Controlling Selectivity in Plasmonic Catalysis: Switching Reaction Pathway from Hydrogenation to Homocoupling Under Visible-Light Irradiation.

Plasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible-light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible-light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon-enhanced H2 desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transformations with target selectivity one step closer to reality.

Spatiotemporal Coke Coupling Enhances para-Xylene Selectivity in Highly Stable MCM-22 Catalysts.

Identifying zeolite catalysts that can simultaneously optimize p-xylene selectivity and feed utilization is critical to toluene alkylation with methanol (TAM). Here, we show that zeolite MCM-22 (MWW) has an exceptional catalyst lifetime in the TAM reaction at high operating pressure, conversion, and selectivity. We systematically probe the catalytic behavior of active sites in distinct topological features of MCM-22, revealing that high p-xylene yield and catalyst stability are predominantly attributed to sinusoidal channels and supercages, respectively. Using a combination of catalyst design and testing, density functional theory, and molecular dynamics simulations, we propose a spatiotemporal coke coupling phenomenon to explain a multistage p-xylene selectivity profile wherein the formation of light coke in supercages initiates the deactivation of unselective external surface sites. Our findings indicate that the specific nature of coke is critical to catalyst performance. Moreover, they provide unprecedented insight into the synchronous roles of distinct topological features giving rise to the exceptional stability and selectivity of MCM-22 in the TAM reaction.

Significant Role of Oxygen Dopants in Photocatalytic PFCA Degradation over h-BN.

The activation of the C(sp3)-F bond is extremely difficult due to its unreactive nature. The importance of this bond activation is recently highlighted because extensive distribution of perfluorocarboxylic acids (PFCAs) (CnF2n+1COOH) has emerged as a challenging environmental issue. Photocatalytic degradation of PFCAs over a few semiconducting light absorbers is known to remove these water and soil resilient contaminants but with limited efficiency. This work reports density functional theory calculations, through which we present a detailed mechanistic study of photocatalytic degradation of CF3COOH (the shortest member of the PFCA family) over hexagonal boron nitride (h-BN). Our results clearly demonstrate that the existence of point defects is necessary to activate the h-BN plane for photocatalytic dissociation of the C-F bond. Specifically, we show that vacancies create strong Lewis acid or base sites (B or N vacancy, respectively) that facilitate the activation of the C(sp3)-F bond considerably. Furthermore, this study presents vivid theoretical evidence for the significant role of oxygen dopants, which mitigate the strength of the active sites and promote PFCA degradation over h-BN. Our calculations suggest that while the very stable intermediates generated during the reaction, in the case of h-BN with B or N vacancies, practically poison the catalyst, oxygen dopants make the degradation much more plausible and controllable. This work thus provides both an explanation for recently observed photocatalytic activity of h-BN to decompose PFCAs and valuable insights for exploring defected two-dimensional materials for activating and removing the fluorine-containing contaminants from water and soil.

Atomic Properties of Monoclinic Ag2Se Thin Film Grown on SrTiO3 Substrate by Molecular Beam Epitaxy.

Silver chalcogenides have attracted a great deal of interest due to their promise for exhibiting novel topological properties. Using scanning tunneling microscopy/spectroscopy (STM/S), we have characterized the atomic structure and electronic properties of a monoclinic Ag2Se thin film, similar to ß-Ag2Te, grown on a SrTiO3 (STO)(001) substrate by molecular beam epitaxy (MBE). Three different types of Ag2Se atomic terminations are observed on the surface: (i) homogeneous hexagonal-like, (ii) rough mixed, and (iii) flat zigzag-striped structures. Structural analysis indicates that the different atomic terminations stem from different growth directions, which can be attributed to the lattice mismatch between the substrate and the Ag2Se film. STS analysis of these atomic terminations uncovers different features near the Fermi level, indicating constituent- and direction-dependent electronic properties. This Letter presents a practical method to grow monoclinic thin film Ag2Se and provides insight into its physical properties.

DFT Study of Solvent Effects in Acid-Catalyzed Diels-Alder Cycloadditions of 2,5-Dimethylfuran and Maleic Anhydride.

Density functional theory electronic structure calculations were used to explore the mechanism for the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride (MA). Reaction paths are reported for uncatalyzed and Lewis and Brønsted acid-catalyzed reactions in vacuum and in a broad range of solvents. The calculations show that, while the uncatalyzed Diels-Alder reaction is thermally feasible in vacuum, a Lewis acid (modeled as Na(+)) lowers the activation barrier by interacting with the dienophile (MA) and decreasing the HOMO-LUMO gap of the reactants. A Brønsted acid (modeled as a proton) can bind to a carbonyl oxygen in MA, changing the reaction mechanism from concerted to stepwise and eliminating the activation barrier. Solvation effects were studied with the SMD model. Electrostatic effects play the largest role in determining the solvation energy of the transition state, which tracks the net dipole moment at the transition state. For the uncatalyzed reaction, the dipole moment is largely determined by charge transfer between the reactants, but in the reactions with ionic catalysts, there is no simple relationship between solvation of the transition state and charge transfer between the reactants. Nonelectrostatic contributions to solvation of the reactants and transition state also make significant contributions to the activation energy.