The Importance of Catalytic Effects in Hot-Electron-Driven Chemical Reactions
Hot electrons (HEs) represent out-of-equilibrium carriers that are capable of facilitating reactions which are inaccessible under conventional conditions. Despite the similarity of the HE process to catalysis, optimization strategies such as orbital alignment and adsorption kinetics have not received significant attention in enhancing the HE-driven reaction yield. Here, we investigate catalytic effects in HE-driven reactions using a compositional catalyst modification (CCM) approach. Through a top-down alloying process and systematic characterization, using electrochemical, photodegradation, and ultrafast spectroscopy, we are able to disentangle chemical effects from competing electronic phenomena. Correlation between reactant energetics and the HE reaction yield demonstrates the crucial role of orbital alignment in HE catalytic efficiency. Optimization of this parameter was found to enhance HE reaction efficiency 5-fold, paving the way for tailored design of HE-based catalysts for sustainable chemistry applications. Finally, our study unveils an emergent ordering effect in photocatalytic HE processes that imparts the catalyst with an unexpected polarization dependence.
Authors
- Ding‐Rui Chen (ORCID: https://orcid.org/0009-0005-9310-1381)
- Min-Chuan Shih
- Y.-S. Wang
- Ya‐Ping Hsieh (ORCID: https://orcid.org/0000-0002-6065-751X)
- Jan Plšek (ORCID: https://orcid.org/0000-0003-4706-0097)
- Martin Kalbáč (ORCID: https://orcid.org/0000-0001-9574-4368)
- Nicholas R. Glavin (ORCID: https://orcid.org/0000-0002-9447-7509)
- Yu‐Jung Lu (ORCID: https://orcid.org/0000-0002-3932-653X)
- Farheen Khurshid (ORCID: https://orcid.org/0000-0002-1371-6150)
- Jeyavelan Muthu (ORCID: https://orcid.org/0000-0001-7715-3628)
- Yen‐Yu Wang (ORCID: https://orcid.org/0000-0001-7696-8446)
- Drake Austin (ORCID: https://orcid.org/0000-0003-0178-3791)
- Mario Hofmann (ORCID: https://orcid.org/0000-0003-1946-2478)
Institutions
- United States Air Force Research Laboratory (US)
- National Taiwan University (TW)
- Wright-Patterson Air Force Base (US)
- Research Center for Applied Science, Academia Sinica (TW)
- Czech Academy of Sciences, J. Heyrovský Institute of Physical Chemistry (CZ)
- Institute of Atomic and Molecular Sciences, Academia Sinica (TW)
- Massachusetts Institute of Technology (US)
Publication Details
- Journal
- ACS Nano
- Published
- 2024-12-04
- DOI
- https://doi.org/10.1021/acsnano.4c12923
- Citations
- 3
- Primary Topic
- Advanced Photocatalysis Techniques
- Type
- article
- Field-Weighted Citation Impact
- 0.31
Funders
- Massachusetts Institute of Technology
- Grantová Agentura České Republiky
- Academia Sinica
- Akademie Věd České Republiky
- National Taiwan University
- National Science and Technology Council
- Air Force Office of Scientific Research
- Materials and Manufacturing Directorate