Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles
Open accessAbstract
Gold (Au) nanoparticles (NPs) are known experimentally to reduce carbon dioxide (CO 2 ) to carbon monoxide (CO), with far superior performance to Au foils. To obtain guidance in designing improved CO 2 catalysts, we want to understand the nature of the active sites on Au NPs. Here, we employed multiscale atomistic simulations to computationally synthesize and characterize a 10 nm thick Au NP on a carbon nanotube (CNT) support, and then we located active sites from quantum mechanics (QM) calculations on 269 randomly selected sites. The standard scaling relation is that the formation energy of *COOH (Δ E *COOH ) is proportional to the binding energy of *CO ( E binding *CO ); therefore, decreasing Δ E *COOH to boost the CO 2 reduction reaction (CO 2 RR) causes an increase of E binding *CO that retards CO 2 RR. We show that the NPs have superior CO 2 RR because there are many sites at the twin boundaries that significantly break this scaling relation.
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
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?
The NCNT performance was attributed to an optimum binding energy, yielding strong *COOH adsorption and *CO desorption.
“This performance was attributed to an optimum binding energy, yielding strong *COOH adsorption and *CO desorption.”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [87]
Wu et al. reported a nitrogen-doped carbon nanotube (NCNT) catalyst which obtained a FECO of 80% at an overpotential of 0.26 V.
“Wu et al. reported a nitrogen-doped carbon nanotube (NCNT) catalyst which obtained a FECO of 80% at an overpotential of 0.26 V. [87]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [87]
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Cites
Embedded-atom-method functions for the fcc metals Cu, Ag, Au, Ni, Pd, Pt, and their alloys
Foiles, S. M., Baskes, M. I., & Daw, M. S. (1986) · Physical review. B, Condensed matter · doi:10.1103/physrevb.33.7983 · Cited by 4,656 · 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
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
Kortlever, R., Shen, J., Schouten, K. J. P., Calle‐Vallejo, F., & Koper, M. T. M. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b01559 · Cited by 2,184 · see citing works
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
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
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
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
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
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
Future climate forcing potentially without precedent in the last 420 million years
Foster, G. L., Royer, D. L., & Lunt, D. J. (2017) · Nature Communications · doi:10.1038/ncomms14845 · Cited by 873 · 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
Grain-Boundary-Dependent CO <sub>2</sub> Electroreduction Activity
Feng, X., Jiang, K., Fan, S., & Kanan, M. W. (2015) · Journal of the American Chemical Society · doi:10.1021/ja5130513 · Cited by 694 · see citing works
Facet Dependence of CO 2 Reduction Paths on Cu Electrodes
Luo, W., Nie, X., Janik, M. J., & Asthagiri, A. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b01967 · Cited by 587 · 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
A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles
Feng, X., Jiang, K., Fan, S., & Kanan, M. W. (2016) · ACS Central Science · doi:10.1021/acscentsci.6b00022 · Cited by 460 · see citing works
Cheng, T., Xiao, H., & Goddard, W. A. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b08534 · Cited by 453 · see citing works
Self-citationInhibited proton transfer enhances Au-catalyzed CO 2 -to-fuels selectivity
Wuttig, A., Yaguchi, M., Motobayashi, K., Osawa, M., & Surendranath, Y. (2016) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1602984113 · Cited by 416 · see citing works
Hori, Y., Murata, A., Kikuchi, K., & Suzuki, S. (1987) · Journal of the Chemical Society Chemical Communications · doi:10.1039/c39870000728 · Cited by 282 · 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
