Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates

Skafte, Theis L.; Guan, Zixuan; Machala, Michael L.; Gopal, Chirranjeevi B.; Monti, Matteo; Martinez, Lev; Stamate, Eugen; Sanna, Simone; Garrido Torres, Jose A.; Crumlin, Ethan J.; García-Melchor, Max; Bajdich, Michal; Chueh, William C.; Graves, Christopher

doi:10.1038/s41560-019-0457-4

Title: Selective high-temperature CO₂ electrolysis enabled by oxidized carbon intermediates

Journal Article · Mon Sep 16 00:00:00 EDT 2019 · Nature Energy

DOI:https://doi.org/10.1038/s41560-019-0457-4· OSTI ID:1577318

^[1]; Guan, Zixuan ^[2];

^[2];

^[2]; Monti, Matteo ^[2];

^[3];

^[4];

^[5];

^[6];

^[4];

^[2];

^[1]

Technical Univ. of Denmark, Roskilde (Denmark); Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., Stanford, CA (United States)
Technical Univ. of Denmark, Roskilde (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Trinity College, Dublin (Ireland)

High-temperature CO₂ electrolysers offer exceptionally efficient storage of renewable electricity in the form of CO and other chemical fuels, but conventional electrodes catalyse destructive carbon deposition. Ceria catalysts are known carbon inhibitors for fuel cell (oxidation) reactions; however, for more severe electrolysis (reduction) conditions, catalyst design strategies remain unclear. In this study, we establish the inhibition mechanism on ceria and show selective CO₂ to CO conversion well beyond the thermodynamic carbon deposition threshold. Operando X-ray photoelectron spectroscopy during CO₂ electrolysis—using thin-film model electrodes consisting of samarium-doped ceria, nickel and/or yttria-stabilized zirconia—together with density functional theory modelling, reveal the crucial role of oxidized carbon intermediates in preventing carbon build-up. Using these insights, we demonstrate stable electrochemical CO₂ reduction with a scaled-up 16 cm² ceria-based solid-oxide cell under conditions that rapidly destroy a nickel-based cell, leading to substantially improved device lifetime.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1577318

Journal Information:: Nature Energy, Vol. 4, Issue 10; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 55 works

Citation information provided by
Web of Science

References (59)

