Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

Lee, Seung-Hoon; Iglesias, Brandon; Everitt, Henry O.; Liu, Jie

doi:10.1039/d3nr00561e

Title: Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

Journal Article · Tue May 09 00:00:00 UTC 2023 · Nanoscale

DOI: https://doi.org/10.1039/d3nr00561e · OSTI ID:2425623

^[1];

^[2];

^[3];

^[1]

Duke Univ., Durham, NC (United States)
Reactwell, L.L.C. Houston, TX (United States)
Rice Univ., Houston, TX (United States). U.S. Army DEVCOM Army Research Laboratory-South; Duke Univ., Durham, NC (United States)

For the conversion of CO₂ into fuels and chemical feedstocks, hybrid gas/liquid-fed electrochemical flow reactors provide advantages in selectivity and production rates over traditional liquid phase reactors. However, fundamental questions remain about how to optimize conditions to produce desired products. Here, using an alkaline electrolyte to suppress hydrogen formation and a gas diffusion electrode catalyst composed of copper nanoparticles on carbon nanospikes, we investigate how hydrocarbon product selectivity in the CO₂ reduction reaction in hybrid reactors depends on three experimentally controllable parameters: (1) supply of dry or humidified CO₂ gas, (2) applied potential, and (3) electrolyte temperature. Changing from dry to humidified CO₂ dramatically alters product selectivity from C₂ products ethanol and acetic acid to ethylene and C₁ products formic acid and methane. Water vapor evidently influences product selectivity of reactions that occur on the gas-facing side of the catalyst by adding a source of protons that alters reaction pathways and intermediates.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0014664

