Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

doi:10.1021/acs.jpclett.7b03180

Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?

Journal Article · 16 January 2018 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.7b03180 · OSTI ID:1430685

Garza, Alejandro J. ^[1];

^[2];

^[3]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO₂ on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10³ s^–1. Oxygen can survive longer in deeper layers, but it does not promote CO₂ adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO₂ adsorption on copper.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1430685

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 3 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders Angewandte Chemie, Vol. 127, Issue 17 https://doi.org/10.1002/ange.201412214	journal	February 2015
Electrocatalytic Production of C3-C4 Compounds by Conversion of CO ₂ on a Chloride-Induced Bi-Phasic Cu ₂ O-Cu Catalyst Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung Angewandte Chemie, Vol. 127, Issue 49 https://doi.org/10.1002/ange.201505730	journal	October 2015
Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander Angewandte Chemie International Edition, Vol. 56, Issue 38 https://doi.org/10.1002/anie.201704613	journal	August 2017
Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO ₂ Reduction Investigated with ¹⁸ O Labeling Lum, Yanwei; Ager, Joel W. Angewandte Chemie International Edition, Vol. 57, Issue 2 https://doi.org/10.1002/anie.201710590	journal	December 2017
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
Diffusivity and solubility of oxygen in solid copper using potentiostatic and potentiometric techniques Narula, M. L.; Tare, V. B.; Worrell, W. L. Metallurgical Transactions B, Vol. 14, Issue 4 https://doi.org/10.1007/BF02653953	journal	December 1983
Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface Kim, Youn-Geun; Javier, Alnald; Baricuatro, Jack H. Electrocatalysis, Vol. 7, Issue 5 https://doi.org/10.1007/s12678-016-0314-1	journal	June 2016
Oxygen-assisted cleavage of OH, NH, and CH bonds on transition metal surfaces: bond-order-conservation-Morse-potential analysis Shustorovich, Evgeny; Bell, Alexis T. Surface Science, Vol. 268, Issue 1-3 https://doi.org/10.1016/0039-6028(92)90979-G	journal	January 1992
Improvement of the selectivity of the electrochemical conversion of CO2 to hydrocarbons using cupreous electrodes with in-situ oxidation by oxygen Engelbrecht, Andreas; Hämmerle, Martin; Moos, Ralf Electrochimica Acta, Vol. 224 https://doi.org/10.1016/j.electacta.2016.12.059	journal	January 2017
Structure and composition of Cu(hkl) surfaces exposed to O2 and emersed from alkaline solutions: Prelude to UHV-EC studies of CO2 reduction at well-defined copper catalysts Baricuatro, Jack H.; Ehlers, Charles B.; Cummins, Kyle D. Journal of Electroanalytical Chemistry, Vol. 716 https://doi.org/10.1016/j.jelechem.2013.10.001	journal	March 2014
Cathodic regeneration of a clean and ordered Cu(1 0 0)-(1×1) surface from an air-oxidized and disordered electrode: An operando STM study Kim, Youn-Geun; Soriaga, Manuel P. Journal of Electroanalytical Chemistry, Vol. 734 https://doi.org/10.1016/j.jelechem.2014.09.010	journal	November 2014
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO ₂ Reduction Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter The Journal of Physical Chemistry C, Vol. 121, Issue 26 https://doi.org/10.1021/acs.jpcc.7b03673	journal	June 2017
Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO ₂ Reduction Liu, Chang; Lourenço, Maicon P.; Hedström, Svante The Journal of Physical Chemistry C, Vol. 121, Issue 45 https://doi.org/10.1021/acs.jpcc.7b08269	journal	October 2017
Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO ₂ Reduction Cavalca, Filippo; Ferragut, Rafael; Aghion, Stefano The Journal of Physical Chemistry C, Vol. 121, Issue 45 https://doi.org/10.1021/acs.jpcc.7b08278	journal	October 2017
Theoretical Insights into a CO Dimerization Mechanism in CO ₂ Electroreduction Montoya, Joseph H.; Shi, Chuan; Chan, Karen The Journal of Physical Chemistry Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acs.jpclett.5b00722	journal	May 2015
Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO ₂ : New Theoretical Insights from an Improved Electrochemical Model Goodpaster, Jason D.; Bell, Alexis T.; Head-Gordon, Martin The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00358	journal	April 2016
Formation of Copper Catalysts for CO ₂ Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy Eilert, André; Roberts, F. Sloan; Friebel, Daniel The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00367	journal	April 2016
Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction Eilert, André; Cavalca, Filippo; Roberts, F. Sloan The Journal of Physical Chemistry Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acs.jpclett.6b02273	journal	December 2016
CO ₂ Electroreduction at Low Overpotential on Oxide-Derived Cu/Carbons Fabricated from Metal Organic Framework Zhao, Kun; Liu, Yanming; Quan, Xie ACS Applied Materials & Interfaces, Vol. 9, Issue 6 https://doi.org/10.1021/acsami.6b15402	journal	February 2017
