Active Sites of Au and Ag Nanoparticle Catalysts for CO2 Electroreduction to CO
Open accessAbstract
Highly active and selective CO2 conversion into useful chemicals is desirable to generate valuable products out of greenhouse gases. To date, various metal-based heterogeneous catalysts have shown promising electrochemical catalytic activities for CO2 reduction, yet there have been no systematic studies of the active sites of these metal catalysts that can guide further experiments. In this study, we use first-principles calculations to identify active sites for the CO2 reduction reaction for Ag and Au metals, the two metals that have been shown to be the most active in producing CO. We compare the catalytic activity and selectivity of three reaction sites of nanoparticles, namely, low-index surfaces, edge sites, and corner sites of these metals. For nanoparticle corner sites, in particular, we find that the size effect is critical, and 309-atom (or larger) nanoparticles should be used to appropriately describe realistic metal nanocatalysts. However, a 55-atom cluster model is often used in the literature to model nanoparticles. From a comparative study, we reveal that corner sites are the most active for the CO2 reduction reaction in the case of Au, whereas edge sites are the most active in the case of Ag. Although Au is generally the more active CO2 reduction catalyst than Ag due to the intrinsically stronger binding of *C-species, our results indicate that reducing the size of Au nanoparticles up to 2 nm also increases the unwanted H2 evolution reaction, as observed in a recent experiment. However, reducing the size of Ag nanoparticles up to 2 nm enhances the CO2 reduction reaction without suffering from the H2 evolution reaction, and on this basis, Ag nanoparticles are a comparable or even better-performing, inexpensive catalyst than Au for electrochemical CO production. Our findings suggest that the catalyst design principle (elemental composition, morphology, and size) is metal-dependent and should be carefully tailored for each system.
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?
A strong correlation between binding energies of various reaction intermediates on transition metals and a lack of ability to independently control them poses a significant intrinsic limitation in developing suitable catalysts for large-scale commercialization of the CO2 reduction reaction.
“general understanding at present is that a strong correlation between binding energies of various reaction intermediates on transition metals and a lack of ability to independently control them poses a significant intrinsic limitation in developing suitable catalysts for large-scale commercialization of the CO2 reduction reaction.”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [3]
For transition metals in general, the binding behaviors of *H, *COOH, and *CO all have the same tendency due to a well-known scaling relation.
“due to a well-known scaling relation, the binding behaviors of *H, *COOH, and *CO all have the same tendency for transition metals in general.3,7”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [3]
Cites
Generalized Gradient Approximation Made Simple
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996) · Physical Review Letters · doi:10.1103/physrevlett.77.3865 · Cited by 215,824 · see citing works
Projector augmented-wave method
Blöchl, P. E. (1994) · Physical Review B · doi:10.1103/physrevb.50.17953 · Cited by 92,732 · see citing works
From ultrasoft pseudopotentials to the projector augmented-wave method
Kresse, G., & Joubert, D. (1999) · Physical Review B · doi:10.1103/physrevb.59.1758 · Cited by 85,307 · see citing works
Kresse, G., & Furthmüller, J. (1996) · Computational Materials Science · doi:10.1016/0927-0256(96)00008-0 · Cited by 75,541 · see citing works
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
Nørskov, J. K., Rossmeisl, J., Logadottir, A., Lindqvist, L., Kitchin, J. R., Bligaard, T., & Jónsson, H. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp047349j · Cited by 13,153 · see citing works
