Understanding the Unique Reactivity of Cu for Electrochemical CO2 Reduction with a 3-Site Model

Varley, Joel B.; Govindarajan, Nitish; Ager, Joel W.

doi:10.1021/acs.jpclett.4c03157

Title: Understanding the Unique Reactivity of Cu for Electrochemical CO₂ Reduction with a 3-Site Model

Journal Article · 07 January 2025 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.4c03157 · OSTI ID:2507504

^[1];

^[2];

^[3]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Nanyang Technological Univ. (Singapore)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); University of California, Berkeley, CA (United States)

Cu-based catalysts for the electrochemical reduction of CO₂ and CO exhibit a perplexingly unique reactivity toward multicarbon based products compared to other studied electrocatalysts. Here, in this study, we use insights gained from a recent phenomenological 3-site microkinetic model and grand-canonical density functional theory calculations to clarify the importance of an underemphasized aspect critical to Cu’s unique reactivity: a population of so-called “reservoir” sites. Using model Cu surface motifs, we discuss how these types can be represented by undercoordinated structural defects like step edges and grain boundaries which form a network of highly anisotropic migration channels. These pathways are found to be amenable for feeding *CO over time to reactive sites like Cu adatoms more active toward C–C coupling. These results highlight an often overlooked aspect of catalyst optimization: reservoir site engineering, which exploits surface mobility and presents an equally important avenue for electrocatalyst engineering oversimply maximizing active site densities.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: US Department of Energy; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; AC52-07NA27344