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
Morphology Matters: Tuning the Product Distribution of CO ₂ Electroreduction on Oxide-Derived Cu Foam Catalysts Dutta, Abhijit; Rahaman, Motiar; Luedi, Nicola C. ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00770	journal	May 2016
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
Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols Gao, Dunfeng; Zegkinoglou, Ioannis; Divins, Nuria J. ACS Nano, Vol. 11, Issue 5 https://doi.org/10.1021/acsnano.7b01257	journal	April 2017
What Makes for a Bad Catalytic Cycle? A Theoretical Study on the Suzuki−Miyaura Reaction within the Energetic Span Model Kozuch, Sebastian; Martin, Jan M. L. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs100129u	journal	February 2011
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts Ren, Dan; Deng, Yilin; Handoko, Albertus Denny ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs502128q	journal	March 2015
Theoretical Study of Trans-metalation Process in Palladium-Catalyzed Borylation of Iodobenzene with Diboron Sumimoto, Michinori; Iwane, Naoki; Takahama, Tomohiko Journal of the American Chemical Society, Vol. 126, Issue 33 https://doi.org/10.1021/ja040020r	journal	August 2004
A Combined Kinetic−Quantum Mechanical Model for Assessment of Catalytic Cycles: Application to Cross-Coupling and Heck Reactions Kozuch, Sebastian; Shaik, Sason Journal of the American Chemical Society, Vol. 128, Issue 10 https://doi.org/10.1021/ja0559146	journal	March 2006
Mechanistic and Computational Study of a Palladacycle-Catalyzed Decomposition of a Series of Neutral Phosphorothioate Triesters in Methanol Liu, C. Tony; Maxwell, Christopher I.; Edwards, David R. Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja107144c	journal	November 2010
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
Kinetic-Quantum Chemical Model for Catalytic Cycles: The Haber−Bosch Process and the Effect of Reagent Concentration Kozuch, Sebastian; Shaik, Sason The Journal of Physical Chemistry A, Vol. 112, Issue 26 https://doi.org/10.1021/jp8004772	journal	July 2008
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12123	journal	June 2016
Electrochemical CO ₂ reduction on Cu ₂ O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons Kas, Recep; Kortlever, Ruud; Milbrat, Alexander Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/C4CP01520G	journal	January 2014
Insights into an autonomously formed oxygen-evacuated Cu ₂ O electrode for the selective production of C ₂ H ₄ from CO ₂ Kim, Dahee; Lee, Seunghwa; Ocon, Joey D. Physical Chemistry Chemical Physics, Vol. 17, Issue 2 https://doi.org/10.1039/C4CP03172E	journal	January 2015
Selective electrochemical reduction of CO ₂ to CO on CuO-derived Cu nanowires Ma, Ming; Djanashvili, Kristina; Smith, Wilson A. Physical Chemistry Chemical Physics, Vol. 17, Issue 32 https://doi.org/10.1039/C5CP03559G	journal	January 2015
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
Kinetics of oxygen adsorption, absorption, and desorption on the Cu(111) surface Bloch, J.; Bottomley, D. J.; Janz, S. The Journal of Chemical Physics, Vol. 98, Issue 11 https://doi.org/10.1063/1.464424	journal	June 1993
Long-range correlation energy calculated from coupled atomic response functions Ambrosetti, Alberto; Reilly, Anthony M.; DiStasio, Robert A. The Journal of Chemical Physics, Vol. 140, Issue 18 https://doi.org/10.1063/1.4865104	journal	May 2014
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra The Journal of Chemical Physics, Vol. 140, Issue 8 https://doi.org/10.1063/1.4865107	journal	February 2014
Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni López-Moreno, S.; Romero, A. H. The Journal of Chemical Physics, Vol. 142, Issue 15 https://doi.org/10.1063/1.4917259	journal	April 2015
Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂ Favaro, Marco; Xiao, Hai; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1701405114	journal	June 2017
Cu metal embedded in oxidized matrix catalyst to promote CO ₂ activation and CO dimerization for electrochemical reduction of CO ₂ Xiao, Hai; Goddard, William A.; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1702405114	journal	June 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Oxygen adsorption and stability of surface oxides on Cu ( 111 ) : A first-principles investigation Soon, Aloysius; Todorova, Mira; Delley, Bernard Physical Review B, Vol. 73, Issue 16 https://doi.org/10.1103/PhysRevB.73.165424	journal	April 2006
Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory Jinnouchi, Ryosuke; Anderson, Alfred B. Physical Review B, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevB.77.245417	journal	June 2008
Density functional study of oxygen on Cu(100) and Cu(110) surfaces Duan, X.; Warschkow, O.; Soon, A. Physical Review B, Vol. 81, Issue 7 https://doi.org/10.1103/PhysRevB.81.075430	journal	February 2010
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation Peng, Haowei; Yang, Zeng-Hui; Perdew, John P. Physical Review X, Vol. 6, Issue 4 https://doi.org/10.1103/PhysRevX.6.041005	journal	October 2016

