Nuclear quantum effect and many-body interaction importantly interplay in the hydrogen on the Pt(111) system under the high coverage conditions of electrochemical interest, as revealed by our ab initio path integral and ring polymer molecular dynamics simulations done at room temperature. At the full monolayer coverage, hydrogen atoms are close-packed either at the atop sites or the fcc sites owing to their strong repulsion and the nearly degenerate nature of the adsorption sites. While at the 2/3 monolayer, they are delocalized over the fcc and hcp sites via the bridge sites because of the hopping. The quantum many-body effect is thus crucially important in determining the coverage dependence and provides a clue for reconciling the long-standing controversy on this system.

Oxide-supported Ag nanoparticles have been widely reported as a good approach to improve the stability and reduce the cost of photocatalysts. In this work, a Ag-nanoparticles-doped porous ZnO photocatalyst was prepared by using metal–organic frameworks as a sacrificial precursor and the catalytic activity over 4-nitrophenol was determined. The Ag-nanoparticles-doped porous ZnO heterostructure was evaluated by UV, XRD, and FETEM, and the catalytic rate constant was calculated by the change in absorbance value at 400 nm of 4-nitrophenol. The photocatalyst with a heterogeneous structure is visible, light-responsive, and beneficial to accelerating the catalytic rate. Under visible light irradiation, the heterostructure showed excellent catalytic activity over 4-nitrophenol due to the hot electrons induced by the localized surface plasmon resonance of Ag nanoparticles. Additionally, the catalytic rates of 4 nm/30 nm Ag nanoparticles and porous/nonporous ZnO were compared. We found that the as-prepared Ag-nanoparticles-doped porous ZnO heterostructure catalyst showed enhanced catalytic performance due to the synergetic effect of Ag nanoparticles and porous ZnO. This study provides a novel heterostructure photocatalyst with potential applications in solar energy and pollutant disposal.

Noble metal nanostructures can produce the surface plasmon resonance under appropriate photoexcitation, which can be used to promote or facilitate chemical reactions, as well as photocatalytic materials, due to their strong plasmon resonance in the visible light region. In the current work, Ag/Au nanoislands (NIs) and Ag NIs/Au film composite systems were designed, and their thermocatalysis performance was investigated using luminescence of Eu³⁺ as a probe. Compared with Ag NIs, the catalytic efficiency and stability of surface plasmons of Ag/Au NIs and Ag NIs/Au film composite systems were greatly improved. It was found that the metal NIs can also generate strong localized heat at low temperature environment, enabling the transition of NaYF₄:Eu³⁺ to Y₂O₃: Eu³⁺, and anti-oxidation was realized by depositing gold on the surface of silver, resulting in the relative stability of the constructed complex.

Localized surface plasmon has been extensively studied and used for the photocatalysis of various chemical reactions. However, the different contributions between plasmon resonance and interband transition in photocatalysis has not been well understood. Here, we study the photothermal and hot electrons effects for crystal transformation by combining controlled experiments with numerical simulations. By photo-excitation of NaYF₄ : Eu³⁺ @Au composite structure, it is found that the plasmonic catalysis is much superior to that of interband transition in the experiments, owing to the hot electrons generated by plasmon decay more energetic to facilitate the reaction. We emphasize that the energy level of hot electrons plays an essential role for improving the photocatalytic activity. The results provide guidelines for improving the efficiency of plasmonic catalysis in future experimental design.