Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
Abstract
One of the main challenges associated with the electrochemical CO or CO 2 reduction is poor selectivity toward energetically rich products. In order to promote selectivity toward hydrocarbons and alcohols, most notably, the hydrogen evolution reaction (HER) should be suppressed. To achieve this goal, we studied intermetallic compounds consisting of transition metal (TM) elements that can reduce CO (Ru, Co, Rh, Ir, Ni, Pd, Pt, and Cu) separated by TM and post transition metal elements (Ag, Au, Cd, Zn, Hg, In, Sn, Pb, Sb, and Bi) that are very poor HER catalysts. In total, 34 different stable binary bulk alloys forming from these elements have been investigated using density functional theory calculations. The electronic and geometric properties of the catalyst surface can be tuned by varying the size of the active centers and the elements forming them. We have identified six different potentially selective intermetallic surfaces on which CO can be reduced to methanol at potentials comparable to or even slightly positive than those for CO/CO 2 reduction to methane on Cu. Common features shared by most of the selective alloys are single TM sites. The role of single sites is to block parasitic HER and thereby promote CO reduction.
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?
To include solvation effects, the adsorption energies calculated in the vacuum approach were corrected by 0.1 eV for CO and CHO, 0.45 eV for OH, and 0.25 eV for R-OH.
“To include solvation effects, such as hydrogen bonding, the adsorption energies calculated in this approach were corrected by 0.1 eV for CO and CHO, 0.45 eV for OH, and 0.25 eV for R-OH, where R denotes a hydrocarbon.[31][32][33]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [31]
Cites
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
Self-citationPowering 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
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
Atlas of Electrochemical Equilibria in Aqueous Solutions
Pourbaix, M. (1974) · doi:10.5006/37502 · Cited by 8,095 · see citing works
Towards the computational design of solid catalysts
Nørskov, J. K., Bligaard, T., Rossmeisl, J., & Christensen, C. H. (2009) · Nature Chemistry · doi:10.1038/nchem.121 · Cited by 4,161 · see citing works
Self-citationComputational high-throughput screening of electrocatalytic materials for hydrogen evolution
Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I., & Nørskov, J. K. (2006) · Nature Materials · doi:10.1038/nmat1752 · Cited by 4,097 · 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
Self-citationAlloys of platinum and early transition metals as oxygen reduction electrocatalysts
Greeley, J., Stephens, I. E. L., Bondarenko, A. S., Johansson, T. P., Hansen, H. A., Jaramillo, T. F., Rossmeisl, J., Chorkendorff, I., & Nørskov, J. K. (2009) · Nature Chemistry · doi:10.1038/nchem.367 · Cited by 3,203 · see citing works
Self-citationSurface science studies of model fuel cell electrocatalysts
Markovic, N. (2002) · Surface Science Reports · doi:10.1016/s0167-5729(01)00022-x · Cited by 2,145 · see citing works
Hori, Y., Wakebe, H., Tsukamoto, T., & Koga, O. (1994) · Electrochimica Acta · doi:10.1016/0013-4686(94)85172-7 · Cited by 2,140 · see citing works
Stamenkovic, V., Mun, B. S., Mayrhofer, K. J. J., Ross, P. N., Markovic, N. M., Rossmeisl, J., Greeley, J., & Nørskov, J. K. (2006) · Angewandte Chemie International Edition · doi:10.1002/anie.200504386 · Cited by 2,109 · see citing works
Self-citationReal-space grid implementation of the projector augmented wave method
Mortensen, J. J., Hansen, L. B., & Jacobsen, K. W. (2005) · Physical Review B · doi:10.1103/physrevb.71.035109 · Cited by 2,050 · 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
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
Enabling direct H2O2 production through rational electrocatalyst design
Siahrostami, S., Verdaguer‐Casadevall, A., Karamad, M., Deiana, D., Malacrida, P., Wickman, B., Escudero‐Escribano, M., Paoli, E. A., Frydendal, R., Hansen, T. W., et al. (2013) · Nature Materials · doi:10.1038/nmat3795 · Cited by 1,616 · see citing works
Self-citationA 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
Kitchin, J. R., Nørskov, J. K., Barteau, M. A., & Chen, J. G. (2004) · Physical Review Letters · doi:10.1103/physrevlett.93.156801 · Cited by 1,491 · 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
Skúlason, E., Tripkovic, V., Björketun, M. E., Gudmundsdóttir, S., Karlberg, G., Rossmeisl, J., Bligaard, T., Jónsson, H., & Nørskov, J. K. (2010) · The Journal of Physical Chemistry C · doi:10.1021/jp1048887 · Cited by 1,271 · see citing works