Daniel, M., & Astruc, D. (2003) · Chemical Reviews · doi:10.1021/cr030698+ · Cited by 12,486 · see citing works
Hammer, B., Hansen, L. B., & Nørskov, J. K. (1999) · Physical Review B · doi:10.1103/physrevb.59.7413 · Cited by 8,270 · see citing works
Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction
Liang, Y., Li, Y., Wang, H., Zhou, J., Wang, J., Regier, T., & Dai, H. (2011) · Nature Materials · doi:10.1038/nmat3087 · Cited by 5,492 · see citing works
Li, Y., Wang, H., Xie, L., Liang, Y., Hong, G., & Dai, H. (2011) · Journal of the American Chemical Society · doi:10.1021/ja201269b · Cited by 5,001 · 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
Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction
Popczun, E. J., McKone, J. R., Read, C. G., Biacchi, A. J., Wiltrout, A. M., Lewis, N. S., & Schaak, R. E. (2013) · Journal of the American Chemical Society · doi:10.1021/ja403440e · Cited by 2,911 · see citing works
The teraton challenge. A review of fixation and transformation of carbon dioxide
Mikkelsen, M. S., Jørgensen, M., & Krebs, F. C. (2009) · Energy & Environmental Science · doi:10.1039/b912904a · Cited by 2,152 · see citing works
Li, C. W., & Kanan, M. W. (2012) · Journal of the American Chemical Society · doi:10.1021/ja3010978 · Cited by 2,000 · see citing works
Electrochemical CO2 Reduction on Metal Electrodes
Hori, Y. (2008) · Springer eBooks · doi:10.1007/978-0-387-49489-0_3 · Cited by 1,904 · see citing works
Activity 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
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
Kuhl, K. P., Hatsukade, T., Cave, E. R., Abram, D. N., Kibsgaard, J., & Jaramillo, T. F. (2014) · Journal of the American Chemical Society · doi:10.1021/ja505791r · Cited by 1,649 · 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
Particle Size Effects in the Catalytic Electroreduction of CO2 on Cu Nanoparticles
Reske, R., Mistry, H., Behafarid, F., Cuenya, B. R., & Strasser, P. (2014) · Journal of the American Chemical Society · doi:10.1021/ja500328k · Cited by 1,435 · 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
Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO
Zhu, W., Michalsky, R., Metin, Ö., Lv, H., Guo, S., Wright, C. J., Sun, X., Peterson, A. A., & Sun, S. (2013) · Journal of the American Chemical Society · doi:10.1021/ja409445p · Cited by 1,379 · see citing works
On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation
López, N. (2004) · Journal of Catalysis · doi:10.1016/j.jcat.2004.01.001 · Cited by 1,215 · see citing works
Size-Dependent Electrocatalytic Reduction of CO 2 over Pd Nanoparticles
Gao, D., Zhou, H., Wang, J., Miao, S., Yang, F., Wang, G., Wang, J., & Bao, X. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b00046 · Cited by 1,096 · see citing works
Catalytic activity of Au nanoparticles
Hvolbæk, B., Janssens, T. V. W., Clausen, B. S., Falsig, H., Christensen, C. H., & Nørskov, J. K. (2007) · Nano Today · doi:10.1016/s1748-0132(07)70113-5 · Cited by 889 · see citing works
Active and Selective Conversion of CO <sub>2</sub> to CO on Ultrathin Au Nanowires
Zhu, W., Zhang, Y.-J., Zhang, H., Lv, H., Li, Q., Michalsky, R., Peterson, A. A., & Sun, S. (2014) · Journal of the American Chemical Society · doi:10.1021/ja5095099 · Cited by 860 · see citing works
Catalytic CO Oxidation by a Gold Nanoparticle: A Density Functional Study
López, N., & Nørskov, J. K. (2002) · Journal of the American Chemical Society · doi:10.1021/ja026998a · Cited by 742 · see citing works
Tang, W., Peterson, A. A., Varela, A. S., Jovanov, Z. P., Bech, L., Durand, W. J., Dahl, S., Nørskov, J. K., & Chorkendorff, I. (2011) · Physical Chemistry Chemical Physics · doi:10.1039/c1cp22700a · Cited by 691 · see citing works
Mistry, H., Reske, R., Zeng, Z., Zhao, Z.-J., Greeley, J., Strasser, P., & Cuenya, B. R. (2014) · Journal of the American Chemical Society · doi:10.1021/ja508879j · Cited by 690 · see citing works
Wu, J., Yadav, R. M., Liu, M., Sharma, P. P., Tiwary, C. S., Ma, L., Zou, X., Zhou, X.-D., Yakobson, B. I., Lou, J., et al. (2015) · ACS Nano · doi:10.1021/acsnano.5b01079 · Cited by 652 · see citing works