Cited By (16)

Electrochemical CO ₂ Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design Kibria, Md Golam; Edwards, Jonathan P.; Gabardo, Christine M. Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201807166	journal	December 2018
Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction Martić, Nemanja; Reller, Christian; Macauley, Chandra Advanced Energy Materials, Vol. 9, Issue 29 https://doi.org/10.1002/aenm.201901228	journal	June 2019
Atomic‐Scale Spacing between Copper Facets for the Electrochemical Reduction of Carbon Dioxide Jeong, Hyung Mo; Kwon, Youngkook; Won, Jong Ho Advanced Energy Materials, Vol. 10, Issue 10 https://doi.org/10.1002/aenm.201903423	journal	March 2020
Strategies for Designing Nanoparticles for Electro‐ and Photocatalytic CO ₂ Reduction Choi, Ji Yong; Choi, Woong; Park, Joon Woo Chemistry – An Asian Journal, Vol. 15, Issue 2 https://doi.org/10.1002/asia.201901533	journal	December 2019
Insight into the Formation and Transfer Process of the First Intermediate of CO ₂ Reduction over Ag‐Decorated Dendritic Cu Yang, Yang; Ajmal, Saira; Feng, Yiqing Chemistry – A European Journal https://doi.org/10.1002/chem.201904063	journal	October 2019
On the Oxidation State of Cu ₂ O upon Electrochemical CO ₂ Reduction: An XPS Study Permyakova, Anastasia A.; Herranz, Juan; El Kazzi, Mario ChemPhysChem, Vol. 20, Issue 22 https://doi.org/10.1002/cphc.201900468	journal	July 2019
Electrochemical Reduction of CO ₂ over Heterogeneous Catalysts in Aqueous Solution: Recent Progress and Perspectives Long, Chang; Li, Xiang; Guo, Jun Small Methods https://doi.org/10.1002/smtd.201800369	journal	December 2018
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
Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface Wang, Hongxia; Tzeng, Yan-Kai; Ji, Yongfei Nature Nanotechnology, Vol. 15, Issue 2 https://doi.org/10.1038/s41565-019-0603-y	journal	January 2020
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
Zn nanosheets coated with a ZnS subnanometer layer for effective and durable CO ₂ reduction Li, Chenglong; Shen, Gurong; Zhang, Rui Journal of Materials Chemistry A, Vol. 7, Issue 4 https://doi.org/10.1039/c8ta10799h	journal	January 2019
Mechanism and kinetics for both thermal and electrochemical reduction of N ₂ catalysed by Ru(0001) based on quantum mechanics Chen, Liang-Yu; Kuo, Tung-Chun; Hong, Zih-Siang Physical Chemistry Chemical Physics, Vol. 21, Issue 32 https://doi.org/10.1039/c9cp03187a	journal	January 2019
New aspects of C2 selectivity in electrochemical CO ₂ reduction over oxide-derived copper Shah, Aamir Hassan; Wang, Yanjie; Hussain, Sajjad Physical Chemistry Chemical Physics, Vol. 22, Issue 4 https://doi.org/10.1039/c9cp06009j	journal	January 2020
Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A. The Journal of Chemical Physics, Vol. 148, Issue 14 https://doi.org/10.1063/1.5024219	journal	April 2018
Origin of structural stability of ScH ₃ molecular nanowires and their chemical-bonding behavior: Correlation effects of the Sc 3d electrons Lou, Ping; Lee, Jin Yong The Journal of Chemical Physics, Vol. 150, Issue 18 https://doi.org/10.1063/1.5093446	journal	May 2019
On the origin of the elusive first intermediate of CO ₂ electroreduction Chernyshova, Irina V.; Somasundaran, Ponisseril; Ponnurangam, Sathish Proceedings of the National Academy of Sciences, Vol. 115, Issue 40 https://doi.org/10.1073/pnas.1802256115	journal	September 2018

Similar Records

The Role of Subsurface Oxygen on Cu Surfaces for CO₂ Electrochemical Reduction

Journal Article · 2018 · Journal of Physical Chemistry. C · OSTI ID:1457147

Fields, Meredith; Hong, Xin; Norskov, Jens K.; +1 more

Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO₂ Reduction

Journal Article · 2017 · Journal of Physical Chemistry. C · OSTI ID:1463314

Cavalca, Filippo; Ferragut, Rafael; Aghion, Stefano; +7 more

Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO₂ reduction

Journal Article · 2018 · Nature Catalysis · OSTI ID:1603501

Lum, Yanwei; Ager, Joel W.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?

Citation Formats

References (48)

Cited By (16)

Similar Records

Related Subjects

Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?