Tuning Adsorbate-Mediated Strong Metal-Support Interaction by Oxygen Vacancy: A Case Study in Ru/TiO2.

The adsorbate-mediated strong metal-support interaction (A-SMSI) offers a reversible means of altering the selectivity of supported metal catalysts, thereby providing a powerful tool for facile modulation of catalytic performance. However, the fundamental understanding of A-SMSI remains inadequate and methods for tuning A-SMSI are still in their nascent stages, impeding its stabilization under reaction conditions. Here, we report that the initial concentration of oxygen vacancy in oxide supports plays a key role in tuning the A-SMSI between Ru nanoparticles and defected titania (TiO2-x). Based on this new understanding, we demonstrate the in-situ formation of A-SMSI under reaction conditions, obviating the typically required CO2-rich pretreatment. The as-formed A-SMSI layer exhibits remarkable stability at various temperatures, enabling excellent activity, selectivity and long-term stability in catalyzing the reverse water gas-shift reaction. This study deepens the understanding of the A-SMSI and the ability to stabilize A-SMSI under reaction conditions represents a key step for practical catalytic applications.

Supra-Photothermal CO2 Methanation over Greenhouse-Like Plasmonic Superstructures of Ultrasmall Cobalt Nanoparticles.

Improving the solar-to-thermal energy conversion efficiency of photothermal nanomaterials at no expense of other physicochemical properties, e.g., the catalytic reactivity of metal nanoparticles, is highly desired for diverse applications but remains a big challenge. Herein, a synergistic strategy is developed for enhanced photothermal conversion by a greenhouse-like plasmonic superstructure of 4 nm cobalt nanoparticles while maintaining their intrinsic catalytic reactivity. The silica shell plays a key role in retaining the plasmonic superstructures for efficient use of the full solar spectrum, and reducing the heat loss of cobalt nanoparticles via the nano-greenhouse effect. The optimized plasmonic superstructure catalyst exhibits supra-photothermal CO2 methanation performance with a record-high rate of 2.3 mol gCo -1 h-1 , close to 100% CH4 selectivity, and desirable catalytic stability. This work reveals the great potential of nanoscale greenhouse effect in enhancing photothermal conversions through the combination with conventional promoting strategies, shedding light on the design of efficient photothermal nanomaterials for demanding applications.

Modulation of the Structure-function Relationship of the "nano-greenhouse effect" towards Optimized Supra-photothermal Catalysis.

Photothermal catalytic CO2 hydrogenation holds great promise for relieving the global environment and energy crises. The "nano-greenhouse effect" has been recognized as a crucial strategy for improving the heat management capabilities of a photothermal catalyst by ameliorating the convective and radiative heat losses. Yet it remains unclear to what degree the respective heat transfer and mass transport efficiencies depend on the specific structures. Herein, the structure-function relationship of the "nano-greenhouse effect" was investigated and optimized in a prototypical Ni@SiO2 core-shell catalyst towards photothermal CO2 catalysis. Experimental and theoretical results indicate that modulation of the thickness and porosity of the SiO2 nanoshell leads to variations in both heat preservation and mass transport properties. This work deepens the understandings on the contributing factor of the "nano-greenhouse effect" towards enhanced photothermal conversion. It also provides insights on the design principles of an ideal photothermal catalyst in balancing heat management and mass transport processes.

Photocatalytic H2O Overall Splitting into H2 Bubbles by Single Atomic Sulfur Vacancy CdS with Spin Polarization Electric Field.

Low efficient transfer of photogenerated charge carriers to redox sites along with high surface reaction barrier is a bottleneck problem of photocatalytic H2O overall splitting. Here, in the absence of cocatalysts, H2O overall splitting has been achieved by single-atomic S vacancy hexagonal CdS with a spin polarization electric field (PEF). Theoretical and experimental results confirm that single-atomic S vacancy-induced spin PEF with opposite direction to the Coulomb field accelerates charge carrier transport dynamics from the bulk phase to surface-redox sites. By systematically tuning the spin PEF intensity with single-atomic S vacancy content, common pristine CdS is converted to a photocatalyst that can efficiently complete H2O overall splitting by releasing a great number of H2 bubbles under natural solar light. This work solves the bottleneck of solar energy conversion in essence by single atom vacancy engineering, which will promote significant photocatalytic performance enhancement for commercialization.