Generative Discovery of Alloy Catalysts for Radical-Mediated Methane-to-Methanol Conversion.

Non-Covalent Host-Guest Extraction of Methanol Enables Enhanced Syngas-to-Methanol Conversion Over Hybrid Oxide-Porous Framework Catalysis.

Product formation is commonly regarded as the endpoint of heterogeneous catalysis, yet the subsequent fate of products near active surfaces critically affects catalytic turnover. For syngas-to-methanol conversion over Cu/Zn/Al (CZA) catalysts, product retention and re-adsorption represent an underappreciated limitation governing both activity and selectivity. Methanol generated at metal-oxide interfaces tends to remain near active sites, where interactions with surface hydroxyls trigger secondary reactions such as the water-gas shift. By physically mixing commercial CZA with hydrogen-bond-rich porous frameworks, we introduce a non-covalent host-guest extraction pathway that captures methanol from the interfacial region and facilitates its release into the gas phase. This extraction shifts the local adsorption-desorption equilibrium, suppresses methanol re-adsorption, and boosts methanol space-time yield by 1.12-1.43 times relative to pristine CZA, while retaining > 92.3% selectivity. In situ spectroscopy, transient kinetics, and simulations confirm the porous framework acts as a molecular sink, regulating methanol residence time and transport without direct catalytic participation. This effect is general across distinct metal-organic and covalent organic frameworks, establishing non-covalent extraction as a transferable strategy. This work demonstrates that non-covalent control of product desorption and transport serves as a complementary design principle for heterogeneous catalysis beyond conventional active-site engineering.

TITLE: Engineering Earth-Abundant Metal Catalysts using Metal-Organic Frameworks (MOFs) for Selective Oxidation of Methane and other Hydrocarbons

Selective Production of Methanol via Bidentate Coordination of an Intermediate on the Dual‐Atom Electro‐Catalyst

Electrochemical CO2 reduction offers a route to produce liquid fuels such as methanol; however, strong competition from hydrogen evolution and limited control over key reaction intermediates lead to low single‐product selectivity and poor stability under operating conditions. Heteronuclear dual‐atom catalysts (DACs) have shown great promise in this regard because two neighboring catalyst atoms can cooperatively bind and polarize oxygenated intermediates. Despite these attractive features, DACs often struggle to stabilize the right early intermediate for methanol, so CO2 protonation defaults back to *COOH (and then *CO), which breaks methanol selectivity. Here, we utilize DAC systems stabilized on a carbon nitride (C3N4) framework to resolve this mechanistic bottleneck at the molecular level using density functional theory and constrained molecular dynamics simulations. A Sn–N2/Cu–N2 DAC embedded in a C3N4 framework, coupled to an explicit aqueous interface and evaluated under an applied potential, is shown to favor methanol formation through a six‐electron *OCHO pathway. The neighboring Sn and Cu sites synergistically stabilize a bidentate *OCHO intermediate through Sn─O p‐orbital interactions, while suppressing formation of *COOH. The results provide a clear design rule for methanol‐selective CO2RR: enforce cooperative bidentate binding that locks in *OCHO and redirects the first protonation step away from *COOH and toward methanol.

Advances in Gaseous Ammonia Decomposition for Hydrogen Production: Catalysts and Emerging Pathways

Ammonia (NH3) is a compelling carbon-free hydrogen carrier. Its catalytic decomposition to produce a hydrogen/nitrogen (H2/N2) gas stream is central to the “NH3-H2” clean energy cycle, provided that residual NH3 is removed to fuel-cell-grade purity downstream. This review integrates advances from the past five years across four major catalytic NH3 decomposition pathways, encompassing conventional thermocatalysis, plasma-catalytic, photo(thermal), and electrically driven catalysis, within a unified mechanistic and practical framework, distinguishing it from existing single-pathway reviews. Noble metal catalysts, particularly Ru-based systems, achieve superior low-temperature activity through support engineering, promoter effects, and active-site construction. However, our analysis reveals that non-noble metal (Fe, Co, Ni) catalysts and their alloys, nitrides, and carbides have made substantial progress, with certain Co-based and bimetallic systems approaching Ru-level performance via interfacial oxygen vacancy engineering and electronic structure modulation. Emerging non-thermal routes effectively overcome thermodynamic barriers, enabling operation at temperatures 200–300 °C below conventional thermal requirements, though each faces distinct challenges in energy efficiency, stability, and scalability. Key challenges remaining across all pathways to practical implementation, including residual NH3 removal and H2 purification, catalyst deactivation and stability, heat management and energy efficiency, start-up/shut-down dynamics, as well as system integration and economics, are critically assessed. This review provides theoretical guidance and practical recommendations for developing scalable, low-temperature NH3 decomposition technologies.

