-KCs) to create dual-end adsorption sites as frustrated Lewis pairs for O 2 , on which the O-O breaking energy is significantly reduced and a *O 2 dissociation pathway towards photocatalytic H 2 O 2 synthesis is realized (*O 2 → 2*O, then *O + *H 2 O → H 2 O 2 ). The CN-KCs presents a competitive photocatalytic H 2 O 2 yield of 1806.6 μmolh −1 , a high quantum efficiency of 72.3% at 420 nm, and a solar-to-H 2 O 2 conversion efficiency of 6.1% with presence of biomass derivative. Here, we show that regulating dual-end adsorption sites opens a door to new *O 2 dissociation avenue for efficient conversion of O 2 to H 2 O 2 .

Metal-organic frameworks (MOFs) offer exceptional structural tunability for targeted gas adsorption and separation; however, traditional pore engineering via organic ligand functionalisation often necessitates complex synthetic routes. In contrast, substituting inorganic secondary building units (SBUs) offers a streamlined strategy for modulating the pore environment, particularly when introducing metals with varied valences that require charge-balancing counterions. Herein, we elucidate the regulatory role of extra-framework cations by conducting a comparative study between the anionic yttrium-based framework (Y-fum-fcu-MOF) and its neutral zirconium analogue (Zr-fum-fcu-MOF, MOF-801). Through high-resolution synchrotron X-ray powder diffraction and Rietveld refinement, we identify a unique 'pincer-like' coordination mechanism within the Y-MOF cavities, where CO2 molecules are synergistically stabilised by Y3+ centres and protonated dimethylammonium (DMA-H+) counteraction. This cooperative interaction effectively constrains the rotational and translational degrees of freedom of the guest molecules, resulting in a significantly enhanced isosteric heat of adsorption (Q(st) = 38 kJ mol(-1)). Consequently, Y-MOF exhibits a CO2 uptake of 85.11 cm(3) g(-1) at 273 K, representing a 46.4% increase over the neutral Zr-MOF, alongside superior CO2/N-2 selectivity. These findings demonstrate that counteraction engineering can induce localised 'electrostatic locking' of guest molecules, providing a robust molecular-level blueprint for designing high-performance adsorbents for industrial carbon capture and gas separation.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) offers a compelling route to close the carbon cycle. However, its industrial viability is severely undermined by the hydrogen evolution reaction (HER), a persistent and competitive side reaction. Traditional catalyst engineering has achieved notable progress, yet it remains fundamentally constrained by linear scaling relations (LSRs). LSRs inextricably link the energetics of CO2 activation to that of proton reduction, creating an inherent trade-off that limits selectivity. This review highlights an emerging quantum-mechanical strategy that can potentially overcome this impasse: the use of chiral nano-catalysts that exploit the Chirality-Induced Spin Selectivity (CISS) effect. By generating spin-polarized electron transport, chiral surfaces may make HH coupling less favorable on selected catalytic interfaces. This spin-dependent effect can reduce the kinetic preference for HER. We examine the underlying spin-filtering mechanisms and survey recent reports on chiral transition-metal catalysts, including those based on Cu, Ag, and Au. Furthermore, we discuss how spin control can be integrated with established microenvironmental engineering strategies. Merging chirality with rational interfacial design offers a potentially powerful and versatile pathway toward highly selective, carbon-neutral energy conversion.

Professor Shik Chi Edman Tsang (1962-2025) made sustained and influential contributions to heterogeneous catalysis through a distinctive approach that integrates nanostructure design, advanced characterization, and mechanistic understanding. This Account, written by his former students, highlights the key research themes that defined his scientific career, centered on the principle that catalytic function arises from the controlled interplay of structure, electronic properties, and interfaces at the atomic scale. Early studies on carbon nanostructures and supported nanoparticles established the importance of direct structural observation in understanding catalytic behavior. These foundations evolved into systematic strategies for nanostructure-controlled catalysis. A central theme of Tsang's work is the role of interfaces and local environment in governing reaction pathways. These principles are exemplified in catalytic processes relevant to energy and sustainability, including hydrogen evolution, CO2 hydrogenation, ammonia synthesis and decomposition, and biomass and plastic conversion. Tsang's contributions also extend to electrocatalysis and photocatalysis, where atomic-scale design is combined with external driving forces, such as electrical bias, light, and thermal energy. In parallel, the integration of advanced characterization techniques, particularly synchrotron-based methods and electron microscopy, has enabled direct observation of active sites and their evolution under working conditions. Importantly, his work bridges fundamental science and practical application, demonstrating how atomic-level catalyst design can inform scalable technologies for sustainable energy and chemical production.

