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Title: Infrared Nanospectroscopy at the Graphene–Electrolyte Interface

Abstract

We present a new methodology that enables studies of the molecular structure of graphene-liquid interfaces with nanoscale spatial resolution. It is based on Fourier transform infrared nanospectroscopy (nano-FTIR), where the infrared (IR) field is plasmonically enhanced near the tip apex of an atomic force microscope (AFM). The graphene seals a liquid electrolyte reservoir while acting also as a working electrode. The photon transparency of graphene enables IR spectroscopy studies of its interface with liquids, including water, propylene carbonate, and aqueous ammonium sulfate electrolyte solutions. Here, we illustrate the method by comparing IR spectra obtained by nano-FTIR and attenuated total reflection (which has a detection depth of a few microns) demonstrating that the nano-FTIR method makes it possible to determine changes in speciation and ion concentration in the electric double and diffuse layers as a function of bias.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [3];  [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1580901
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 19; Journal Issue: 8; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; SNOM; graphene; solid−liquid interface; electrical double layer; near-field; nano-FTIR

Citation Formats

Lu, Yi-Hsien, Larson, Jonathan M., Baskin, Artem, Zhao, Xiao, Ashby, Paul D., Prendergast, David, Bechtel, Hans A., Kostecki, Robert, and Salmeron, Miquel. Infrared Nanospectroscopy at the Graphene–Electrolyte Interface. United States: N. p., 2019. Web. doi:10.1021/acs.nanolett.9b01897.
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Lu, Yi-Hsien, Larson, Jonathan M., Baskin, Artem, Zhao, Xiao, Ashby, Paul D., Prendergast, David, Bechtel, Hans A., Kostecki, Robert, & Salmeron, Miquel. Infrared Nanospectroscopy at the Graphene–Electrolyte Interface. United States. https://doi.org/10.1021/acs.nanolett.9b01897
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Lu, Yi-Hsien, Larson, Jonathan M., Baskin, Artem, Zhao, Xiao, Ashby, Paul D., Prendergast, David, Bechtel, Hans A., Kostecki, Robert, and Salmeron, Miquel. Mon . "Infrared Nanospectroscopy at the Graphene–Electrolyte Interface". United States. https://doi.org/10.1021/acs.nanolett.9b01897. https://www.osti.gov/servlets/purl/1580901.
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@article{osti_1580901,
title = {Infrared Nanospectroscopy at the Graphene–Electrolyte Interface},
author = {Lu, Yi-Hsien and Larson, Jonathan M. and Baskin, Artem and Zhao, Xiao and Ashby, Paul D. and Prendergast, David and Bechtel, Hans A. and Kostecki, Robert and Salmeron, Miquel},
abstractNote = {We present a new methodology that enables studies of the molecular structure of graphene-liquid interfaces with nanoscale spatial resolution. It is based on Fourier transform infrared nanospectroscopy (nano-FTIR), where the infrared (IR) field is plasmonically enhanced near the tip apex of an atomic force microscope (AFM). The graphene seals a liquid electrolyte reservoir while acting also as a working electrode. The photon transparency of graphene enables IR spectroscopy studies of its interface with liquids, including water, propylene carbonate, and aqueous ammonium sulfate electrolyte solutions. Here, we illustrate the method by comparing IR spectra obtained by nano-FTIR and attenuated total reflection (which has a detection depth of a few microns) demonstrating that the nano-FTIR method makes it possible to determine changes in speciation and ion concentration in the electric double and diffuse layers as a function of bias.},
doi = {10.1021/acs.nanolett.9b01897},
journal = {Nano Letters},
number = 8,
volume = 19,
place = {United States},
year = {Mon Jul 15 00:00:00 EDT 2019},
month = {Mon Jul 15 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.nanolett.9b01897
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Cited by: 36 works
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Figures / Tables:

Figure 1 Figure 1: (a) Schematic of our graphene-capped liquid cell design with a cross-sectional view. A cavity in the body center is the liquid electrolyte reservoir. A Pt counter electrode is fed through the cell wall. The cell is sealed by a Si chip covered with a 50 nm thick perforatedmore » silicon nitride (Si3N4) membrane, coated with gold (~ 20 nm) and capped with graphene. The holes have diameters ranging from hundreds of nm to m. (b) AFM image showing a region of a graphene-covered hole array (500 nm diameter). (c) Raman spectrum of graphene shows the characteristic peaks of monolayer graphene. (d) Schematic of a single graphene-capped hole with a tip apex on top, showing the incident and scattered IR beams.« less
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