Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
Abstract
Fuels and industrial chemicals that are conventionally derived from fossil resources could potentially be produced in a renewable, sustainable manner by an electrochemical process that operates at room temperature and atmospheric pressure, using only water, CO2, and electricity as inputs. To enable this technology, improved catalysts must be developed. Herein, we report trends in the electrocatalytic conversion of CO2 on a broad group of seven transition metal surfaces: Au, Ag, Zn, Cu, Ni, Pt, and Fe. Contrary to conventional knowledge in the field, all metals studied are capable of producing methane or methanol. We quantify reaction rates for these two products and describe catalyst activity and selectivity in the framework of CO binding energies for the different metals. While selectivity toward methane or methanol is low for most of these metals, the fact that they are all capable of producing these products, even at a low rate, is important new knowledge. This study reveals a richer surface chemistry for transition metals than previously known and provides new insights to guide the development of improved CO2 conversion catalysts.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Atomistic modelling has revealed a deeper understanding of catalytic activity of GB on Au surfaces, including broken scaling relations and broken local spatial symmetry near the GB.
“Atomistic modelling has revealed a deeper understanding of the catalytic activity of GB on Au surfaces, including broken scaling relations [81] and broken local spatial symmetry near the GB.[82]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [82]
The predicted theoretical limiting potential for CH3OH production using Pt@dv-Gr is significantly less negative than any catalysts that produce CH4 or CH3OH in the literature, whether synthesized (-0.5 to -1.0 V) or predicted (-0.3 to -1.0 V).
“In particular, as in the free energy diagram shown in Fig. 4 in detail, the predicted theoretical limiting potential (U L) for CH3OH production using Pt@dv-Gr is significantly less negative than any catalysts that produce CH4 or CH3OH in the literature, synthesized (–0.5 to –1.0 V)35,37,38 or predicted (–0.3 V to –1.0 V).4,6,39,40”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [35]
In experiments, polycrystalline Ni and Pt produced H2 gas as a major product almost exclusively and only a trace of CH4 at -1.08 V and -0.67 V vs. RHE, respectively, while Cu produced CH4, C2H4, and H2 in similar amounts at -1.05 V vs. RHE.
“However, in an experiment for the CO2 reduction reaction, polycrystalline Ni and Pt produced H2 gas as a major product almost exclusively and only a trace of CH4 with a total current density of 5 mA cm–2 at –1.08 V and –0.67 V vs. RHE, respectively, while Cu produced CH4, C2H4, and H2 in similar amounts with a total current density of 5 mA cm–2 at –1.05 V vs. RHE.35”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [35]
The experimental product selectivity is significantly different for Ni, Pt and Cu, even though their theoretical limiting potentials for the CO2 reduction reaction are similar.
“It is thus noteworthy that the experimental product selectivity is significantly different for Ni, Pt and Cu, even though their theoretical limiting potentials for the CO2 reduction reaction are similar.”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [35]
Cites
Powering the planet: Chemical challenges in solar energy utilization
Lewis, N. S., & Nocera, D. G. (2006) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0603395103 · Cited by 8,316 · see citing works
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J., & Nørskov, J. K. (2010) · Energy & Environmental Science · doi:10.1039/c0ee00071j · Cited by 3,784 · see citing works
Handbook of fuel cells: fundamentals, technology, and applications
(2003) · Focus on Catalysts · doi:10.1016/s1351-4180(03)00850-x · Cited by 3,327 · see citing works
