DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Reactor design and integration with product detection to accelerate screening of electrocatalysts for carbon dioxide reduction

Abstract

Identifying new catalyst materials for complex reactions such as the electrochemical reduction of CO2 poses substantial instrumentation challenges due to the need to integrate reactor control with electrochemical and analytical instrumentation. Performing accelerated screening to enable exploration of a broad span of catalyst materials poses additional challenges due to the long time scales associated with accumulation of reaction products and the detection of the reaction products with traditional separation-based analytical methods. The catalyst screening techniques that have been reported for combinatorial studies of (photo)electrocatalysts do not meet the needs of CO2 reduction catalyst research, prompting our development of a new electrochemical cell design and its integration to gas and liquid chromatography instruments. To enable rapid chromatography measurements while maintaining sensitivity to minor products, the electrochemical cell features low electrolyte and head space volumes compared to the catalyst surface area. Additionally, the cell is operated as a batch reactor with electrolyte recirculation to rapidly concentrate reaction products, which serves the present needs for rapidly detecting minor products and has additional implications for enabling product separations in industrial CO2 electrolysis systems. To maintain near-saturation of CO2 in aqueous electrolytes, we employ electrolyte nebulization through a CO2-rich headspace, achieving similar gas-liquid equilibration asmore » vigorous CO2 bubbling but without gas flow. The instrument is demonstrated with a series of electrochemical experiments on an Au-Pd combinatorial library, revealing non-monotonic variations in product distribution with respect to catalyst composition. The highly integrated analytical electrochemistry system is engineered to enable automation for rapid catalyst screening as well as deployment for a broad range of electrochemical reactions where product distribution is critical to the assessment of catalyst performance.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]
  1. California Institute of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1610788
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Review of Scientific Instruments
Additional Journal Information:
Journal Volume: 89; Journal Issue: 12; Journal ID: ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION; Instruments & Instrumentation; Physics; Gas-liquid chromatography; Catalysts and; Catalysis; Chemical compounds; Electrolysis; Electrochemistry; Reactor control

Citation Formats

Jones, Ryan R., Wang, Yu, Lai, Yungchieh, Shinde, Aniketa, and Gregoire, John M. Reactor design and integration with product detection to accelerate screening of electrocatalysts for carbon dioxide reduction. United States: N. p., 2018. Web. doi:10.1063/1.5049704.
Jones, Ryan R., Wang, Yu, Lai, Yungchieh, Shinde, Aniketa, & Gregoire, John M. Reactor design and integration with product detection to accelerate screening of electrocatalysts for carbon dioxide reduction. United States. https://doi.org/10.1063/1.5049704
Jones, Ryan R., Wang, Yu, Lai, Yungchieh, Shinde, Aniketa, and Gregoire, John M. Wed . "Reactor design and integration with product detection to accelerate screening of electrocatalysts for carbon dioxide reduction". United States. https://doi.org/10.1063/1.5049704. https://www.osti.gov/servlets/purl/1610788.
@article{osti_1610788,
title = {Reactor design and integration with product detection to accelerate screening of electrocatalysts for carbon dioxide reduction},
author = {Jones, Ryan R. and Wang, Yu and Lai, Yungchieh and Shinde, Aniketa and Gregoire, John M.},
abstractNote = {Identifying new catalyst materials for complex reactions such as the electrochemical reduction of CO2 poses substantial instrumentation challenges due to the need to integrate reactor control with electrochemical and analytical instrumentation. Performing accelerated screening to enable exploration of a broad span of catalyst materials poses additional challenges due to the long time scales associated with accumulation of reaction products and the detection of the reaction products with traditional separation-based analytical methods. The catalyst screening techniques that have been reported for combinatorial studies of (photo)electrocatalysts do not meet the needs of CO2 reduction catalyst research, prompting our development of a new electrochemical cell design and its integration to gas and liquid chromatography instruments. To enable rapid chromatography measurements while maintaining sensitivity to minor products, the electrochemical cell features low electrolyte and head space volumes compared to the catalyst surface area. Additionally, the cell is operated as a batch reactor with electrolyte recirculation to rapidly concentrate reaction products, which serves the present needs for rapidly detecting minor products and has additional implications for enabling product separations in industrial CO2 electrolysis systems. To maintain near-saturation of CO2 in aqueous electrolytes, we employ electrolyte nebulization through a CO2-rich headspace, achieving similar gas-liquid equilibration as vigorous CO2 bubbling but without gas flow. The instrument is demonstrated with a series of electrochemical experiments on an Au-Pd combinatorial library, revealing non-monotonic variations in product distribution with respect to catalyst composition. The highly integrated analytical electrochemistry system is engineered to enable automation for rapid catalyst screening as well as deployment for a broad range of electrochemical reactions where product distribution is critical to the assessment of catalyst performance.},
doi = {10.1063/1.5049704},
journal = {Review of Scientific Instruments},
number = 12,
volume = 89,
place = {United States},
year = {Wed Dec 26 00:00:00 EST 2018},
month = {Wed Dec 26 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Electrochemical Photolysis of Water at a Semiconductor Electrode
journal, July 1972

