Insight into Electrochemical CO 2 Reduction on Surface-Molecule-Mediated Ag Nanoparticles
Abstract
The electrochemical CO 2 reduction reaction to form valued hydrocarbon molecules is an attractive process, because it can be coupled with renewable energy resources for carbon recycling. For an efficient CO 2 conversion, designing a catalyst with high activity and selectivity is crucial, because the CO 2 reduction reaction in aqueous media competes with the hydrogen evolution reaction (HER) intensely. We have developed a strategy to tune CO 2 reduction activity by modulating the binding energies of the intermediates on the electrocatalyst surfaces with the assistance of molecules that contain the functional group. We discovered that the amine functional group on Ag nanoparticle is highly effective in improving selective CO production (Faradaic efficiency to 94.2%) by selectively suppressing HER, while the thiol group rather increases HER activity. A density functional theory (DFT) calculation supports the theory that attaching amine molecules to Ag nanoparticles destabilizes the hydrogen binding, which effectively suppresses HER selectively, while an opposite tendency is found with thiol molecules. In addition, changes in the product selectivity, depending on the functional group, are also observed when the organic molecules are added after nanoparticle synthesis or nanoparticles are immobilized with an amine (or thiol)-containing anchoring agent. CO Faradaic efficiencies were consistently improved when the Ag nanoparticle was modified with amine groups, compared with that of its thiol counterpart.
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?
Differences in the oxidation state of Cu is another potential factor that may alter CO2RR activity.
“Differences in the oxidation state of Cu is another potential factor that may alter CO2RR activity.[92,93]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [92]
Haas et al. generated CO at 50 mA/cm2 for over 1000 h by forcing CO2 through their gas diffusion electrode, but did not operate at higher current densities without sacrificing selectivity.
“Recently, Haas et al. generated CO at 50 mA/cm 2 for over 1000 h by forcing the CO2 through their gas diffusion electrode; however, they did not operate at higher current densities without sacrificing selectivity.[92]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [92]
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
The SIESTA method for ab initio order- N materials simulation
Soler, J. M., Artacho, E., Gale, J. D., Garcı́a, A., Junquera, J., Ordejón, P., & Sánchez‐Portal, D. (2002) · Journal of Physics Condensed Matter · doi:10.1088/0953-8984/14/11/302 · Cited by 12,302 · see citing works
Self-consistent order- N density-functional calculations for very large systems
Ordejón, P., Artacho, E., & Soler, J. M. (1996) · Physical review. B, Condensed matter · doi:10.1103/physrevb.53.r10441 · Cited by 2,628 · 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
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 realizable renewable energy future
Turner, J. A. (1999) · Science · doi:10.1126/science.285.5428.687 · Cited by 1,642 · 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 selective and efficient electrocatalyst for carbon dioxide reduction
Lu, Q., Rosen, J., Zhou, Y., Hutchings, G. S., Kimmel, Y. C., Chen, J. G., & Jiao, F. (2014) · Nature Communications · doi:10.1038/ncomms4242 · Cited by 1,474 · see citing works
Prospects of CO 2 Utilization via Direct Heterogeneous Electrochemical Reduction
Whipple, D. T., & Kenis, P. J. A. (2010) · The Journal of Physical Chemistry Letters · doi:10.1021/jz1012627 · Cited by 1,419 · 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
Centi, G., Quadrelli, E. A., & Perathoner, S. (2013) · Energy & Environmental Science · doi:10.1039/c3ee00056g · Cited by 1,260 · see citing works
Sustainable hydrocarbon fuels by recycling CO 2 and H 2 O with renewable or nuclear energy
Graves, C., Ebbesen, S. D., Mogensen, M. B., & Lackner, K. S. (2010) · Renewable and Sustainable Energy Reviews · doi:10.1016/j.rser.2010.07.014 · Cited by 1,058 · 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
Kim, C., Jeon, H. S., Eom, T., Jee, M. S., Kim, H., Friend, C. M., Min, B. K., & Hwang, Y. J. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b06568 · Cited by 702 · see citing works
Self-citationZhang, S., Kang, P., Ubnoske, S. M., Brennaman, M. K., Song, N., House, R. L., Glass, J. T., & Meyer, T. J. (2014) · Journal of the American Chemical Society · doi:10.1021/ja5031529 · Cited by 659 · see citing works
Varela, A. S., Sahraie, N. R., Steinberg, J., Ju, W., Oh, H., & Strasser, P. (2015) · Angewandte Chemie International Edition · doi:10.1002/anie.201502099 · Cited by 617 · see citing works
