Doctor of Philosophy, Rice University (2022)
Ph.D., Rice University, Chemistry (2022)
B.S., Beijing Institute of Technology, Applied Physics (2017)
Jennifer Dionne, Postdoctoral Faculty Sponsor
Plasmonic Photocatalysis with Chemically and Spatially Specific Antenna-Dual Reactor Complexes
Plasmonic antenna-reactor photocatalysts have been shown to convert light efficiently to chemical energy. Virtually all chemical reactions mediated by such complexes to date, however, have involved relatively simple reactions that require only a single type of reaction site. Here, we investigate a planar Al nanodisk antenna with two chemically distinct and spatially separated active sites in the form of Pd and Fe nanodisks, fabricated in 90° and 180° trimer configurations. The photocatalytic reactions H2 + D2 → 2HD and NH3 + D2 → NH2D + HD were both investigated on these nanostructured complexes. While the H2-D2 exchange reaction showed an additive behavior for the linear (180°) nanodisk complex, the NH3 + D2 reaction shows a clear synergistic effect of the position of the reactor nanodisks relative to the central Al nanodisk antenna. This study shows that light-driven chemical reactions can be performed with both chemical and spatial control of the specific reaction steps, demonstrating precisely designed antennas with multiple reactors for tailored control of chemical reactions of increasing complexity.
View details for DOI 10.1021/acsnano.2c08191
View details for Web of Science ID 000866432500001
View details for PubMedID 36201312
Al@TiO2 Core-Shell Nanoparticles for Plasmonic Photocatalysis
2022; 16 (4): 5839-5850
Plasmon-induced photocatalysis is a topic of rapidly increasing interest, due to its potential for substantially lowering reaction barriers and temperatures and for increasing the selectivity of chemical reactions. Of particular interest for plasmonic photocatalysis are antenna-reactor nanoparticles and nanostructures, which combine the strong light-coupling of plasmonic nanostructures with reactors that enhance chemical specificity. Here, we introduce Al@TiO2 core-shell nanoparticles, combining earth-abundant Al nanocrystalline cores with TiO2 layers of tunable thickness. We show that these nanoparticles are active photocatalysts for the hot electron-mediated H2 dissociation reaction as well as for hot hole-mediated methanol dehydration. The wavelength dependence of the reaction rates suggests that the photocatalytic mechanism is plasmonic hot carrier generation with subsequent transfer of the hot carriers into the TiO2 layer. The Al@TiO2 antenna-reactor provides an earth-abundant solution for the future design of visible-light-driven plasmonic photocatalysts.
View details for DOI 10.1021/acsnano.1c10995
View details for Web of Science ID 000813107000001
View details for PubMedID 35293740