Harvesting Localized Plasmons on Noble Metal Nanostructures for Efficient Electrochemical and Photochemical Reactions
Abstract
A comprehensive investigation to realize the implications of a nanophotonic phenomenon of localized surface plasmon resonance (LSPR) for improving the efficiency of the charge transfers across electrochemical and photochemical interfaces is proposed. This study will specifically explore the utilization of hot carriers, generated by LSPR directly on metallic nanostructured electrocatalysts, by coupling with charge transfers across an electrochemical interface. In addition, we aim to significantly improve absorption cross-section and solar-bandwidth utilization of photocatalyst by efficiently harvesting and steering hot carriers from metallic nanostructures and to the adjacent semiconductor, respectively. The following scientific objectives have been conceived for this purpose: a) Design of novel plasmonic structures with broader band-width utilization and enhanced absorption cross-section to efficiently harvest solar energy, b) Development of extended choice of noble metals and their support materials for LSPR applications in photoelectrochemical systems, c) Fundamental understanding of time-resolved processes associated with LSPR induced hot-carriers and d) Experimental realization and quantification of LSPR promoted charge-transfers during photoelectrochemical conversions. An interdisciplinary approach comprising design, synthesis, and characterization efforts, in combination with theoretical calculations, modeling, simulations, advanced spectroscopic tools will be employed. Specifically, the following scientific approaches are proposed for this purpose: 1) Model and design of higher-order plasmonic modes having periodic arrays with multi-layer structures, 2) Development of noble metal nanostructures beyond Au and Ag (Pt, Pd, Cu, Pb), nanoalloys formed thereof: Pt-Cu, Pt-Pd, Pt-Au, Cu-Ag, etc.; and various supporting nanomaterials such as semiconductors, insulators, ceramics, metal oxides, carbon, graphene, etc. 3) Use of optical pump-probe measurements to study ultrafast carrier dynamics, life-times associated photo-generated hot-carriers and their mutual interactions and 4) To implement in-situ or operando-based plasmon enhanced Vibrational (Raman & FTIR) and X-ray absorption spectroscopies for experimental realization of LSPR promoted charge-transfers. This fundamental understanding of these key processes associated with optimization and implication of LSPR in extend choice of materials likely opens a new horizon in the field of solar-electrochemical energy conversion. Moreover, these materials and methods can be extended to develop solar driven heterogenous catalysts for gas-phase reactions, especially when activation energy is too large to overcome using thermally induced processes.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Mar 18, 2019
- Source ID
- W911NF1910164
Entities
People
- Sanjeev Mukerjee
Organizations
- Army Contracting Command
- Northeastern University
- United States Army