Self-Organization of Alloy Catalysts into Selectively Active Ensembles

The active sites of alloy catalysts may emerge only under reaction conditions, yet how reactive atmospheres select these sites remains unresolved. Here, we reveal how reactive atmospheres reorganize complex alloy surfaces into functional active-state distributions by using a machine-learning-potential-accelerated multiscale framework. Using selective acetylene hydrogenation on Pd–Ag alloys as a model reaction, we show that adsorbates reverse the intrinsic Ag-segregation tendency, enrich Pd in the outermost layer, and generate a distribution of Pd3 hollow ensembles with distinct second-shell coordination environments. These dynamically formed ensembles, rather than the as-prepared isolated Pd sites, govern the calculated activity and selectivity trends. Ensemble-resolved energetics and kinetics identify the adsorption free-energy gap between ethylene and acetylene as a predictive descriptor that captures the activity-selectivity trade-off and defines an optimal window balancing acetylene hydrogenation and ethylene desorption. Extending the analysis across multiple alloy families further reveals a general scaling relationship in which adsorbate-driven self-organization is governed by adsorption asymmetry and alloy stability. These results establish dynamic ensemble selection as a transferable framework for understanding and designing adaptive alloy catalysts, shifting catalyst optimization from static structural descriptors toward reaction-condition-directed control of active-state distributions.

Electrocatalytic Partial Oxidation of Methane to Liquid Fuels over Metal Oxide Catalysts

Methane to high-value liquid fuel conversion is critical for enabling efficient utilization of abundant natural gas resources while overcoming challenges associated with methane storage and transportation. 1 However, the conventional industrial routes for converting methane into liquid products rely largely on indirect reforming processes that require high-temperature operation (> 800 o C), multistep processing, and substantial energy input. 2 From a molecular perspective, the high bond dissociation energy of methane (104 kcal mol -1 ) imposes severe kinetic barriers to C-H activation, while the thermodynamic preference for complete oxidation drives partially oxidized intermediates toward CO 2 formation. 3 This intrinsic coupling of kinetic difficulty and thermodynamic over-oxidation fundamentally limits the simultaneous achievement of high activity and selectivity. Consequently, electrocatalytic partial oxidation of methane has attracted increasing interest, since electrochemical systems allow precise regulation of reaction potential and oxidation pathways under mild conditions. 4 Nevertheless, selectively activating methane while suppressing over-oxidation remains a fundamental challenge for current catalytic technologies. 5 In this work, a series of MOₓ (M = Fe, Cu, Ni) catalysts is designed to regulate methane electrocatalytic oxidation through controlled metal–oxide interactions. Tailoring the intrinsic redox properties of the metal oxides modulates oxygen vacancy formation energies, lattice oxygen participation, and interfacial charge transfer, thereby decoupling methane activation from over-oxidation pathways. This study elucidates the role of metal–oxide interactions in controlling methane oxidation behavior and demonstrates enhanced activity in three-electrode electrochemical systems. Beyond intrinsic catalytic insights, the metal oxide catalysts are further integrated into membrane–electrode assemblies (MEAs) to evaluate their performance and stability under device-relevant electrochemical conditions. Reference N. F. Dummer et al., Chemical Reviews , 123 , 6359–6411 (2023). S. Yuan et al., Advanced Energy Materials , 10 , 1–19 (2020). M. R. A. Kishore, S. Lee, and J. S. Yoo, Advanced Science , 10 , 1–18 (2023). N. Xu et al., Applied Catalysis B: Environmental , 282 , 119572 (2021) . 5. K. Shen et al., Journal of the American Chemical Society , 145 , 6927–6943 (2023).