The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations
Tripković, V., Skúlason, E., Siahrostami, S., Nørskov, J. K., & Rossmeisl, J. (2010) · Electrochimica Acta · doi:10.1016/j.electacta.2010.02.056 · Cited by 597 · 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
Insights into the reactivity of supported Au nanoparticles: combining theory and experiments
Janssens, T. V. W., Clausen, B. S., Hvolbæk, B., et al. (2007) · Topics in Catalysis · doi:10.1007/s11244-007-0335-3 · Cited by 437 · 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
Core/Shell Pd/FePt Nanoparticles as an Active and Durable Catalyst for the Oxygen Reduction Reaction
Mazumder, V., Chi, M., More, K. L., & Sun, S. (2010) · Journal of the American Chemical Society · doi:10.1021/ja1024436 · Cited by 373 · see citing works
Yang, H., Vogel, W., Lamy, C., & Alonso‐Vante, N. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp049034+ · Cited by 322 · see citing works
Electrochemical reduction of CO2 on single crystal electrodes of silver Ag(111), Ag(100) and Ag(110)
Hoshi, N., Kato, M., & Hori, Y. (1997) · Journal of Electroanalytical Chemistry · doi:10.1016/s0022-0728(97)00447-6 · Cited by 304 · see citing works
Chen, S., Ferreira, P. J., Sheng, W., Yabuuchi, N., Allard, L. F., & Shao‐Horn, Y. (2008) · Journal of the American Chemical Society · doi:10.1021/ja802513y · Cited by 277 · see citing works
Finite Size Effects in Chemical Bonding: From Small Clusters to Solids
Kleis, J., Greeley, J., Romero, N. A., Morozov, V., Falsig, H., Larsen, A. H., Lu, J., Mortensen, J. J., Dułak, M., Thygesen, K. S., et al. (2011) · Catalysis Letters · doi:10.1007/s10562-011-0632-0 · Cited by 271 · 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
Selective Heterogeneous CO<sub>2</sub> Electroreduction to Methanol
Back, S., Kim, H., & Jung, Y. (2015) · ACS Catalysis · doi:10.1021/cs501600x · Cited by 201 · see citing works
Self-citationCO oxidation on gold nanoparticles: Theoretical studies
Remediakis, I. N., López, N., & Nørskov, J. K. (2005) · Applied Catalysis A General · doi:10.1016/j.apcata.2005.01.052 · Cited by 192 · see citing works
Han, B., Miranda, C. R., & Ceder, G. (2008) · Physical Review B · doi:10.1103/physrevb.77.075410 · Cited by 188 · see citing works
Rasul, S., Anjum, D. H., Jedidi, A., Minenkov, Y. V., Cavallo, L., & Takanabe, K. (2014) · Angewandte Chemie · doi:10.1002/ange.201410233 · Cited by 143 · see citing works
Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
Karamad, M., Tripkovic, V., & Rossmeisl, J. (2014) · ACS Catalysis · doi:10.1021/cs500328c · Cited by 125 · see citing works
Tang, D., & Hu, C. (2011) · The Journal of Physical Chemistry Letters · doi:10.1021/jz201290x · Cited by 72 · see citing works
First-principles studies for CO and O2 on gold nanocluster
Xie, Y., & Gong, X.-G. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3455714 · Cited by 28 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
Liu, M., Pang, Y., Zhang, B., De Luna, P., Voznyy, O., Xu, J., Zheng, X., Dinh, C. T., Fan, F., Cao, C., et al. (2016) · Nature · doi:10.1038/nature19060 · Cited by 2,000 · 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
Self-citationMetallenes as functional materials in electrocatalysis
Prabhu, P., & Lee, J.-M. (2021) · Chemical Society Reviews · doi:10.1039/d0cs01041c · Cited by 427 · 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
Self-citationInfluencing electrocatalytic processes through topographically disordered atomic sites
Prabhu, P., & Lee, J.-M. (2023) · Chem Catalysis · doi:10.1016/j.checat.2023.100621 · Cited by 84 · see citing works
Cheng, T., Huang, Y., Xiao, H., & Goddard, W. A. (2017) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.7b01335 · Cited by 50 · see citing works
Gong, S., Xiao, X., Wang, W., Sam, D. K., Lu, R., Xu, Y., Liu, J., Wu, C., & Lv, X. (2021) · Journal of Colloid and Interface Science · doi:10.1016/j.jcis.2021.05.054 · Cited by 42 · see citing works
- Authors
- Back, S., Yeom, M. S., & Jung, Y.
