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Title: Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering

Abstract

Porous, high-surface-area electrode architectures are described that allow structural characterization of interfacial amorphous thin films with high spatial resolution under device-relevant functional electrochemical conditions using high-energy X-ray (>50 keV) scattering and pair distribution function (PDF) analysis. Porous electrodes were fabricated from glass-capillary array membranes coated with conformal transparent conductive oxide layers, consisting of either a 40 nm–50 nm crystalline indium tin oxide or a 100 nm–150 nm-thick amorphous indium zinc oxide deposited by atomic layer deposition. These porous electrodes solve the problem of insufficient interaction volumes for catalyst thin films in two-dimensional working electrode designs and provide sufficiently low scattering backgrounds to enable high-resolution signal collection from interfacial thin-film catalysts. For example, PDF measurements were readily obtained with 0.2 Å spatial resolution for amorphous cobalt oxide films with thicknesses down to 60 nm when deposited on a porous electrode with 40 µm-diameter pores. This level of resolution resolves the cobaltate domain size and structure, the presence of defect sites assigned to the domain edges, and the changes in fine structure upon redox state change that are relevant to quantitative structure–function modeling. The results suggest the opportunity to leverage the porous, electrode architectures for PDF analysis of nanometre-scale surface-supported molecular catalysts.more » In addition, a compact 3D-printed electrochemical cell in a three-electrode configuration is described which is designed to allow for simultaneous X-ray transmission and electrolyte flow through the porous working electrode.« less

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [7]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States). Argonne Northwestern Solar Energy Research (ANSER) Center and Northwestern-Argonne Inst. of Science and Engineering; Argonne National Lab. (ANL), Lemont, IL (United States). Materials Science Div. and Chemical Sciences and Engineering Div.
  2. Seoul National Univ., Gwanak-gu (South Korea). Nano Fabrication Laboratory, Research Institute of Advanced Materials, Department of Materials Science and Engineering
  3. Argonne National Lab. (ANL), Lemont, IL (United States). Materials Science Div.; Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  4. Argonne National Lab. (ANL), Lemont, IL (United States). Materials Science Div.; Korea Institute of Science and Technology (KIST), Seoul (Korea)
  5. Argonne National Lab. (ANL), Lemont, IL (United States). X-ray Science Div.
  6. Argonne National Lab. (ANL), Lemont, IL (United States)
  7. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Div.
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1575070
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Synchrotron Radiation (Online)
Additional Journal Information:
Journal Name: Journal of Synchrotron Radiation (Online); Journal Volume: 26; Journal Issue: 5; Journal ID: ISSN 1600-5775
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; atomic layer deposition; catalysts; electrochemistry; electrode architectures; high-energy X-ray scattering; pair distribution functions; ultra-thin films

Citation Formats

Kwon, Gihan, Cho, Yeong -Ho, Kim, Ki -Bum, Emery, Jonathan D., Kim, In Soo, Zhang, Xiaoyi, Martinson, Alex B. F., and Tiede, Davd M. Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering. United States: N. p., 2019. Web. doi:10.1107/s1600577519007240.
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Kwon, Gihan, Cho, Yeong -Ho, Kim, Ki -Bum, Emery, Jonathan D., Kim, In Soo, Zhang, Xiaoyi, Martinson, Alex B. F., & Tiede, Davd M. Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering. United States. doi:10.1107/s1600577519007240.
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Kwon, Gihan, Cho, Yeong -Ho, Kim, Ki -Bum, Emery, Jonathan D., Kim, In Soo, Zhang, Xiaoyi, Martinson, Alex B. F., and Tiede, Davd M. Fri . "Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering". United States. doi:10.1107/s1600577519007240. https://www.osti.gov/servlets/purl/1575070.
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@article{osti_1575070,
title = {Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering},
author = {Kwon, Gihan and Cho, Yeong -Ho and Kim, Ki -Bum and Emery, Jonathan D. and Kim, In Soo and Zhang, Xiaoyi and Martinson, Alex B. F. and Tiede, Davd M.},
abstractNote = {Porous, high-surface-area electrode architectures are described that allow structural characterization of interfacial amorphous thin films with high spatial resolution under device-relevant functional electrochemical conditions using high-energy X-ray (>50 keV) scattering and pair distribution function (PDF) analysis. Porous electrodes were fabricated from glass-capillary array membranes coated with conformal transparent conductive oxide layers, consisting of either a 40 nm–50 nm crystalline indium tin oxide or a 100 nm–150 nm-thick amorphous indium zinc oxide deposited by atomic layer deposition. These porous electrodes solve the problem of insufficient interaction volumes for catalyst thin films in two-dimensional working electrode designs and provide sufficiently low scattering backgrounds to enable high-resolution signal collection from interfacial thin-film catalysts. For example, PDF measurements were readily obtained with 0.2 Å spatial resolution for amorphous cobalt oxide films with thicknesses down to 60 nm when deposited on a porous electrode with 40 µm-diameter pores. This level of resolution resolves the cobaltate domain size and structure, the presence of defect sites assigned to the domain edges, and the changes in fine structure upon redox state change that are relevant to quantitative structure–function modeling. The results suggest the opportunity to leverage the porous, electrode architectures for PDF analysis of nanometre-scale surface-supported molecular catalysts. In addition, a compact 3D-printed electrochemical cell in a three-electrode configuration is described which is designed to allow for simultaneous X-ray transmission and electrolyte flow through the porous working electrode.},
doi = {10.1107/s1600577519007240},
journal = {Journal of Synchrotron Radiation (Online)},
number = 5,
volume = 26,
place = {United States},
year = {2019},
month = {8}
}
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DOI:  10.1107/s1600577519007240
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