Abstract Spin-state engineering has emerged as a powerful strategy for regulating the reactivity of single-atom catalysts (SACs) beyond conventional coordination and electronic structure optimization. In electrocatalytic NOx and COx conversion, many elementary steps involve open-shell intermediates, spin-dependent electron transfer, and radical-like transition states, making catalytic activity and selectivity highly sensitive to the spin configuration of the isolated metal centers. This Perspective introduces a spin-centered framework for SAC electrocatalysis in which spin polarization, spin crossover, and spin-selective orbital interactions govern access to spin-allowed pathways and stabilize key reaction intermediates. We first outline the fundamental spin-chemistry principles relevant to small-molecule activation, including spin selection rules, d-orbital occupation, spin polarization, and spin–orbit coupling. We then discuss how coordination environments, support interactions, adsorbate binding, electrochemical potentials, and external fields can be used to modulate the spin states of SACs under both static and operating conditions. Representative examples in NOx and COx electrocatalysis are highlighted to illustrate how spin-state engineering reshapes adsorption energetics, proton-coupled electron transfer, bond activation, and catalytic selectivity. Finally, we identify emerging opportunities in operando spin characterization, predictive electronic structure theory, and dynamically programmable catalyst design. By integrating spin chemistry with single-atom catalysis, this Perspective establishes the spin state as an active and programmable design parameter for next-generation electrocatalytic transformations.

Spin-state plays a crucial role in defining the electronic structure and catalytic reactivity of transition metal catalysts. However, precise manipulation of spin states is challenging, and their impact on catalytic mechanisms remains poorly understood. Here, we show that the curvature of carbon nanotubes (CNTs) tunes the spin state of cobalt phthalocyanine (CoPc) anchored on CNTs, thereby affecting the activity and selectivity in the electroreduction of nitric oxide (NORR) to ammonia. As the CNT diameter falls below 3 nm, the Co2+ center spontaneously transitions from a low-spin (LS) to a high-spin (HS) state. Density functional theory calculations and in situ spectroscopic measurements show that the HS state weakens the N=O bond and promotes bent *NO, which favors NH3 generation. As a result, the optimized catalyst achieves a high partial current density with a Faradaic efficiency of >90% at -0.5 V versus the reversible hydrogen electrode (RHE), while maintaining good stability. This work highlights spin-state engineering via support curvature for selective electrochemical transformations.

Stable extra-large-pore zeolites are highly desirable for catalysis and molecular separation, but most remain microporous, limiting their effectiveness for bulky substrates. Among the few extra-large-pore zeolites that exhibit mesoporosity, the pores typically form as elongated, noncircular pore apertures. We report that NJU120-6, a stable silicate zeolite with an intrinsic cylindrical mesoporous system, has the currently largest 36-ring windows with a free diameter of 25.71 angstroms by 19.12 angstroms. NJU120-6 exhibits the lowest framework density of 9.39 silicon atoms per cubic nanometer and a pore volume of 0.66 cubic centimeters per gram. It remains stable up to 1173 kelvin and can incorporate aluminum and titanium, enabling superior performance in catalytic cracking and in liquid-phase alkene oxidation of bulky molecules, respectively.