Net-zero emissions energy systems Davis, Steven J.; Lewis, Nathan S.; Shaner, Matthew Science, Vol. 360, Issue 6396 https://doi.org/10.1126/science.aas9793	journal	June 2018
Atomic-scale imaging of carbon nanofibre growth Helveg, Stig; López-Cartes, Carlos; Sehested, Jens Nature, Vol. 427, Issue 6973 https://doi.org/10.1038/nature02278	journal	January 2004
Photoelectron spectroscopy under ambient pressure and temperature conditions Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2 https://doi.org/10.1016/j.nima.2008.12.155	journal	March 2009
Industrial scale experience on steam reforming of CO 2 -rich gas Mortensen, Peter Mølgaard; Dybkjær, Ib Applied Catalysis A: General, Vol. 495 https://doi.org/10.1016/j.apcata.2015.02.022	journal	April 2015
Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan Journal of Power Sources, Vol. 373 https://doi.org/10.1016/j.jpowsour.2017.10.097	journal	January 2018
A direct-methane fuel cell with a ceria-based anode Murray, E. Perry; Tsai, T.; Barnett, S. A. Nature, Vol. 400, Issue 6745 https://doi.org/10.1038/23220	journal	August 1999
Oxidation stages of Ni electrodes in solid oxide fuel cell environments El Gabaly, Farid; McCarty, Kevin F.; Bluhm, Hendrik Physical Chemistry Chemical Physics, Vol. 15, Issue 21 https://doi.org/10.1039/c3cp50366f	journal	January 2013
New model for electron‐impact ionization cross sections of molecules Hwang, W.; Kim, Y. ‐K.; Rudd, M. E. The Journal of Chemical Physics, Vol. 104, Issue 8 https://doi.org/10.1063/1.471116	journal	February 1996
In Situ Probing of the Mechanisms of Coking Resistance on Catalyst-Modified Anodes for Solid Oxide Fuel Cells Li, Xiaxi; Liu, Mingfei; Lai, Samson Y. Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm503852v	journal	January 2015
Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS) Czekaj, Izabela; Loviat, Francois; Raimondi, Fabio Applied Catalysis A: General, Vol. 329 https://doi.org/10.1016/j.apcata.2007.06.027	journal	October 2007
Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO ₂ Electrolysis Investigated by Operando Photoelectron Spectroscopy Opitz, Alexander K.; Nenning, Andreas; Rameshan, Christoph ACS Applied Materials & Interfaces, Vol. 9, Issue 41 https://doi.org/10.1021/acsami.7b10673	journal	October 2017
A Raman spectroscopic study of the carbon deposition mechanism on Ni/CGO electrodes during CO/CO ₂ electrolysis Duboviks, V.; Maher, R. C.; Kishimoto, M. Phys. Chem. Chem. Phys., Vol. 16, Issue 26 https://doi.org/10.1039/C4CP01503G	journal	January 2014
Carbon deposition on Ni/YSZ anodes exposed to CO/H2 feeds Alzate-Restrepo, Vanesa; Hill, Josephine M. Journal of Power Sources, Vol. 195, Issue 5 https://doi.org/10.1016/j.jpowsour.2009.09.014	journal	March 2010
High electrochemical activity of the oxide phase in model ceria–Pt and ceria–Ni composite anodes Chueh, William C.; Hao, Yong; Jung, WooChul Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3184	journal	December 2011
Threshold catalytic onset of carbon formation on CeO ₂ during CO ₂ electrolysis: mechanism and inhibition Wang, Jiayue; Bishop, Sean R.; Sun, Lixin Journal of Materials Chemistry A, Vol. 7, Issue 25 https://doi.org/10.1039/C9TA03265G	journal	January 2019
Improving the Carbon Resistance of Ni-Based Steam Reforming Catalyst by Alloying with Rh: A Computational Study Coupled with Reforming Experiments and EXAFS Characterization Guo, Jiahua; Xie, Chao; Lee, Kyungtae ACS Catalysis, Vol. 1, Issue 6 https://doi.org/10.1021/cs2000472	journal	April 2011
Carbon monoxide-fueled solid oxide fuel cell Homel, Michael; Gür, Turgut M.; Koh, Joon Ho Journal of Power Sources, Vol. 195, Issue 19 https://doi.org/10.1016/j.jpowsour.2010.04.020	journal	October 2010
CO ₂ activation and carbonate intermediates: an operando AP-XPS study of CO ₂ electrolysis reactions on solid oxide electrochemical cells Yu, Yi; Mao, Baohua; Geller, Aaron Phys. Chem. Chem. Phys., Vol. 16, Issue 23 https://doi.org/10.1039/C4CP01054J	journal	January 2014
Advanced Test Method of Solid Oxide Cells in a Plug-Flow Setup Jensen, So̸ren Ho̸jgaard; Hauch, Anne; Hendriksen, Peter Vang Journal of The Electrochemical Society, Vol. 156, Issue 6 https://doi.org/10.1149/1.3116247	journal	January 2009
Carbon and Redox Tolerant Infiltrated Oxide Fuel-Electrodes for Solid Oxide Cells Skafte, T. L.; Sudireddy, B. R.; Blennow, P. ECS Transactions, Vol. 72, Issue 7 https://doi.org/10.1149/07207.0201ecst	journal	April 2016
Steam Reforming and Graphite Formation on Ni Catalysts Bengaard, H. S.; Nørskov, J. K.; Sehested, J. Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3579	journal	July 2002
Catalysis-Hub.org, an open electronic structure database for surface reactions Winther, Kirsten T.; Hoffmann, Max J.; Boes, Jacob R. Scientific Data, Vol. 6, Issue 1 https://doi.org/10.1038/s41597-019-0081-y	journal	May 2019
Carbon dioxide activation and dissociation on ceria (110): A density functional theory study Cheng, Zhuo; Sherman, Brent J.; Lo, Cynthia S. The Journal of Chemical Physics, Vol. 138, Issue 1, Article No. 014702 https://doi.org/10.1063/1.4773248	journal	January 2013
Large scale electrochemical synthesis of high quality carbon nanodots and their photocatalytic property Ming, Hai; Ma, Zheng; Liu, Yang Dalton Transactions, Vol. 41, Issue 31 https://doi.org/10.1039/c2dt30985h	journal	January 2012
Hydrocarbon steam reforming on Ni alloys at solid oxide fuel cell operating conditions Nikolla, E.; Schwank, J.; Linic, S. Catalysis Today, Vol. 136, Issue 3-4 https://doi.org/10.1016/j.cattod.2008.03.028	journal	July 2008
Sustainable hydrocarbon fuels by recycling CO 2 and H 2 O with renewable or nuclear energy Graves, Christopher; Ebbesen, Sune D.; Mogensen, Mogens Renewable and Sustainable Energy Reviews, Vol. 15, Issue 1 https://doi.org/10.1016/j.rser.2010.07.014	journal	January 2011
Electronic Structure of Magnesia−Ceria Model Catalysts, CO ₂ Adsorption, and CO ₂ Activation: A Synchrotron Radiation Photoelectron Spectroscopy Study Staudt, Thorsten; Lykhach, Yaroslava; Tsud, Nataliya The Journal of Physical Chemistry C, Vol. 115, Issue 17 https://doi.org/10.1021/jp200382y	journal	April 2011
Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15360	journal	May 2017
Surface electrochemistry of CO ₂ reduction and CO oxidation on Sm-doped CeO _2−x : coupling between Ce ³⁺ and carbonate adsorbates Feng, Zhuoluo A.; Machala, Michael L.; Chueh, William C. Physical Chemistry Chemical Physics, Vol. 17, Issue 18 https://doi.org/10.1039/C5CP00114E	journal	January 2015
