A. Marimuthu

Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures

The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝ intensity(n), with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State

Copper in the Spotlight Elemental copper should, in principle, be a productive catalyst for the commercial preparation of propylene oxide; however, in practice, surface oxidation under industrial conditions quickly diminishes selectivity below a useful threshold. Marimuthu et al. (p. 1590) now show that irradiating the copper with visible light during the reaction excites surface plasmon resonances that lead to reduction of the oxide coating and restore selectivity. In situ visible light irradiation reverses the oxidative degradation of a copper catalyst, thereby enhancing its viability. Oxidation of functioning copper has restricted its applicability as a catalyst for commercially important epoxidation of propylene to form propylene oxide. Here, we report that steady-state selectivity in propylene epoxidation on copper (Cu) nanoparticles increases sharply when the catalyst is illuminated with visible light. The selectivity increase is accompanied by light-induced reduction of the surface Cu atoms, which is brought about by photoexcitation of the localized surface plasmon resonance (LSPR) of Cu. We discuss multiple mechanisms by which Cu LSPR weakens the Cu-O bonds, reducing Cu2O.

Catalytic and photocatalytic transformations on metal nanoparticles with targeted geometric and plasmonic properties.

Heterogeneous catalysis by metals was among the first enabling technologies that extensively relied on nanoscience. The early intersections of catalysis and nanoscience focused on the synthesis of catalytic materials with high surface to volume ratio. These synthesis strategies mainly involved the impregnation of metal salts on high surface area supports. This would usually yield quasi-spherical nanoparticles capped by low-energy surface facets, typically with closely packed metal atoms. These high density areas often function as the catalytically active surface sites. Unfortunately, strategies to control the functioning surface facet (i.e., the geometry of active sites that performs catalytic turnover) are rare and represent a significant challenge in our ability to fine-tune and optimize the reactive surfaces. Through recent developments in colloidal chemistry, chemists have been able to synthesize metallic nanoparticles of both targeted size and desired shape. This has opened new possibilities for the design of heterogeneous catalytic materials, since metal nanoparticles of different shapes are terminated with different surface facets. By controlling the surface facet exposed to reactants, we can start affecting the chemical transformations taking place on the metal particles and changing the outcome of catalytic processes. Controlling the size and shape of metal nanoparticles also allows us to control the optical properties of these materials. For example, noble metals nanoparticles (Au, Ag, Cu) interact with UV-vis light through an excitation of localized surface plasmon resonance (LSPR), which is highly sensitive to the size and shape of the nanostructures. This excitation is accompanied by the creation of short-lived energetic electrons on the surface of the nanostructure. We showed recently that these energetic electrons could drive photocatalytic transformations on these nanostructures. The photocatalytic, electron-driven processes on metal nanoparticles represent a new family of chemical transformations exhibiting fundamentally different behavior compared with phonon-driven thermal processes, potentially allowing selective bond activation. In this Account, we discuss both the impact of the shape of metal nanoparticles on the outcome of heterogeneous catalytic reactions and the direct, electron-driven photocatalysis on plasmonic metal nanostructures of noble metals. These two phenomena are important examples of taking advantage of physical properties of metal materials that are controlled at nanoscales to affect chemical transformations.

ENZYMATIC DEGRADATION OF POLY(SOYBEAN OIL-g-METHYL METHACRYLATE)

This study discusses grafting of methyl methacrylate units from thepolymeric soybean oil peroxide to produce poly(soybean oil-graft-methyl methacrylate) (PSO-g-PMMA). The degradation of this copolymer in solution was evaluated in the presence of different lipases, viz Candida rugosa (CR), Lipolase 100T (LP), Novozym 435 (N435) and Porcine pancreas (PP), at different temperatures The copolymer degraded by specific chain end scission and the mass fraction of the specific product evolved was determined The degradation was modeled using continuous distribution kinetics to determine the rate coefficients ofmenzymatic chain end scission and deactivation of the enzyme The enzymes, CR. LP and N435 exhibited maximum activity for the degradation of PSO-g-PMMA at 60 degrees C, while PP was most active at 50 degrees C. The thermal degradability of the copolymer, assessed by thermo-gravimetry, indicated that the activation energy of degradation of the copolymer was 154 kJ mol(-1), which was lesser than that of the PMMA homopolymer.