OSTI ID:: 2507504

Report Number(s):: LLNL--JRNL-871243; 1108696

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 2 Vol. 16; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps Nie, Xiaowa; Esopi, Monica R.; Janik, Michael J. Angewandte Chemie, Vol. 125, Issue 9 https://doi.org/10.1002/ange.201208320	journal	January 2013
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes Pérez-Gallent, Elena; Figueiredo, Marta C.; Calle-Vallejo, Federico Angewandte Chemie, Vol. 129, Issue 13 https://doi.org/10.1002/ange.201700580	journal	February 2017
A Simple Rule of Thumb for Diffusion on Transition-Metal Surfaces Nilekar, Anand Udaykumar; Greeley, Jeff; Mavrikakis, Manos Angewandte Chemie International Edition, Vol. 45, Issue 42 https://doi.org/10.1002/anie.200602223	journal	October 2006
Stability and Degradation Mechanisms of Copper‐Based Catalysts for Electrochemical CO ₂ Reduction Popović, Stefan; Smiljanić, Milutin; Jovanovič, Primož Angewandte Chemie International Edition, Vol. 59, Issue 35 https://doi.org/10.1002/anie.202000617	journal	June 2020
Real‐time Monitoring Reveals Dissolution/Redeposition Mechanism in Copper Nanocatalysts during the Initial Stages of the CO ₂ Reduction Reaction Vavra, Jan; Shen, Tzu‐Hsien; Stoian, Dragos Angewandte Chemie International Edition, Vol. 60, Issue 3 https://doi.org/10.1002/anie.202011137	journal	November 2020
Insights into CC Coupling in CO ₂ Electroreduction on Copper Electrodes Montoya, Joseph H.; Peterson, Andrew A.; Nørskov, Jens K. ChemCatChem, Vol. 5, Issue 3 https://doi.org/10.1002/cctc.201200564	journal	January 2013
Theoretical Investigation of the Adsorbate and Potential‐Induced Stability of Cu Facets During Electrochemical CO₂ and CO Reduction Yu, Henry; Govindarajan, Nitish; Weitzner, Stephen E. ChemPhysChem, Vol. 25, Issue 10 https://doi.org/10.1002/cphc.202300959	journal	March 2024
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Grain boundary properties of elemental metals Zheng, Hui; Li, Xiang-Guo; Tran, Richard Acta Materialia, Vol. 186 https://doi.org/10.1016/j.actamat.2019.12.030	journal	March 2020
Site heterogeneity and broad surface-binding isotherms in modern catalysis: Building intuition beyond the Sabatier principle Mayer, James M. Journal of Catalysis, Vol. 439 https://doi.org/10.1016/j.jcat.2024.115725	journal	November 2024
The influence of pH on the reduction of CO and CO 2 to hydrocarbons on copper electrodes Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M. Journal of Electroanalytical Chemistry, Vol. 716 https://doi.org/10.1016/j.jelechem.2013.08.033	journal	March 2014
CO-CO coupling on Cu facets: Coverage, strain and field effects Sandberg, Robert B.; Montoya, Joseph H.; Chan, Karen Surface Science, Vol. 654 https://doi.org/10.1016/j.susc.2016.08.006	journal	December 2016
Theories for Electrolyte Effects in CO₂ Electroreduction Xu, Aoni; Govindarajan, Nitish; Kastlunger, Georg Accounts of Chemical Research, Vol. 55, Issue 4 https://doi.org/10.1021/acs.accounts.1c00679	journal	February 2022
Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B. Chemical Reviews, Vol. 119, Issue 12 https://doi.org/10.1021/acs.chemrev.8b00705	journal	April 2019
Diffusion Barriers for Carbon Monoxide on the Cu(001) Surface Using Many-Body Perturbation Theory and Various Density Functionals Wei, Ziyang; Göltl, Florian; Sautet, Philippe Journal of Chemical Theory and Computation, Vol. 17, Issue 12 https://doi.org/10.1021/acs.jctc.1c00946	journal	November 2021
Solvation Entropy Made Simple Garza, Alejandro J. Journal of Chemical Theory and Computation, Vol. 15, Issue 5 https://doi.org/10.1021/acs.jctc.9b00214	journal	March 2019
Surface Engineering of Copper Catalyst through CO* Adsorbate Yu, Henry; Weitzner, Stephen E.; Varley, Joel B. The Journal of Physical Chemistry C, Vol. 127, Issue 4 https://doi.org/10.1021/acs.jpcc.2c06456	journal	January 2023
A Comparative Study of Electrical Double Layer Effects for CO Reduction Reaction Kinetics Pasumarthi, Viswanath; Yu, Henry; Akhade, Sneha A. The Journal of Physical Chemistry C, Vol. 127, Issue 34 https://doi.org/10.1021/acs.jpcc.3c02953	journal	August 2023
Toward Engineering of Solution Microenvironments for the CO ₂ Reduction Reaction: Unraveling pH and Voltage Effects from a Combined Density-Functional–Continuum Theory Weitzner, Stephen E.; Akhade, Sneha A.; Varley, Joel B. The Journal of Physical Chemistry Letters, Vol. 11, Issue 10 https://doi.org/10.1021/acs.jpclett.0c00957	journal	April 2020
Using pH Dependence to Understand Mechanisms in Electrochemical CO Reduction Kastlunger, Georg; Wang, Lei; Govindarajan, Nitish ACS Catalysis, Vol. 12, Issue 8 https://doi.org/10.1021/acscatal.1c05520	journal	March 2022
Combining First-Principles Kinetics and Experimental Data to Establish Guidelines for Product Selectivity in Electrochemical CO₂ Reduction Kastlunger, Georg; Heenen, Hendrik H.; Govindarajan, Nitish ACS Catalysis, Vol. 13, Issue 7 https://doi.org/10.1021/acscatal.3c00228	journal	March 2023
Importance of Site Diversity and Connectivity in Electrochemical CO Reduction on Cu Kim, Chansol; Govindarajan, Nitish; Hemenway, Sydney ACS Catalysis, Vol. 14, Issue 5 https://doi.org/10.1021/acscatal.3c05904	journal	February 2024
Electrochemical CO ₂ Reduction: Classifying Cu Facets Bagger, Alexander; Ju, Wen; Varela, Ana Sofia ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01899	journal	July 2019
The Role of Roughening to Enhance Selectivity to C ₂₊ Products during CO ₂ Electroreduction on Copper Gauthier, Joseph A.; Stenlid, Joakim Halldin; Abild-Pedersen, Frank ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01485	journal	August 2021
Identification of the Selective Sites for Electrochemical Reduction of CO to C 2+ Products on Copper Nanoparticles by Combining Reactive Force Fields, Density Functional Theory, and Machine Learning Huang, Yufeng; Chen, Yalu; Cheng, Tao ACS Energy Letters, Vol. 3, Issue 12 https://doi.org/10.1021/acsenergylett.8b01933	journal	November 2018