Carbon Deposition in Solid Oxide Cells during Co-Electrolysis of H ₂ O and CO ₂ Tao, Youkun; Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg Journal of The Electrochemical Society, Vol. 161, Issue 3 https://doi.org/10.1149/2.079403jes	journal	December 2013
Data for the publication "Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates" Skafte, Theis Løye; Guan, Zixuan; Machala, Michael L. Technical University of Denmark https://doi.org/10.11583/DTU.4479050	dataset	January 2019
(Invited) High Performance Nano-Ceria Electrodes for Solid Oxide Cells Graves, C.; Martinez, L.; Sudireddy, B. R. ECS Transactions, Vol. 72, Issue 7 https://doi.org/10.1149/07207.0183ecst	journal	April 2016
Fundamental Concepts in Heterogeneous Catalysis Nørskov, Jens K.; Studt, Felix; Abild-Pedersen, Frank John Wiley & Sons, Inc. https://doi.org/10.1002/9781118892114	book	January 2014
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers Irvine, John T. S.; Neagu, Dragos; Verbraeken, Maarten C. Nature Energy, Vol. 1, Issue 1 https://doi.org/10.1038/nenergy.2015.14	journal	January 2016
Large-scale electricity storage utilizing reversible solid oxide cells combined with underground storage of CO ₂ and CH ₄ Jensen, S. H.; Graves, C.; Mogensen, M. Energy & Environmental Science, Vol. 8, Issue 8 https://doi.org/10.1039/C5EE01485A	journal	January 2015
Strategies for Carbon and Sulfur Tolerant Solid Oxide Fuel Cell Materials, Incorporating Lessons from Heterogeneous Catalysis Boldrin, Paul; Ruiz-Trejo, Enrique; Mermelstein, Joshua Chemical Reviews, Vol. 116, Issue 22 https://doi.org/10.1021/acs.chemrev.6b00284	journal	October 2016
Promoted Ceria: A Structural, Catalytic, and Computational Study Farra, Ramzi; García-Melchor, Max; Eichelbaum, Maik ACS Catalysis, Vol. 3, Issue 10 https://doi.org/10.1021/cs4005002	journal	September 2013
Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment Paier, Joachim; Penschke, Christopher; Sauer, Joachim Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr3004949	journal	December 2012
Reply to “Comment on ‘Taming multiple valency with density functionals: A case study of defective ceria' ” Fabris, Stefano; de Gironcoli, Stefano; Baroni, Stefano Physical Review B, Vol. 72, Issue 23 https://doi.org/10.1103/PhysRevB.72.237102	journal	December 2005
Efficient Reduction of CO₂ in a Solid Oxide Electrolyzer Bidrawn, F.; Kim, G.; Corre, G. Electrochemical and Solid-State Letters, Vol. 11, Issue 9, p. B167-B170 https://doi.org/10.1149/1.2943664	journal	January 2008
Note: Fixture for characterizing electrochemical devices in-operando in traditional vacuum systems Whaley, Josh A.; McDaniel, Anthony H.; El Gabaly, Farid Review of Scientific Instruments, Vol. 81, Issue 8 https://doi.org/10.1063/1.3479384	journal	August 2010
Localized carbon deposition in solid oxide electrolysis cells studied by multiphysics modeling Navasa, Maria; Frandsen, Henrik Lund; Skafte, Theis Løye Journal of Power Sources, Vol. 394 https://doi.org/10.1016/j.jpowsour.2018.05.039	journal	August 2018
Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy Zhang, Chunjuan; Grass, Michael E.; McDaniel, Anthony H. Nature Materials, Vol. 9, Issue 11 https://doi.org/10.1038/nmat2851	journal	September 2010
Oxygen Production from Mars Atmosphere Carbon Dioxide Using Solid Oxide Electrolysis Hartvigsen, Joseph; Elangovan, S.; Elwell, Jessica ECS Transactions, Vol. 78, Issue 1 https://doi.org/10.1149/07801.2953ecst	journal	May 2017
Electrochemically modified, robust solid oxide fuel cell anode for direct-hydrocarbon utilization Choi, Yoonseok; Brown, Evan C.; Haile, Sossina M. Nano Energy, Vol. 23 https://doi.org/10.1016/j.nanoen.2016.03.015	journal	May 2016
XPS, Raman spectroscopy, X-ray diffraction, specular X-ray reflectivity, transmission electron microscopy and elastic recoil detection analysis of emissive carbon film characterization: Emissive carbon film characterization Ermolieff, A.; Chabli, A.; Pierre, F. Surface and Interface Analysis, Vol. 31, Issue 3 https://doi.org/10.1002/sia.955	journal	March 2001
Hydrogen and synthetic fuel production from renewable energy sources Jensen, Søren H.; Larsen, Peter H.; Mogensen, Mogens International Journal of Hydrogen Energy, Vol. 32, Issue 15 https://doi.org/10.1016/j.ijhydene.2007.04.042	journal	October 2007
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia Angewandte Chemie International Edition, Vol. 52, Issue 19 https://doi.org/10.1002/anie.201210077	journal	April 2013
Carbon Deposits and Pt/YSZ Overpotentials In CO/CO2 Solid Oxide Electrochemical Cells Yu, Y.; Geller, A. I.; Mao, B. ECS Transactions, Vol. 57, Issue 1 https://doi.org/10.1149/05701.3119ecst	journal	October 2013
Direct oxidation of hydrocarbons in a solid-oxide fuel cell Park, Seungdoo; Vohs, John M.; Gorte, Raymond J. Nature, Vol. 404, Issue 6775 https://doi.org/10.1038/35005040	journal	March 2000
C 1s excitation studies of diamond (111). II. Unoccupied surface states Morar, J. F.; Himpsel, F. J.; Hollinger, G. Physical Review B, Vol. 33, Issue 2 https://doi.org/10.1103/PhysRevB.33.1346	journal	January 1986
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2 Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda Review of Scientific Instruments, Vol. 81, Issue 5 https://doi.org/10.1063/1.3427218	journal	May 2010
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
Innovation and science in the process industry Rostrup-Nielsen, Jens R.; Alstrup, Ib Catalysis Today, Vol. 53, Issue 3 https://doi.org/10.1016/S0920-5861(99)00125-X	journal	November 1999
Eliminating degradation in solid oxide electrochemical cells by reversible operation Graves, Christopher; Ebbesen, Sune Dalgaard; Jensen, Søren Højgaard Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4165	journal	December 2014
Enhanced Sulfur and Coking Tolerance of a Mixed Ion Conductor for SOFCs: BaZr_0.1Ce_0.7Y_0.2–xYb_xO_3–δ Yang, L.; Wang, S.; Blinn, K. Science, Vol. 326, Issue 5949, p. 126-129 https://doi.org/10.1126/science.1174811	journal	October 2009
Reassignment of the Vibrational Spectra of Carbonates, Formates, and Related Surface Species on Ceria: A Combined Density Functional and Infrared Spectroscopy Investigation Vayssilov, Georgi N.; Mihaylov, Mihail; Petkov, Petko St. The Journal of Physical Chemistry C, Vol. 115, Issue 47 https://doi.org/10.1021/jp208050a	journal	November 2011
Data for the publication "Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates" Skafte, Theis Løye; Guan, Zixuan; Machala, Michael L. Technical University of Denmark https://doi.org/10.11583/dtu.4479050.v1	dataset	January 2019
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia Angewandte Chemie, Vol. 125, Issue 19 https://doi.org/10.1002/ange.201210077	journal	April 2013