OSTI ID:: 2425623

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 21 Vol. 15; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO ₂ Reduction Reaction Löwe, Armin; Rieg, Carolin; Hierlemann, Tim ChemElectroChem, Vol. 6, Issue 17 https://doi.org/10.1002/celc.201900872	journal	August 2019
Investigating Electrode Flooding in a Flowing Electrolyte, Gas‐Fed Carbon Dioxide Electrolyzer Leonard, McLain E.; Clarke, Lauren E.; Forner‐Cuenca, Antoni ChemSusChem, Vol. 13, Issue 2 https://doi.org/10.1002/cssc.201902547	journal	December 2019
High-Selectivity Electrochemical Conversion of CO ₂ to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode Song, Yang; Peng, Rui; Hensley, Dale K. ChemistrySelect, Vol. 1, Issue 19 https://doi.org/10.1002/slct.201601169	journal	September 2016
Electroreduction of CO2 on polycrystalline copper: Effect of temperature on product selectivity Ahn, Steven T.; Abu-Baker, Ismael; Palmore, G. Tayhas R. Catalysis Today, Vol. 288 https://doi.org/10.1016/j.cattod.2016.09.028	journal	June 2017
Fundamentals and Challenges of Electrochemical CO2 Reduction Using Two-Dimensional Materials Sun, Zhenyu; Ma, Tao; Tao, Hengcong Chem, Vol. 3, Issue 4 https://doi.org/10.1016/j.chempr.2017.09.009	journal	October 2017
Modulating Local CO2 Concentration as a General Strategy for Enhancing C−C Coupling in CO2 Electroreduction Tan, Ying Chuan; Lee, Kelvin Berm; Song, Hakhyeon Joule, Vol. 4, Issue 5 https://doi.org/10.1016/j.joule.2020.03.013	journal	May 2020
Electrolytic CO ₂ Reduction in a Flow Cell Weekes, David M.; Salvatore, Danielle A.; Reyes, Angelica Accounts of Chemical Research, Vol. 51, Issue 4 https://doi.org/10.1021/acs.accounts.8b00010	journal	March 2018
Effect of Humidity on C₁, C₂ Product Selectivity for CO₂ Reduction in a Hybrid Gas/Liquid Electrochemical Reactor Lee, Seung-Hoon; Song, Yang; Iglesias, Brandon ACS Applied Energy Materials, Vol. 5, Issue 8 https://doi.org/10.1021/acsaem.2c02226	journal	July 2022
Facet Dependence of CO ₂ Reduction Paths on Cu Electrodes Luo, Wenjia; Nie, Xiaowa; Janik, Michael J. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01967	journal	December 2015
Calculations of Product Selectivity in Electrochemical CO ₂ Reduction Hussain, Javed; Jónsson, Hannes; Skúlason, Egill ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.7b03308	journal	April 2018
Mechanism of CO ₂ Reduction at Copper Surfaces: Pathways to C ₂ Products Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03477	journal	January 2018
Role of H 2 O in CO 2 Electrochemical Reduction As Studied in a Water-in-Salt System Dong, Qi; Zhang, Xizi; He, Da ACS Central Science, Vol. 5, Issue 8 https://doi.org/10.1021/acscentsci.9b00519	journal	July 2019
Managing Hydration at the Cathode Enables Efficient CO ₂ Electrolysis at Commercially Relevant Current Densities Reyes, Angelica; Jansonius, Ryan P.; Mowbray, Benjamin A. W. ACS Energy Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsenergylett.0c00637	journal	April 2020
Computational Comparison of Late Transition Metal (100) Surfaces for the Electrocatalytic Reduction of CO to C ₂ Species Hanselman, Selwyn; Koper, Marc T. M.; Calle-Vallejo, Federico ACS Energy Letters, Vol. 3, Issue 5 https://doi.org/10.1021/acsenergylett.8b00326	journal	April 2018
High Rate, Selective, and Stable Electroreduction of CO ₂ to CO in Basic and Neutral Media Dinh, Cao-Thang; García de Arquer, F. Pelayo; Sinton, David ACS Energy Letters, Vol. 3, Issue 11 https://doi.org/10.1021/acsenergylett.8b01734	journal	October 2018
Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm Higgins, Drew; Hahn, Christopher; Xiang, Chengxiang ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02035	journal	December 2018
Introductory Guide to Assembling and Operating Gas Diffusion Electrodes for Electrochemical CO ₂ Reduction Liu, Kai; Smith, Wilson A.; Burdyny, Thomas ACS Energy Letters, Vol. 4, Issue 3 https://doi.org/10.1021/acsenergylett.9b00137	journal	February 2019
Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes Schouten, Klaas Jan P.; Qin, Zisheng; Pérez Gallent, Elena Journal of the American Chemical Society, Vol. 134, Issue 24 https://doi.org/10.1021/ja302668n	journal	June 2012
Understanding the Roadmap for Electrochemical Reduction of CO ₂ to Multi-Carbon Oxygenates and Hydrocarbons on Copper-Based Catalysts Zheng, Yao; Vasileff, Anthony; Zhou, Xianlong Journal of the American Chemical Society, Vol. 141, Issue 19 https://doi.org/10.1021/jacs.9b02124	journal	April 2019
Efficient Methane Electrosynthesis Enabled by Tuning Local CO ₂ Availability Wang, Xue; Xu, Aoni; Li, Fengwang Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b12445	journal	January 2020
Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction Kas, Recep; Hummadi, Khalid Khazzal; Kortlever, Ruud Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10748	journal	February 2016
Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on indium surfaces Ma, Wenchao; Xie, Shunji; Zhang, Xia-Guang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08805-x	journal	February 2019
Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption Li, Jun; Xu, Aoni; Li, Fengwang Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17499-5	journal	July 2020
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C. Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0450-y	journal	September 2019
Gas diffusion electrodes and membranes for CO2 reduction electrolysers Lees, Eric W.; Mowbray, Benjamin A. W.; Parlane, Fraser G. L. Nature Reviews Materials, Vol. 7, Issue 1 https://doi.org/10.1038/s41578-021-00356-2	journal	September 2021
High-rate electroreduction of carbon monoxide to multi-carbon products Jouny, Matthew; Luc, Wesley; Jiao, Feng Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0133-2	journal	August 2018
Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products Gao, Dunfeng; Arán-Ais, Rosa M.; Jeon, Hyo Sang Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0235-5	journal	March 2019
Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate Luc, Wesley; Fu, Xianbiao; Shi, Jianjian Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0269-8	journal	April 2019
Designing materials for electrochemical carbon dioxide recycling Ross, Michael B.; De Luna, Phil; Li, Yifan Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0306-7	journal	July 2019
Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C–C coupling over fluorine-modified copper Ma, Wenchao; Xie, Shunji; Liu, Tongtong Nature Catalysis, Vol. 3, Issue 6 https://doi.org/10.1038/s41929-020-0450-0	journal	April 2020
The effect of electrolyte composition on the electroreduction of CO ₂ to CO on Ag based gas diffusion electrodes Verma, Sumit; Lu, Xun; Ma, Sichao Physical Chemistry Chemical Physics, Vol. 18, Issue 10 https://doi.org/10.1039/C5CP05665A	journal	January 2016
Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO ₂ reduction electrocatalysts Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee Physical Chemistry Chemical Physics, Vol. 18, Issue 38 https://doi.org/10.1039/C6CP05287H	journal	January 2016
Modeling gas-diffusion electrodes for CO ₂ reduction Weng, Lien-Chun; Bell, Alexis T.; Weber, Adam Z. Physical Chemistry Chemical Physics, Vol. 20, Issue 25 https://doi.org/10.1039/C8CP01319E	journal	January 2018
CO ₂ reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions Burdyny, Thomas; Smith, Wilson A. Energy & Environmental Science, Vol. 12, Issue 5 https://doi.org/10.1039/C8EE03134G	journal	January 2019
Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO₂ reduction reaction on copper electrodes Gao, Shu-Ting; Xiang, Shi-Qin; Shi, Jun-Lin Physical Chemistry Chemical Physics, Vol. 22, Issue 17 https://doi.org/10.1039/C9CP06824D	journal	January 2020
Gas diffusion electrode design for electrochemical carbon dioxide reduction Nguyen, Tu N.; Dinh, Cao-Thang Chemical Society Reviews, Vol. 49, Issue 21 https://doi.org/10.1039/D0CS00230E	journal	January 2020
Strategies in catalysts and electrolyzer design for electrochemical CO ₂ reduction toward C ₂₊ products Fan, Lei; Xia, Chuan; Yang, Fangqi Science Advances, Vol. 6, Issue 8 https://doi.org/10.1126/sciadv.aay3111	journal	February 2020
CO ₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam Science, Vol. 360, Issue 6390 https://doi.org/10.1126/science.aas9100	journal	May 2018
What would it take for renewably powered electrosynthesis to displace petrochemical processes? De Luna, Phil; Hahn, Christopher; Higgins, Drew Science, Vol. 364, Issue 6438 https://doi.org/10.1126/science.aav3506	journal	April 2019
CO ₂ electrolysis to multicarbon products at activities greater than 1 A cm ⁻² García de Arquer, F. Pelayo; Dinh, Cao-Thang; Ozden, Adnan Science, Vol. 367, Issue 6478 https://doi.org/10.1126/science.aay4217	journal	February 2020
Recent Advances in the Catalyst Design and Mass Transport Control for the Electrochemical Reduction of Carbon Dioxide to Formate Alfath, Muhammad; Lee, Chan Woo Catalysts, Vol. 10, Issue 8 https://doi.org/10.3390/catal10080859	journal	August 2020

Similar Records

Separation of isoprene from biologically-derived gas streams

Journal Article · Wed Mar 09 00:00:00 UTC 2022 · Separation Science and Technology · OSTI ID:1905080

Klaehn, John R.; Orme, Christopher J.; Ginosar, Daniel M.

PROTOPLANETARY DISK STRUCTURE WITH GRAIN EVOLUTION: THE ANDES MODEL

Journal Article · Wed Mar 20 04:00:00 UTC 2013 · Astrophysical Journal · OSTI ID:22167594

Akimkin, V.; Wiebe, D.; Pavlyuchenkov, Ya.; +4 more

Electrolyte-Guided Design of Electroreductive CO Coupling on Copper Surfaces

Journal Article · Mon Aug 09 00:00:00 UTC 2021 · ACS Applied Energy Materials · OSTI ID:1828656

Akhade, Sneha A.; Jayathilake, Buddhinie S.; Weitzner, Stephen E.; +12 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction reaction
Chemistry
Materials Science
Physics
Science & Technology - Other Topics
electrochemical flow reactor
hybrid gas/liquid reactor
product selectivity
three-phase interface

Title: Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

Citation Formats

References (41)

Similar Records

Related Subjects