Oxidation State and Surface Reconstruction of Cu under CO ₂ Reduction Conditions from In Situ X-ray Characterization Lee, Soo Hong; Lin, John C.; Farmand, Maryam Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c10017	journal	December 2020
H and CO Co-Induced Roughening of Cu Surface in CO₂ Electroreduction Conditions Zhang, Zisheng; Gee, Winston; Sautet, Philippe Journal of the American Chemical Society, Vol. 146, Issue 23 https://doi.org/10.1021/jacs.4c03515	journal	May 2024
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b06227	journal	July 2015
Structure- and Potential-Dependent Cation Effects on CO Reduction at Copper Single-Crystal Electrodes Pérez-Gallent, Elena; Marcandalli, Giulia; Figueiredo, Marta Costa Journal of the American Chemical Society, Vol. 139, Issue 45 https://doi.org/10.1021/jacs.7b10142	journal	November 2017
Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts Peterson, Andrew A.; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201461p	journal	January 2012
Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO ₂ Reduction to CO Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A. The Journal of Physical Chemistry Letters, Vol. 4, Issue 3 https://doi.org/10.1021/jz3021155	journal	January 2013
Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction Huang, Jianfeng; Hörmann, Nicolas; Oveisi, Emad Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05544-3	journal	August 2018
Unraveling the rate-determining step of C2+ products during electrochemical CO reduction Deng, Wanyu; Zhang, Peng; Qiao, Yu Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-45230-1	journal	January 2024
Key intermediates and Cu active sites for CO2 electroreduction to ethylene and ethanol Zhan, Chao; Dattila, Federico; Rettenmaier, Clara Nature Energy, Vol. 9, Issue 12 https://doi.org/10.1038/s41560-024-01633-4	journal	September 2024
Operando studies reveal active Cu nanograins for CO2 electroreduction Yang, Yao; Louisia, Sheena; Yu, Sunmoon Nature, Vol. 614, Issue 7947 https://doi.org/10.1038/s41586-022-05540-0	journal	February 2023
Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction Lum, Yanwei; Ager, Joel W. Nature Catalysis, Vol. 2, Issue 1 https://doi.org/10.1038/s41929-018-0201-7	journal	December 2018
Experimental evidence of distinct sites for CO2-to-CO and CO conversion on Cu in the electrochemical CO2 reduction reaction Gao, Wenqiang; Xu, Yifei; Fu, Linke Nature Catalysis, Vol. 6, Issue 10 https://doi.org/10.1038/s41929-023-01002-6	journal	August 2023
Atomic-scale surface restructuring of copper electrodes under CO2 electroreduction conditions Amirbeigiarab, Reihaneh; Tian, Jing; Herzog, Antonia Nature Catalysis, Vol. 6, Issue 9 https://doi.org/10.1038/s41929-023-01009-z	journal	August 2023
Solution-based Cu+ transient species mediate the reconstruction of copper electrocatalysts for CO2 reduction Vavra, Jan; Ramona, Gaétan P. L.; Dattila, Federico Nature Catalysis, Vol. 7, Issue 1 https://doi.org/10.1038/s41929-023-01070-8	journal	January 2024
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
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Implicit self-consistent electrolyte model in plane-wave density-functional theory Mathew, Kiran; Kolluru, V. S. Chaitanya; Mula, Srinidhi The Journal of Chemical Physics, Vol. 151, Issue 23 https://doi.org/10.1063/1.5132354	journal	December 2019
Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches Heenen, Hendrik H.; Gauthier, Joseph A.; Kristoffersen, Henrik H. The Journal of Chemical Physics, Vol. 152, Issue 14 https://doi.org/10.1063/1.5144912	journal	April 2020
Effects of surface diffusion in electrocatalytic CO2 reduction on Cu revealed by kinetic Monte Carlo simulations Li, Jinghan; Maresi, Ilaria; Lum, Yanwei The Journal of Chemical Physics, Vol. 155, Issue 16 https://doi.org/10.1063/5.0068517	journal	October 2021
An implicit electrolyte model for plane wave density functional theory exhibiting nonlinear response and a nonlocal cavity definition Islam, S. M. Rezwanul; Khezeli, Foroogh; Ringe, Stefan The Journal of Chemical Physics, Vol. 159, Issue 23 https://doi.org/10.1063/5.0176308	journal	December 2023
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Electrode potential from density functional theory calculations combined with implicit solvation theory Haruyama, Jun; Ikeshoji, Tamio; Otani, Minoru Physical Review Materials, Vol. 2, Issue 9 https://doi.org/10.1103/PhysRevMaterials.2.095801	journal	September 2018
How pH affects electrochemical processes Govindarajan, Nitish; Xu, Aoni; Chan, Karen Science, Vol. 375, Issue 6579 https://doi.org/10.1126/science.abj2421	journal	January 2022
Structure Sensitivity and Catalyst Restructuring for CO₂ Electro-Reduction on Copper Cheng, Dongfang; Nguyen, Khanh-Ly; Heyde, Markus ECS Meeting Abstracts, Vol. MA2024-02, Issue 62 https://doi.org/10.1149/MA2024-02624231mtgabs	journal	November 2024

Similar Records

The presence and role of the intermediary CO reservoir in heterogeneous electroreduction of CO ₂

Journal Article · 2022 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1865973

Louisia, Sheena; Kim, Dohyung; Li, Yifan; +4 more

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO₂ electroreduction toward multicarbon products

Journal Article · 2023 · Nature Communications · OSTI ID:2470252

Du, Cheng; Mills, Joel P.; Yohannes, Asfaw G.; +16 more

Enhanced CO₂ Reactive Capture and Conversion Using Aminothiolate Ligand–Metal Interface

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2371805

Wan, Mingyu; Yang, Zhengyang; Morgan, Heba; +6 more

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
Energy - Conversion
cataysts
chemical reactions
defects
genetics
grain boundaries

Title: Understanding the Unique Reactivity of Cu for Electrochemical CO2 Reduction with a 3-Site Model

Citation Formats

References (50)

Similar Records

Related Subjects

Title: Understanding the Unique Reactivity of Cu for Electrochemical CO₂ Reduction with a 3-Site Model