Cited By (1)

DFT+U study of CO2 reduction and CO oxidation on a reconstructed CeO2−(110) facet Kildgaard, J. V.; Hansen, H. A.; Vegge, T. Materials Today Advances, Vol. 8 https://doi.org/10.1016/j.mtadv.2020.100111	journal	December 2020

Similar Records

Long term durability test and post mortem for metal-supported solid oxide electrolysis cells

Journal Article · Mon Jul 27 00:00:00 EDT 2020 · Journal of Power Sources · OSTI ID:1577318

Shen, Fengyu; Wang, Ruofan; Tucker, Michael C.

A novel solid oxide electrolytic cell with reduced endothermic load for CO₂ electrolysis using (La_0.80Sr_0.20)_0.95MnO_3-δcathode

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · Journal of CO2 Utilization · OSTI ID:1577318

Velraj, Samgopiraj; Daramola, Damilola A.; Trembly, Jason P.

Threshold catalytic onset of carbon formation on CeO₂ during CO₂ electrolysis: mechanism and inhibition

Journal Article · Wed May 22 00:00:00 EDT 2019 · Journal of Materials Chemistry. A · OSTI ID:1577318

Wang, Jiayue; Bishop, Sean R.; Sun, Lixin; +9 more

Related Subjects

25 ENERGY STORAGE

Title: Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates

Citation Formats

References (59)

Cited By (1)

Similar Records

Related Subjects

Title: Selective high-temperature CO₂ electrolysis enabled by oxidized carbon intermediates