- Affiliations
- Korea Advanced Institute of Science and Technology (KR)
- KISTI National Supercomputing Center (KR)
- Corresponding author
- Jung, Yousung
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-07-13
- Volume
- 5
- Issue
- 9
- Pages
- 5089-5096
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2497854141
- Cited by
- 545
- References
- 45
- Citations by year
- 2026: 28 · 2025: 33 · 2024: 57 · 2023: 53 · 2022: 61 · 2021: 70 · 2020: 52 · 2019: 77 · 2018: 54 · 2017: 35 · 2016: 25
- FWCI
- 11.23
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- ACS Catalysis (publishedVersion, other-oa)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- U.S. Department of Energy (DE-FG01-05EW07033)
- National Science Foundation (DMR-1407658, CHE-0847262, CHE-1306730)
- Villum Fonden (10096)
- European Cooperation in Science and Technology (CM1204)
- Agence Nationale de la Recherche (ANR-08-BLAN-0065)
- Ministry of Education, Culture, Sports, Science, and Technology (22350064)
- National Natural Science Foundation of China (20937002, 21120102040, 21274013, 21275004, 21275119, 21372255, 21472251, 41276146, 51073036, 51373034, U1403301)
- Ministry of Education of the People's Republic of China (141gjc16, NA, XDJK2014A012)
- Dalian Institute of Chemical Physics (NA)
- National Research Foundation of Korea (2011-35B-C00024, 2013R1A1A2061694, 2014R1A1A1002642, NRF-2014H1A2A1016055)
- Program for New Century Excellent Talents in University (NCET-12-0932)
- Ministry of Land and Resources of the People's Republic of China (201305017)
- Seventh Framework Programme (608575)
- Agency for Defense Development (UD140047GD)
- Innovation Fund Denmark (0603-00462B)
- Ministarstvo Prosvete, Nauke i Tehnoloskog Razvoja, Republika Srbija (171020)
- The National Basic Research Program of China (2013CB430002, 2013CB430004)
- AKTION (70p10, NA)
- European Regional Development Fund (CZ.1.05/1.1.00/02.0068)
- Ministerio de Economia y Competitividad (FIS2010-21282-C02-01, FIS2012-30996, NA)
- Beta Cat Pharmaceuticals LLC (NA)
- CEITEC Central European Institute of Technology (NA)
- New Century Excellent Talent Program of MOE (NA, NCET-12-0932)
- Technology Agency of the Czech Republic (NA, TE01020233)
- Fundamental Research Funds for the Central Universities (XDJK2014A012)
- 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 › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Keywords
- electrochemical CO2 reduction, gold nanoparticles, silver nanoparticles, active site, corner sites, edge sites, low-index surfaces, nanoparticle size effects, catalyst selectivity
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