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
Kuhl, K. P., Cave, E. R., Abram, D. N., & Jaramillo, T. F. (2012) · Energy & Environmental Science · doi:10.1039/c2ee21234j · Cited by 3,160 · see citing works
Self-citationActivity Descriptors for CO <sub>2</sub> Electroreduction to Methane on Transition-Metal Catalysts
Peterson, A. A., & Nørskov, J. K. (2012) · The Journal of Physical Chemistry Letters · doi:10.1021/jz201461p · Cited by 1,667 · see citing works
Aqueous CO 2 Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles
Chen, Y., Li, C. W., & Kanan, M. W. (2012) · Journal of the American Chemical Society · doi:10.1021/ja309317u · Cited by 1,661 · see citing works
Ionic Liquid–Mediated Selective Conversion of CO <sub>2</sub> to CO at Low Overpotentials
Rosen, B. A., Salehi-Khojin, A., Thorson, M. R., Zhu, W., Whipple, D. T., Kenis, P. J. A., & Masel, R. I. (2011) · Science · doi:10.1126/science.1209786 · Cited by 1,558 · see citing works
A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper
Gattrell, M., Gupta, N., & Co, A. C. (2006) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2006.05.013 · Cited by 1,499 · see citing works
Hori, Y., Kikuchi, K., & Suzuki, S. (1985) · Chemistry Letters · doi:10.1246/cl.1985.1695 · Cited by 1,401 · see citing works
Anthropogenic Chemical Carbon Cycle for a Sustainable Future
Olah, G. A., Prakash, G. K. S., & Goeppert, A. (2011) · Journal of the American Chemical Society · doi:10.1021/ja202642y · Cited by 1,378 · see citing works
Schouten, K. J. P., Kwon, Y., van der Ham, C. J. M., Qin, Z., & Koper, M. T. M. (2011) · Chemical Science · doi:10.1039/c1sc00277e · Cited by 960 · see citing works
Hull, J. F., Himeda, Y., Wang, W., Hashiguchi, B. G., Periana, R. A., Szalda, D. J., Muckerman, J. T., & Fujita, E. (2012) · Nature Chemistry · doi:10.1038/nchem.1295 · Cited by 936 · see citing works
Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
Nie, X., Esopi, M. R., Janik, M. J., & Asthagiri, A. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201208320 · Cited by 927 · see citing works
Electrochemical Reduction of CO at a Copper Electrode
Hori, Y., Takahashi, R., Yoshinami, Y., & Murata, A. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp970284i · Cited by 818 · see citing works
Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO
Hansen, H. A., Varley, J. B., Peterson, A. A., & Nørskov, J. K. (2013) · The Journal of Physical Chemistry Letters · doi:10.1021/jz3021155 · Cited by 753 · see citing works
Electrocatalytic CO 2 Conversion to Oxalate by a Copper Complex
Angamuthu, R., Byers, P. M., Lutz, M., Spek, A. L., & Bouwman, E. (2010) · Science · doi:10.1126/science.1177981 · Cited by 592 · see citing works
Photocatalytic CO2 reduction by TiO2 and related titanium containing solids
Dhakshinamoorthy, A., Navalón, S., Corma, A., & Garcı́a, H. (2012) · Energy & Environmental Science · doi:10.1039/c2ee21948d · Cited by 565 · see citing works
Cole, E. B., Lakkaraju, P. S., Rampulla, D. M., Morris, A. J., Abelev, E., & Bocarsly, A. B. (2010) · Journal of the American Chemical Society · doi:10.1021/ja1023496 · Cited by 557 · see citing works
Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
Shi, C., Hansen, H. A., Lausche, A. C., & Nørskov, J. K. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c3cp54822h · Cited by 465 · see citing works
Nanoparticle Silver Catalysts That Show Enhanced Activity for Carbon Dioxide Electrolysis
Salehi‐Khojin, A., Jhong, H. “., Rosen, B. A., Zhu, W. D., Ma, S., Kenis, P. J. A., & Masel, R. I. (2012) · The Journal of Physical Chemistry C · doi:10.1021/jp310509z · Cited by 432 · see citing works
Woolerton, T. W., Sheard, S., Reisner, E., Pierce, E., Ragsdale, S. W., & Armstrong, F. A. (2010) · Journal of the American Chemical Society · doi:10.1021/ja910091z · Cited by 431 · see citing works
Artificial Photosynthesis over Crystalline TiO2-Based Catalysts: Fact or Fiction?