Carbon Dioxide Capture from the Air Using a Polyamine Based Regenerable Solid Adsorbent
Goeppert, A., Czaun, M., May, R. B., Prakash, G. K. S., Olah, G. A., & Narayanan, S. R. (2011) · Journal of the American Chemical Society · doi:10.1021/ja2100005 · Cited by 558 · 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
Ionic Liquids for CO2 Capture and Emission Reduction
Brennecke, J. F., & Gurkan, B. (2010) · The Journal of Physical Chemistry Letters · doi:10.1021/jz1014828 · Cited by 551 · see citing works
Reversing the size-dependence of surface plasmon resonances
Peng, S., McMahon, J. M., Schatz, G. C., Gray, S. K., & Sun, Y. (2010) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1007524107 · Cited by 493 · 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
Silver Nanoparticles Capped by Oleylamine: Formation, Growth, and Self-Organization
Chen, M., Feng, Y., Wang, X., Li, T., Zhang, J., & Qian, D. (2007) · Langmuir · doi:10.1021/la700553d · Cited by 422 · see citing works
Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO<sub>2</sub>
Lim, H.-K., Shin, H., Goddard, W. A., Hwang, Y. J., Min, B. K., & Kim, H. (2014) · Journal of the American Chemical Society · doi:10.1021/ja503782w · Cited by 222 · see citing works
Self-citationLi, F., Zhao, S., Chen, L., Khan, A. A., MacFarlane, D. R., & Zhang, J. (2015) · Energy & Environmental Science · doi:10.1039/c5ee02879e · Cited by 191 · see citing works
Nitrogen-Based Catalysts for the Electrochemical Reduction of CO <sub>2</sub> to CO
Tornow, C. E., Thorson, M. R., Ma, S., Gewirth, A. A., & Kenis, P. J. A. (2012) · Journal of the American Chemical Society · doi:10.1021/ja308217w · Cited by 190 · see citing works
Size-controlled synthesis and characterization of thiol-stabilized gold nanoparticles
Frenkel, A. I., Nemzer, S., Pister, I., et al. (2005) · The Journal of Chemical Physics · doi:10.1063/1.2126666 · Cited by 125 · see citing works
Schmitt, K. G., & Gewirth, A. A. (2014) · The Journal of Physical Chemistry C · doi:10.1021/jp503598y · Cited by 118 · see citing works
Jee, M. S., Jeon, H. S., Kim, C., Lee, H., Koh, J. H., Cho, J., Min, B. K., & Hwang, Y. J. (2015) · Applied Catalysis B: Environmental · doi:10.1016/j.apcatb.2015.06.046 · Cited by 84 · see citing works
Self-citationde Castro, E. G., Salvatierra, R. V., Schreiner, W. H., Oliveira, M. M., & Zarbin, A. J. G. (2009) · Chemistry of Materials · doi:10.1021/cm902748k · Cited by 76 · see citing works
Structural and magnetic characterization of oleic acid and oleylamine-capped gold nanoparticles
de la Presa, P. M., Multigner, M., de la Venta, J., et al. (2006) · Journal of Applied Physics · doi:10.1063/1.2401314 · Cited by 74 · see citing works
Kim, C., & Lee, H. J. (2009) · Catalysis Communications · doi:10.1016/j.catcom.2009.02.013 · Cited by 68 · see citing works
Self-citationShin, H., Ha, Y., & Kim, H. (2016) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.6b01876 · Cited by 61 · see citing works
Self-citationJeon, H. S., Koh, J. H., Park, S. J., Jee, M. S., Ko, D.-H., Hwang, Y. J., & Min, B. K. (2014) · Journal of Materials Chemistry A · doi:10.1039/c4ta06495j · Cited by 56 · see citing works
Self-citationBattocchio, C., Fratoddi, I., Fontana, L., et al. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c4cp01264j · Cited by 44 · see citing works
Flagged first, then by citations
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
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
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
- Authors
- Kim, C., Eom, T., Jee, M. S., Jung, H., Kim, H., Min, B. K., & Hwang, Y. J.
- Affiliations
- Korea Institute of Science and Technology (KR)
- Korea Advanced Institute of Science and Technology (KR)
- Korea University (KR)
- Corresponding author
- Kim, Hyungjun
- Min, Byoung Koun
- Hwang, Yun Jeong
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-12-21
- Volume
- 7
- Issue
- 1
- Pages
- 779-785
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2560046959
- Cited by
- 265
- References
- 34
- Citations by year
- 2026: 17 · 2025: 21 · 2024: 24 · 2023: 30 · 2022: 31 · 2021: 47 · 2020: 32 · 2019: 35 · 2018: 18 · 2017: 10
- FWCI
- 5.70
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Seoul National University Open Repository (Seoul National University) (submittedVersion)
- Funders
- National Research Foundation of Korea
- Korea Institute of Science and Technology
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
- Keywords
- electrochemical CO2 reduction, silver nanoparticles, amine functionalization, thiol functionalization, hydrogen evolution suppression, CO selectivity, Faradaic efficiency, intermediate binding energy, surface modification, carbon recycling
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
