Swearer, Dayne F. and Gottheim, Samuel and Simmons, Jay G. and Phillips, Dane J. and Kale, Matthew J. and McClain, Michael J. and Christopher, Phillip and Halas, Naomi J. and Everitt, Henry O. (2018) Monitoring Chemical Reactions with Terahertz Rotational Spectroscopy. ACS Photonics, 5 (8). pp. 3097-3106. ISSN 2330-4022. https://resolver.caltech.edu/CaltechAUTHORS:20180521-075659625
![[img]](https://authors.library.caltech.edu/style/images/fileicons/application_pdf.png) |
PDF (ACS AuthorChoice)
- Published Version
See Usage Policy. 3177Kb |
|
PDF (Additional details regarding materials and experimental methods; description of the quantification procedure and experimental calibration curves, description of the limits of detection, and supplementary figures)
- Supplemental Material
See Usage Policy. 756Kb |
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180521-075659625
Abstract
Rotational spectroscopy is introduced as a new in situ method for monitoring gas-phase reactants and products during chemical reactions. Exploiting its unambiguous molecular recognition specificity and extraordinary detection sensitivity, rotational spectroscopy at terahertz frequencies was used to monitor the decomposition of carbonyl sulfide (OCS) over an aluminum nanocrystal (AlNC) plasmonic photocatalyst. The intrinsic surface oxide on AlNCs is discovered to have a large number of strongly basic sites that are effective for mediating OCS decomposition. Spectroscopic monitoring revealed two different photothermal decomposition pathways for OCS, depending on the absence or presence of H_2O. The strength of rotational spectroscopy is witnessed through its ability to detect and distinguish isotopologues of the same mass from an unlabeled OCS precursor at concentrations of <1 nanomolar or partial pressures of <10 μTorr. These attributes recommend rotational spectroscopy as a compelling alternative for monitoring gas-phase chemical reactants and products in real time.
| Item Type: | Article | ||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Related URLs: |
| ||||||||||||||
| ORCID: |
| ||||||||||||||
| Additional Information: | © 2018 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: March 16, 2018; Published: May 18, 2018. The authors thank C. Neese and M. Reish for discussions regarding rotational spectroscopy, J. Yang, A. Alabastri, and P. Nordlander for discussions regarding photothermal heating of the Al NCs in vacuo, and Hossein Robatjazi for the instrument schematic in Figure 1a. This work was funded by the Air Force Office of Scientific Research Multidisciplinary Research Program of the University Research Initiative (AFOSR MURI FA9550-15-1-0022), the Army Research Office (MURI W911NF-12-1-0407), Defense Threat Reduction Agency (HDTRA 1-16-1-0042), the Army Aviation and Missile RD&E Center In-house Laboratory Innovative Research program, and the Welch Foundation under grant C-1220 (N.J.H.). D.F.S. acknowledges the National Science Foundation for a Graduate Research Fellowship under grant no. 1450681. Author Contributions: The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Author Contributions: D. F. Swearer and S. Gottheim contributed equally. The authors declare no competing financial interest. | ||||||||||||||
| Funders: |
| ||||||||||||||
| Subject Keywords: | plasmonics, photocatalysis, rotational spectroscopy, carbonyl sulfide, aluminum nanocrystals | ||||||||||||||
| Issue or Number: | 8 | ||||||||||||||
| Record Number: | CaltechAUTHORS:20180521-075659625 | ||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180521-075659625 | ||||||||||||||
| Official Citation: | Monitoring Chemical Reactions with Terahertz Rotational Spectroscopy. Dayne F. Swearer, Samuel Gottheim, Jay G. Simmons, Dane J. Phillips, Matthew J. Kale, Michael J. McClain, Phillip Christopher, Naomi J. Halas, and Henry O. Everitt. ACS Photonics 2018 5 (8), 3097-3106. DOI: 10.1021/acsphotonics.8b00342 | ||||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
| ID Code: | 86487 | ||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||
| Deposited By: | Tony Diaz | ||||||||||||||
| Deposited On: | 21 May 2018 16:03 | ||||||||||||||
| Last Modified: | 03 Oct 2019 19:44 |
Repository Staff Only: item control page