Comprehensive Summary Catalytic hydrogenation of carbon dioxide (CO 2 ) into aromatic hydrocarbons has emerged as a promising route for the high‐value CO 2 utilization and sustainable aromatics production to alleviate fossil resource dependence under the carbon‐neutrality goals. By integrating CO 2 activation/hydrogenation with the downstream C–C coupling and aromatization, bifunctional catalytic systems, typically comprising metal or metal oxide components coupled with acidic zeolites, enable the direct synthesis of valuable aromatics ( e.g. , benzene, toluene, and xylene) from CO 2 . Recently, significant progress has been made in the rational design of such catalysts, particularly through the precise tailoring of the zeolite component for regulating the reaction pathways, product selectivity, and catalyst stability. This minireview summarizes recent advances in CO 2 hydrogenation to aromatics achieved by bifunctional catalysts, with a specific focus on the decisive role of the zeolite properties in governing the aromatization behaviors. Various zeolite modification strategies, such as acidity regulation, metal and non‐metal functionalization, pore‐structure engineering, and morphology control, are systematically discussed in relation to their effects on the intermediate transformation and aromatic selectivity. Finally, perspectives on future research are presented, emphasizing the importance of advanced characterization techniques and theoretical modeling for the rational design of more efficient, selective, and stable CO 2 ‐to‐aromatics catalysts and technologies. Key Scientists

Li-rich Mn-based oxides (LRMO) hold great promise for the high-energy-density lithium-ion batteries due to their unique oxygen anionic redox chemistry. However, their electrochemical performance is challenged by the nucleophilic attack and electrochemical oxidative decomposition of the conventional carbonate electrolyte during cycling, which jointly induce parasitic side reactions and the interfacial and structural degradation, subsequently accelerating the capacity/voltage decay. Herein, we propose electrolyte engineering to precisely fabricate a thin, homogeneous, and F-rich organic-inorganic composite cathode-electrolyte interphase (CEI) on LRMO to enhance the interfacial stability, achieved via the rational utilization of the nucleophilic reaction between surface reactive oxygen species of LRMO and the electrolyte. Specifically, we employed 3,3,3-trifluoropropylene carbonate (TFPC) as the electrolyte, which tends to selectively adsorb nucleophilic oxygen species and preferentially decomposes to construct an interfacial passivation layer on LRMO, featuring inter organic-rich and outer inorganic-rich gradient distribution. Such a multifunctional interphase can promptly and effectively scavenge the irreversible superoxide species and inhibit the continuous electrolyte decomposition and transition metal dissolution. Additionally, the LiF-rich component within the CEI promotes the interfacial Li+ transport and enhances the electrochemical dynamics. Therefore, with the optimized TFPC electrolyte, the LRMO exhibits ultra-stable cycling performance at 1 C after 200 cycles, with a prominent capacity retention of 90.20% and superior rate performance. Surprisingly, the assembled Li & Vert;LRMO pouch cell matched with the designed electrolyte can operate stably for 50 cycles at 4.8 V, achieving an energy density of approximately 520 Wh kg-1. This work highlights an advanced electrolyte design strategy for leveraging the nucleophilic reactions to prolong the lifetime of high-voltage LRMO batteries.

Liquid organic hydrogen carriers (LOHCs) are considered promising carriers for large-scale H2 storage and transportation, among which the toluene-methylcyclohexane cycle has attracted great attention from industry and academia because of the low cost and its compatibility with the current infrastructure facility for the transportation of chemicals. The large-scale deployment of the H2 storage/transportation plants based on the toluene-methylcyclohexane cycle relies on the use of high-performance catalysts, especially for the H2 release process through the dehydrogenation of methylcyclohexane. In this work, we have developed a highly efficient catalyst for MCH dehydrogenation reaction by incorporating subnanometer PtFe clusters with precisely controlled composition and location within a rigid zeolite matrix. The resultant zeolite-encapsulated PtFe clusters exhibit the up-to-date highest reaction rate for dehydrogenation of methylcyclohexane to toluene, very high chemoselectivity to toluene (enabling the production of H2 with purity >99.9%), remarkably high stability (>2000 h) and regenerability over consecutive reaction-regeneration cycles. The large-scale deployment of H2 storage/transportation plants using the toluene-methylcyclohexane cycle depends on high-performance catalysts. Here, subnanometer bimetallic PtFe clusters confined within MFI zeolite demonstrate remarkable activity and stability for the dehydrogenation of methylcyclohexane, offering great potential for H2 storage systems based on liquid organic hydrogen carriers.