Transport and Interfacial Injection of d-Band Hot Holes Control Plasmonic Chemistry

Journal article

Harnessing nonequilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field with the potential to control photochemical reactions, particularly for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot-carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence among plasmon excitation, hot-carrier generation, transport, and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiency at the solid/liquid interface. Measuring the internal quantum efficiency of ultrathin (14–33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is limited by hot hole collection at the metal/electrolyte interface. Our solid- and liquid-state experimental approach, combined with ab initio simulations, demonstrates more efficient collection of high-energy d-band holes traveling in the [111] orientation, enhancing oxidation reactions on {111} surfaces. These findings establish new guidelines for optimizing plasmonic photocatalytic systems and optoelectronic devices

Authors: Kiani, F; Bowman, AR; Sabzehparvar, M; Karaman, CO; Sundararaman, R

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: ACS Energy Letters
• Volume: 8
• Issue: 10
• Pages: 4242-4250
• Publication date: 2023-09-19
• DOI: 10.1021/acsenergylett.3c01505
• EISSN: 2380-8195
• ISSN: 2380-8195
• Language: English
• Keywords: Nanotechnology; Catalysis; Optoelectronics; Plasmon; Photocatalysis; Chemistry; Materials science; Charge carrier; Heterojunction