  • Fujishima, Akira; Honda, Kenichi
  • Nature, Vol. 238, Issue 5358, p. 37-38
  • DOI: 10.1038/238037a0

One-Pot Soft-Template Synthesis of Nanostructured Copper-Supported Mesoporous Carbon FDU-15 Electrocatalysts for Efficient CO 2 Reduction
journal, April 2018

  • Şahin, Nihat Ege; Comminges, Clément; Le Valant, Anthony
  • ChemPhysChem, Vol. 19, Issue 11
  • DOI: 10.1002/cphc.201701352

High efficiency electrochemical reduction of CO 2 beyond the two-electron transfer pathway on grain boundary rich ultra-small SnO 2 nanoparticles
journal, January 2018

  • Liang, Chenglu; Kim, Byoungsu; Yang, Shize
  • Journal of Materials Chemistry A, Vol. 6, Issue 22
  • DOI: 10.1039/c8ta01367e

Correction to “Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO”
journal, July 2017

  • Zhu, Wenlei; Michalsky, Ronald; Metin, Önder
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b05685

Electrochemical Reduction of Carbon Dioxide at Various Metal Electrodes in Aqueous Potassium Hydrogen Carbonate Solution
journal, September 1990

  • Noda, Hidetomo; Ikeda, Shoichiro; Oda, Yoshiyuki
  • Bulletin of the Chemical Society of Japan, Vol. 63, Issue 9, p. 2459-2462
  • DOI: 10.1246/bcsj.63.2459

Scanning droplet cell for high throughput electrochemical and photoelectrochemical measurements
journal, February 2013

  • Gregoire, John M.; Xiang, Chengxiang; Liu, Xiaonao
  • Review of Scientific Instruments, Vol. 84, Issue 2
  • DOI: 10.1063/1.4790419

Combinatorial thin film composition mapping using three dimensional deposition profiles
journal, March 2015

  • Suram, Santosh K.; Zhou, Lan; Becerra-Stasiewicz, Natalie
  • Review of Scientific Instruments, Vol. 86, Issue 3
  • DOI: 10.1063/1.4914466

A New Approach for Simultaneous DEMS and EQCM: Electro-oxidation of Adsorbed CO on Pt and Pt-Ru
journal, January 1999

  • Jusys, Z.
  • Journal of The Electrochemical Society, Vol. 146, Issue 3
  • DOI: 10.1149/1.1391726

Coupling of a high throughput microelectrochemical cell with online multielemental trace analysis by ICP-MS
journal, December 2011

  • Klemm, Sebastian O.; Topalov, Angel A.; Laska, Claudius A.
  • Electrochemistry Communications, Vol. 13, Issue 12
  • DOI: 10.1016/j.elecom.2011.10.017

On-line mass spectrometry system for measurements at single-crystal electrodes in hanging meniscus configuration
journal, August 2006

  • Wonders, A. H.; Housmans, T. H. M.; Rosca, V.
  • Journal of Applied Electrochemistry, Vol. 36, Issue 11
  • DOI: 10.1007/s10800-006-9173-4

Screening of material libraries for electrochemical CO2 reduction catalysts – Improving selectivity of Cu by mixing with Co
journal, November 2016


New on-line mass spectrometer system designed for platinum-single crystal electrode and electroreduction of acetylene
journal, July 1994

  • Gao, Yunzhi; Tsuji, Hideto; Hattori, Hideshi
  • Journal of Electroanalytical Chemistry, Vol. 372, Issue 1-2
  • DOI: 10.1016/0022-0728(93)03291-v

Boosting the performance of Cu2O photocathodes for unassisted solar water splitting devices
journal, May 2018


Mathematical Modeling of a Cation-Exchange Membrane Containing Two Cations
journal, January 2008

