C. S. Praveen

The strong metal–support interaction (SMSI) has traditionally been viewed as a static phenomenon that modulates catalysis through site blocking. Here, we challenge this classical view by demonstrating that SMSI in Au/ZnO is an atmosphere‐dependent dynamic process that can be harnessed to engineer catalytic interfaces. Using in situ transmission electron microscopy, infrared spectroscopy, and X‐ray photoelectron spectroscopy, we track the structural evolution of the Au/ZnO interface throughout redox cycles and reaction conditions. Under H ₂ , oxygen vacancy formation triggers ZnO _x encapsulation, followed by AuZn alloying at elevated temperature, which induces nanoparticle reconstruction and expands the metal‐support interfacial area. Upon exposure to O ₂ , the alloy decomposes, and the ZnO _x overlayer dewets into nanoislands, with some regions undergoing complete retraction. Under CO oxidation conditions, the fully encapsulated state is lost, yet the H ₂ ‐pretreated catalyst exhibits superior activity and stability. This enhancement arises from alloying‐induced interface reconstruction together with residual ZnO nanoislands that persist after dewetting, creating an enlarged and highly active metal–oxide interface. Our work demonstrates a transient‐overlayer strategy for catalyst design, in which a pre‐formed SMSI layer serves as a precursor that, through controlled redox cycling or reaction conditions, transforms into a high‐interface area, sintering‐resistant catalytic architecture, thereby transcending the classical encapsulation‐activity dilemma.

The strong metal–support interaction (SMSI) has traditionally been viewed as a static phenomenon that modulates catalysis through site blocking. Here, we challenge this classical view by demonstrating that SMSI in Au/ZnO is an atmosphere‐dependent dynamic process that can be harnessed to engineer catalytic interfaces. Using in situ transmission electron microscopy, infrared spectroscopy, and X‐ray photoelectron spectroscopy, we track the structural evolution of the Au/ZnO interface throughout redox cycles and reaction conditions. Under H ₂ , oxygen vacancy formation triggers ZnO _x encapsulation, followed by AuZn alloying at elevated temperature, which induces nanoparticle reconstruction and expands the metal‐support interfacial area. Upon exposure to O ₂ , the alloy decomposes, and the ZnO _x overlayer dewets into nanoislands, with some regions undergoing complete retraction. Under CO oxidation conditions, the fully encapsulated state is lost, yet the H ₂ ‐pretreated catalyst exhibits superior activity and stability. This enhancement arises from alloying‐induced interface reconstruction together with residual ZnO nanoislands that persist after dewetting, creating an enlarged and highly active metal–oxide interface. Our work demonstrates a transient‐overlayer strategy for catalyst design, in which a pre‐formed SMSI layer serves as a precursor that, through controlled redox cycling or reaction conditions, transforms into a high‐interface area, sintering‐resistant catalytic architecture, thereby transcending the classical encapsulation‐activity dilemma.

The electrocatalytic CO₂ reduction reaction (e-CO₂RR) on Cu-based catalysts has been extensively studied; however, achieving high selectivity for C₂₊ products and long-term durability remains challenging. Here, we introduce a straightforward approach that enhances both C₂H₄ selectivity and catalyst durability by incorporating a nitrogen-rich Schiff-base Network (SNW), leveraging a synergistic interaction between Cu and SNW. Notably, Cu cubes with SNW, predominantly exposing the Cu(200) facet, achieve a Faradaic Efficiency (FE) of 71.2% for C₂H₄ at a current density of 265 mA cm⁻², which not only exceeds tetrahedral and spherical Cu with or without SNW, but also ranks competitively among state‑of‑the‑art Cu-based catalysts reported to date. Theoretical calculations suggest that the presence of SNW on Cu facilitates the *CO-*CHO coupling and/or the C₂H₄ desorption, thereby enhancing C₂H₄ formation. Furthermore, the Cu(200)-SNW surface exhibits optimized Gibbs free energies for the reaction steps compared to bare Cu and other SNW-modified Cu surfaces, which rationalizes the experimental observations. In situ electron microscopy further suggests that SNW confers durability by stabilizing Cu facets and preventing corrosion and dissolution under reaction conditions.

The electrochemical conversion of CO ₂ to value‐added products is perceived to be a promising strategy for mitigating CO ₂ emissions and promoting environmental sustainability. This work reports the preparation of a series of N‐doped porous carbons containing ultrafine dispersions of bismuth using a facile metal‐organic framework‐assisted strategy. The Bi/NC catalyst with optimal bismuth loading (24.8 wt.%) demonstrates appreciable catalytic activity toward electrochemical CO ₂ reduction reaction (eCO ₂ RR) by the effective conversion of CO ₂ to formate with a more positive onset potential of −0.6 V (vs RHE) and high electrochemically active surface area. As a result, the catalyst possesses formate faradaic efficiency of 91% at −0.8 V (vs RHE) with a long‐term stability of 24 h in 0.5 m KHCO ₃ solution. The remarkable catalytic activity of the catalyst is ascribed to the combined effect of enhanced metallic active sites and the enhanced mass transport facilitated via micro‐meso porous carbon matrix containing dominant pyridinic N sites. Notably, DFT calculations reveal that pyridinic N‐ doping in a carbon matrix containing bismuth nanoparticles lowers the energy barrier of ^* OCHO formation and suppresses the competitive hydrogen evolution reaction.

Controlling the selectivity of CO2 hydrogenation remains a challenge in catalysis. In this study, we demonstrate that the well-defined silica supported PtGa and PtZn alloy nanoparticles, synthesized via a surface organometallic chemistry (SOMC) approach, display greatly different product selectivity in CO2 hydrogenation. While the PtZn@SiO2 catalyst shows almost exclusive CO selectivity (~99%), PtGa@SiO2 primarily produces CH3OH with 54% selectivity, despite both catalysts showing similar activities. While both PtM (M = Zn or Ga) forms bulk alloys, in situ spectroscopic studies complemented with DFT calculations reveal that their surface properties differ under reaction conditions, determining the product selectivity. The surface of the PtZn alloy remains stable without undergoing surface oxidation during CO2 hydrogenation, resulting in the decomposition of formate (HCOO*) species to produce CO. In contrast, the surface of the PtGa alloy undergoes dynamic redox process forming PtGa-GaOx interfaces during reaction conditions, key to promoting methanol synthesis via a HCOO*→CH3O* reaction pathway.

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

The CatBoost method, combined with cluster filtering, accurately predicts adsorption energies on metal alloys. The approach uses local chemical descriptors to understand chemisorption on metal alloys, which is essential for catalytic applications.

A schematic illustration of PANI–MnMoO₄synthesis for overall water splitting is demonstrated with excellent electrocatalytic activity and stability.