Yang, C., Yu, Y., van der Linden, B., Wu, J. C. S., & Mul, G. (2010) · Journal of the American Chemical Society · doi:10.1021/ja101318k · Cited by 375 · see citing works
Yui, T., Kan, A., Saitoh, C., Koike, K., Ibusuki, T., & Ishitani, O. (2011) · ACS Applied Materials & Interfaces · doi:10.1021/am200425y · Cited by 311 · see citing works
Hori, Y., Wakebe, H., Tsukamoto, T., & Koga, O. (1995) · Surface Science · doi:10.1016/0039-6028(95)00441-6 · Cited by 276 · see citing works
Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces
Jiang, T., Mowbray, D. J., Dobrin, S., et al. (2009) · The Journal of Physical Chemistry C · doi:10.1021/jp811185g · Cited by 276 · see citing works
Greeley, J., & Marković, N. M. (2012) · Energy & Environmental Science · doi:10.1039/c2ee21754f · Cited by 272 · see citing works
On the importance of reducing the energetic and material demands of electrical energy storage
Barnhart, C. J., & Benson, S. M. (2013) · Energy & Environmental Science · doi:10.1039/c3ee24040a · Cited by 255 · see citing works
Gattrell, M., Gupta, N., & Co, A. C. (2006) · Energy Conversion and Management · doi:10.1016/j.enconman.2006.09.019 · Cited by 249 · see citing works
Adsorption of CO, intermediately formed in electrochemical reduction of CO2, at a copper electrode
Hori, Y., Murata, A., & Yoshinami, Y. (1991) · Journal of the Chemical Society Faraday Transactions · doi:10.1039/ft9918700125 · Cited by 162 · see citing works
CatApp: A Web Application for Surface Chemistry and Heterogeneous Catalysis
Hummelshøj, J. S., Abild‐Pedersen, F., Studt, F., Bligaard, T., & Nørskov, J. K. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201107947 · Cited by 155 · see citing works
Interaction of Co with an Fe(111) surface
Seip, U., Tsai, M.-C., Christmann, K., et al. (1984) · Surface Science · doi:10.1016/0039-6028(84)90006-2 · Cited by 154 · see citing works
Ionic Liquid Co-catalyzed Artificial Photosynthesis of CO
Lin, J., Ding, Z., Hou, Y., & Wang, X. (2013) · Scientific Reports · doi:10.1038/srep01056 · Cited by 83 · see citing works
Gonzalez, L., Miranda, R., & Ferrer, S. (1982) · Surface Science · doi:10.1016/0039-6028(82)90187-x · Cited by 65 · see citing works
Taguchi, S., Aramata, A., & Enyo, M. (1994) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(93)03287-y · Cited by 53 · see citing works
Hori, Y., Koga, O., Aramata, A., & Enyo, M. (1992) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.65.3008 · Cited by 29 · see citing works
Koga, O., Matsuo, T., Yamazaki, H., & Hori, Y. (1998) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.71.315 · Cited by 18 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Combining theory and experiment in electrocatalysis: Insights into materials design
Seh, Z. W., Kibsgaard, J., Dickens, C. F., Chorkendorff, I., Nørskov, J. K., & Jaramillo, T. F. (2017) · Science · doi:10.1126/science.aad4998 · Cited by 12,114 · see citing works
Self-citationProgress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte
Nitopi, S., Bertheussen, E., Scott, S. B., Liu, X., Engstfeld, A. K., Horch, S., Seger, B., Stephens, I. E. L., Chan, K., Hahn, C., et al. (2019) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00705 · Cited by 5,223 · see citing works
Self-citationGeneral Techno-Economic Analysis of CO <sub>2</sub> Electrolysis Systems
Jouny, M., Luc, W., & Jiao, F. (2018) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.7b03514 · Cited by 1,628 · see citing works
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide
Zhu, D. D., Liu, J. L., & Qiao, S. Z. (2016) · Advanced Materials · doi:10.1002/adma.201504766 · Cited by 1,594 · see citing works
Kibria, M. G., Edwards, J. P., Gabardo, C. M., Dinh, C., Seifitokaldani, A., Sinton, D., & Sargent, E. H. (2019) · Advanced Materials · doi:10.1002/adma.201807166 · Cited by 1,331 · see citing works
Electrocatalysis for CO <sub>2</sub> conversion: from fundamentals to value-added products
Wang, G., Chen, J., Ding, Y., Cai, P., Yi, L., Li, Y., Tu, C., Hou, Y., Wen, Z., & Dai, L. (2021) · Chemical Society Reviews · doi:10.1039/d0cs00071j · Cited by 1,295 · see citing works
Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials
Sun, Z., Ma, T., Tao, H., Fan, Q., & Han, B. (2017) · Chem · doi:10.1016/j.chempr.2017.09.009 · Cited by 1,224 · see citing works
Ren, D., Deng, Y., Handoko, A. D., Chen, C. S., Malkhandi, S., & Yeo, B. S. (2015) · ACS Catalysis · doi:10.1021/cs502128q · Cited by 930 · see citing works
Large-Scale and Highly Selective CO2 Electrocatalytic Reduction on Nickel Single-Atom Catalyst
Zheng, T., Jiang, K., Ta, N., Hu, Y., Zeng, J., Liu, J., & Wang, H. (2019) · Joule · doi:10.1016/j.joule.2018.10.015 · Cited by 887 · see citing works
Metal‐Free Carbon Materials for CO<sub>2</sub> Electrochemical Reduction
Duan, X., Xu, J., Wei, Z., Ma, J., Guo, S., Wang, S., Liu, H., & Dou, S. (2017) · Advanced Materials · doi:10.1002/adma.201701784 · Cited by 754 · see citing works
Electric Field Effects in Electrochemical CO <sub>2</sub> Reduction
Chen, L. D., Urushihara, M., Chan, K., & Nørskov, J. K. (2016) · ACS Catalysis · doi:10.1021/acscatal.6b02299 · Cited by 702 · see citing works
Verma, S., Kim, B., Jhong, H. “., Ma, S., & Kenis, P. J. A. (2016) · ChemSusChem · doi:10.1002/cssc.201600394 · Cited by 655 · see citing works
Active Sites of Au and Ag Nanoparticle Catalysts for CO2 Electroreduction to CO
Back, S., Yeom, M. S., & Jung, Y. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b00462 · Cited by 545 · see citing works
Back, S., Lim, J., Kim, N.-Y., Kim, Y.-H., & Jung, Y. (2017) · Chemical Science · doi:10.1039/c6sc03911a · Cited by 542 · see citing works
Strategies for design of electrocatalysts for hydrogen evolution under alkaline conditions
Wang, X., Zheng, Y., Sheng, W., Xu, Z. J., Jaroniec, M., & Qiao, S.-Z. (2020) · Materials Today · doi:10.1016/j.mattod.2019.12.003 · Cited by 533 · see citing works
Ma, M., Trześniewski, B. J., Xie, J., & Smith, W. A. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201604654 · Cited by 530 · see citing works
Xiao, H., Cheng, T., & Goddard, W. A. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b06846 · Cited by 458 · see citing works
Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction
Eilert, A., Cavalca, F., Roberts, F. S., Osterwalder, J., Liu, C., Favaro, M., Crumlin, E. J., Ogasawara, H., Friebel, D., Pettersson, L. G. M., et al. (2017) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.6b02273 · Cited by 443 · see citing works
Lum, Y., & Ager, J. W. (2018) · Angewandte Chemie International Edition · doi:10.1002/anie.201710590 · Cited by 410 · see citing works
Jiang, K., Siahrostami, S., Akey, A. J., Li, Y., Lu, Z., Lattimer, J., Hu, Y., Stokes, C., Gangishetty, M., Chen, G., et al. (2017) · Chem · doi:10.1016/j.chempr.2017.09.014 · Cited by 406 · see citing works
Lum, Y., & Ager, J. W. (2018) · Nature Catalysis · doi:10.1038/s41929-018-0201-7 · Cited by 322 · see citing works
Torelli, D. A., Francis, S. A., Crompton, J. C., Javier, A., Thompson, J. R., Brunschwig, B. S., Soriaga, M. P., & Lewis, N. S. (2016) · ACS Catalysis · doi:10.1021/acscatal.5b02888 · Cited by 306 · see citing works
Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
Lum, Y., Cheng, T., Goddard, W. A., & Ager, J. W. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.8b03986 · Cited by 251 · see citing works
Effects of Anion Identity and Concentration on Electrochemical Reduction of CO <sub>2</sub>
Resasco, J., Lum, Y., Clark, E., Zeledon, J. Z., & Bell, A. T. (2018) · ChemElectroChem · doi:10.1002/celc.201701316 · Cited by 250 · see citing works
Tuning of CO<sub>2</sub> Reduction Selectivity on Metal Electrocatalysts
Wang, Y., Liu, J., Wang, Y., Al‐Enizi, A. M., & Zheng, G. (2017) · Small · doi:10.1002/smll.201701809 · Cited by 241 · see citing works
Face the Edges: Catalytic Active Sites of Nanomaterials
Ni, B., & Wang, X. (2015) · Advanced Science · doi:10.1002/advs.201500085 · Cited by 219 · see citing works
Hydronium-Induced Switching between CO2 Electroreduction Pathways
Seifitokaldani, A., Gabardo, C. M., Burdyny, T., Dinh, C.-T., Edwards, J. P., Kibria, M. G., Bushuyev, O. S., Kelley, S. O., Sinton, D., & Sargent, E. H. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.7b13542 · Cited by 179 · see citing works
Role of oxygen-bound reaction intermediates in selective electrochemical CO <sub>2</sub> reduction
Zhi, X., Vasileff, A., Zheng, Y., Jiao, Y., & Qiao, S.-Z. (2021) · Energy & Environmental Science · doi:10.1039/d1ee00740h · Cited by 149 · see citing works
The Role of Adsorbed CN and Cl on an Au Electrode for Electrochemical CO<sub>2</sub> Reduction
Cho, M., Song, J. T., Back, S., Jung, Y., & Oh, J. (2018) · ACS Catalysis · doi:10.1021/acscatal.7b03449 · Cited by 127 · see citing works
Liang, C., Kim, B., Yang, S., Yang Liu, Y. L., Francisco Woellner, C., Li, Z., Vajtai, R., Yang, W., Wu, J., Kenis, P. J. A., et al. (2018) · Journal of Materials Chemistry A · doi:10.1039/c8ta01367e · Cited by 124 · see citing works
Cavalca, F., Ferragut, R., Aghion, S., Eilert, A., Diaz-Morales, O., Liu, C., Koh, A. L., Hansen, T. W., Pettersson, L. G. M., & Nilsson, A. (2017) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.7b08278 · Cited by 123 · see citing works
Advanced manufacturing for electrosynthesis of fuels and chemicals from CO <sub>2</sub>
Corral, D., Feaster, J. T., Sobhani, S., DeOtte, J. R., Lee, D. U., Wong, A. A., Hamilton, J., Beck, V. A., Sarkar, A., Hahn, C., et al. (2021) · Energy & Environmental Science · doi:10.1039/d0ee03679j · Cited by 98 · see citing works
Self-citation
- Authors
- Kuhl, K. P., Hatsukade, T., Cave, E. R., Abram, D. N., Kibsgaard, J., & Jaramillo, T. F.
- Affiliations
- Stanford University (US)
- Corresponding author
- Jaramillo, Thomas F.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-09-26
- Volume
- 136
- Issue
- 40
- Pages
- 14107-14113
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2318989366
- Cited by
- 1,649
- References
- 36
- Citations by year
- 2026: 102 · 2025: 145 · 2024: 163 · 2023: 150 · 2022: 146 · 2021: 168 · 2020: 179 · 2019: 179 · 2018: 160 · 2017: 123 · 2016: 89 · 2015: 44
- FWCI
- 28.17
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (1066515)
- Ford Foundation
- Division of Graduate Education (DGE-1147470)
- Stanford University
- Mohr Davidow Ventures
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- electrochemical CO2 reduction, CO2 to methanol, transition metal surfaces, CO binding energy, catalyst selectivity, reaction rate, gold, silver, zinc, copper, nickel, platinum, iron, renewable fuels
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