  • Delacourt, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 155, Issue 11, p. B1210-B1217
  • DOI: 10.1149/1.2977960

Electrochemical Reduction of CO 2 at Multi-Metallic Interfaces
journal, April 2018


Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell
journal, May 2008

  • Barton, Emily E.; Rampulla, David M.; Bocarsly, Andrew B.
  • Journal of the American Chemical Society, Vol. 130, Issue 20
  • DOI: 10.1021/ja0776327

Combinatorial and High-Throughput Screening of Materials Libraries: Review of State of the Art
journal, August 2011

  • Potyrailo, Radislav; Rajan, Krishna; Stoewe, Klaus
  • ACS Combinatorial Science, Vol. 13, Issue 6
  • DOI: 10.1021/co200007w

Combinatorial and high-throughput approaches in polymer science
journal, December 2004

  • Zhang, Huiqi; Hoogenboom, Richard; Meier, Michael A. R.
  • Measurement Science and Technology, Vol. 16, Issue 1
  • DOI: 10.1088/0957-0233/16/1/027

Surface-Morphology-Dependent Electrolyte Effects on Gold-Catalyzed Electrochemical CO 2 Reduction
journal, October 2017

  • Kim, Haeri; Park, Hyun Seo; Hwang, Yun Jeong
  • The Journal of Physical Chemistry C, Vol. 121, Issue 41
  • DOI: 10.1021/acs.jpcc.7b06286

Differential Electrochemical Mass Spectroscopy (DEMS) - a New Method for the Study of Electrode Processes
journal, January 1984

  • Wolter, O.; Heitbaum, J.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 88, Issue 1
  • DOI: 10.1002/bbpc.19840880103

Effect of Cations on the Electrochemical Conversion of CO2 to CO
journal, November 2012

  • Thorson, M. R.; Siil, K. I.; Kenis, P. J. A.
  • Journal of the Electrochemical Society, Vol. 160, Issue 1, p. F69-F74
  • DOI: 10.1149/2.052301jes

Measuring Electrocatalytic Activity on a Local Scale with Scanning Differential Electrochemical Mass Spectrometry
journal, January 2003

  • Jambunathan, K.; Hillier, A. C.
  • Journal of The Electrochemical Society, Vol. 150, Issue 6
  • DOI: 10.1149/1.1570823

Direct Observation of the Local Reaction Environment during the Electrochemical Reduction of CO 2
journal, April 2018

  • Clark, Ezra L.; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 140, Issue 22
  • DOI: 10.1021/jacs.8b04058

Electrolytic CO 2 Reduction in a Flow Cell
journal, March 2018

  • Weekes, David M.; Salvatore, Danielle A.; Reyes, Angelica
  • Accounts of Chemical Research, Vol. 51, Issue 4
  • DOI: 10.1021/acs.accounts.8b00010

Importance of Ag–Cu Biphasic Boundaries for Selective Electrochemical Reduction of CO 2 to Ethanol
journal, November 2017


New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012

  • Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21234j

Coupling of a scanning flow cell with online electrochemical mass spectrometry for screening of reaction selectivity
journal, October 2014

  • Grote, Jan-Philipp; Zeradjanin, Aleksandar R.; Cherevko, Serhiy
  • Review of Scientific Instruments, Vol. 85, Issue 10
  • DOI: 10.1063/1.4896755

Differential Electrochemical Mass Spectrometer Cell Design for Online Quantification of Products Produced during Electrochemical Reduction of CO 2
journal, July 2015


Differential electrochemical mass spectrometry
journal, December 2004


Combinatorial and High-Throughput Development of Sensing Materials:  The First 10 Years
journal, February 2008

  • Potyrailo, Radislav A.; Mirsky, Vladimir M.
  • Chemical Reviews, Vol. 108, Issue 2
  • DOI: 10.1021/cr068127f

Selective Electrochemical Reduction of CO 2 to Ethylene on Nanopores-Modified Copper Electrodes in Aqueous Solution
journal, September 2017

  • Peng, Yuecheng; Wu, Tian; Sun, Libo
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 38
  • DOI: 10.1021/acsami.7b10421

Works referencing / citing this record:

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO 2 by Molecular Catalysts
journal, May 2019

  • Elouarzaki, Kamal; Kannan, Vishvak; Jose, Vishal
  • Advanced Energy Materials, Vol. 9, Issue 24
  • DOI: 10.1002/aenm.201900090