Kim, K.-S., Kim, W. J., Lim, H.-K., Lee, E. K., & Kim, H. (2016) · ACS Catalysis · doi:10.1021/acscatal.6b00412 · Cited by 123 · see citing works
Development of Interatomic ReaxFF Potentials for Au–S–C–H Systems
Järvi, T. T., van Duin, A. C. T., Nordlund, K., et al. (2011) · The Journal of Physical Chemistry A · doi:10.1021/jp201496x · Cited by 102 · see citing works
A DFT-based genetic algorithm search for AuCu nanoalloy electrocatalysts for CO 2 reduction
Lysgaard, S., Mýrdal, J. S. G., Hansen, H. A., & Vegge, T. (2015) · Physical Chemistry Chemical Physics · doi:10.1039/c5cp00298b · Cited by 76 · see citing works
Flagged first, then by citations
Research works printed but not linked: 6
- To summarize, we employed multiscale simulations to 213 computationally "synthesize" a Au NP with a thickness of 10 214 nm on a CNT support. The XRD of this Au NP (Figure S1) 215 shows the FCC crystal structure, consistent with the 216 experimental results. The simulated TEM image (Figure 1B) 217 shows clear GB structures. A dislocation analysis shows that 1/ 218 6⟨112⟩ Shockley partial dislocations are most abundant, which 219 induces stacking defects on the surface. 220 To locate the active sites for CO 2 RR, we randomly selected 221 269 response sites out of 11 360 total sites (2.4%) for QM 222 calculations. The QM results show a linear relationship 223 between ΔE *COOH and ΔE CO , showing that most sites exhibit 224 the normal scaling relationship between *COOH stabilization, 225 *CO desorption, and HER. However, we find a substantial 226 fraction (10%) of NP sites on GBs or twin boundaries that 227 significantly decrease ΔE *COOH without increasing ΔE CO , 228 leading to superior CO 2 RR performance. 229 ■ ASSOCIATED CONTENT 230 * S Supporting Information 231 The Supporting Information is available free of charge on the 232 ACS Publications website at DOI: 10.1021/acs.jpclett.7b01335. 233 Simulation details, simulated XRD patterns, equation of 234 state of FCC Au, a Au octahedral model, and ReaxFF 235 parameters of Au and C (PDF) 236 ■ AUTHOR INFORMATION 237 Corresponding Author 238 *E-mail: wag@wag.caltech.edu. 239 ORCID 240 · DOI
- Nanoparticles. J. Am. Chem. Soc. 2014, 136, 6978-6986. (10) 285
- Zheng, X.; Dinh, C. T.; Fan, F.; Cao, C.; et al. Enhanced 287 Electrocatalytic CO 2 Reduction via Field-Induced Reagent Concen- 288 tration. Nature 2016, 537, 382-386. (11) 289
- Calculations with Explicit Water. J. Am. Chem. Soc. 2016, 138, 13802- 310 13805. (17311
- Elementary Steps. Angew. Chem., Int. Ed. 2013, 52, 2459-2462. (19) 316
- Electroreduction to Methane on Transition-Metal Catalysts. J. Phys. 322 Chem. Lett. 2012, 3, 251-258.
Cited by
Sorted by citations
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
- Authors
- Cheng, T., Huang, Y., Xiao, H., & Goddard, W. A.
- Affiliations
- California Institute of Technology (US)
- Corresponding author
- Goddard, William A.
- Venue
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-07-07
- Volume
- 8
- Issue
- 14
- Pages
- 3317-3320
- ISSN
- 1948-7185 (ISSN-L)
- OpenAlex
- W2731127878
- Cited by
- 50
- References
- 23
- Citations by year
- 2026: 3 · 2025: 1 · 2024: 2 · 2023: 7 · 2022: 5 · 2021: 7 · 2020: 5 · 2019: 7 · 2018: 12 · 2017: 1
- FWCI
- 1.83
- Type
- journal article
- Language
- en
- Open access
- green
- www.osti.gov
- Locations
- The Journal of Physical Chemistry Letters (publishedVersion)
- PubMed (publishedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- CaltechAUTHORS (California Institute of Technology) (submittedVersion)
- Funders
- Office of Science (DE-SC0004993)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Materials Science › Materials Chemistry › Catalytic Processes in Materials Science
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Keywords
- gold nanoparticles, carbon dioxide reduction, active site, CO adsorption, twin boundaries, carbon nanotube support, scaling laws, electrocatalysis
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