Self-citationUnderstanding the electrocatalysis of oxygen reduction on platinum and its alloys
Stephens, I. E. L., Bandarenka, A. S., Vej-Hansen, U. G., Rossmeisl, J., & Chorkendorff, I. (2012) · Energy & Environmental Science · doi:10.1039/c2ee03590a · Cited by 1,179 · see citing works
Self-citationSchouten, 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
Marković, N. M., Grgur, B. N., & Ross, P. N. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp970930d · Cited by 913 · see citing works
Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation
DuBois, M. R., & DuBois, D. L. (2009) · Accounts of Chemical Research · doi:10.1021/ar900110c · Cited by 823 · see citing works
Single Atom Hot-Spots at Au–Pd Nanoalloys for Electrocatalytic H 2 O 2 Production
Jirkovsky, J. S., Panas, I., Ahlberg, E., Halasa, M., Romani, S., & Schiffrin, D. J. (2011) · Journal of the American Chemical Society · doi:10.1021/ja206477z · Cited by 787 · 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
Hori, Y., Kikuchi, K., Murata, A., & Suzuki, S. (1986) · Chemistry Letters · doi:10.1246/cl.1986.897 · Cited by 668 · see citing works
The Role of Atomic Ensembles in the Reactivity of Bimetallic Electrocatalysts
Maroun, F., Ozanam, F., Magnussen, O. M., & Behm, R. J. (2001) · Science · doi:10.1126/science.1061696 · Cited by 480 · see citing works
Neurock, M., Janik, M. J., & Więckowski, A. (2008) · Faraday Discussions · doi:10.1039/b804591g · Cited by 446 · see citing works
Calculated Phase Diagrams for the Electrochemical Oxidation and Reduction of Water over Pt(111)
Rossmeisl, J., Nørskov, J. K., Taylor, C. D., Janik, M. J., & Neurock, M. (2006) · The Journal of Physical Chemistry B · doi:10.1021/jp0631735 · Cited by 441 · see citing works
Self-citationSurface Strain versus Substrate Interaction in Heteroepitaxial Metal Layers: Pt on Ru(0001)
Schlapka, A., Lischka, M., Groß, A., Käsberger, U., & Jakob, P. (2003) · Physical Review Letters · doi:10.1103/physrevlett.91.016101 · Cited by 354 · see citing works
Hori, Y., Murata, A., Takahashi, R., & Suzuki, S. (1987) · Journal of the American Chemical Society · doi:10.1021/ja00250a044 · Cited by 354 · see citing works
Wang, K., Gasteiger, H. A., Marković, N. M., & ROSS, P. N. J. (1996) · Electrochimica Acta · doi:10.1016/0013-4686(96)00079-5 · Cited by 346 · see citing works
Strmcnik, D. S., Escudero‐Escribano, M., Kodama, K., Stamenković, V. R., Cuesta, Á., & Marković, N. M. (2010) · Nature Chemistry · doi:10.1038/nchem.771 · Cited by 336 · see citing works
Karlberg, G. S., Rossmeisl, J., & Nørskov, J. K. (2007) · Physical Chemistry Chemical Physics · doi:10.1039/b705938h · Cited by 322 · see citing works
Self-citationAbild‐Pedersen, F., & Andersson, M. (2007) · Surface Science · doi:10.1016/j.susc.2007.01.052 · Cited by 305 · see citing works
Electrochemical CO 2 and CO Reduction on Metal-Functionalized Porphyrin-like Graphene
Tripković, V., Vanin, M., Karamad, M., Björketun, M. E., Jacobsen, K. W., Thygesen, K. S., & Rossmeisl, J. (2013) · The Journal of Physical Chemistry C · doi:10.1021/jp306172k · Cited by 304 · see citing works
Self-citationElectrochemical Processing of Carbon Dioxide
Oloman, C. W., & Li, H. (2008) · ChemSusChem · doi:10.1002/cssc.200800015 · Cited by 288 · 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
Significance of single-electron energies for the description of CO on Pt(111)
Kresse, G., Gil, A., & Sautet, P. (2003) · Physical review. B, Condensed matter · doi:10.1103/physrevb.68.073401 · Cited by 256 · see citing works
Cuesta, Á. (2006) · Journal of the American Chemical Society · doi:10.1021/ja0644172 · Cited by 232 · see citing works
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces
Mason, S. E., Grinberg, I., & Rappe, A. M. (2004) · Physical Review B · doi:10.1103/physrevb.69.161401 · Cited by 229 · see citing works
Reactivity descriptors for direct methanol fuel cell anode catalysts
Ferrin, P. A., Nilekar, A. U., Greeley, J., Mavrikakis, M., & Rossmeisl, J. (2008) · Surface Science · doi:10.1016/j.susc.2008.08.011 · Cited by 191 · see citing works
Self-citationAdsorption-Driven Surface Segregation of the Less Reactive Alloy Component
Andersson, K. J., Calle‐Vallejo, F., Rossmeisl, J., & Chorkendorff, I. (2009) · Journal of the American Chemical Society · doi:10.1021/ja8089087 · Cited by 189 · see citing works
Self-citationStructure of Dealloyed PtCu3 Thin Films and Catalytic Activity for Oxygen Reduction
Yang, R., Leisch, J. E., Strasser, P., & Toney, M. F. (2010) · Chemistry of Materials · doi:10.1021/cm101090p · Cited by 181 · see citing works
Perspectives on the first principles elucidation and the design of active sites
Neurock, M. (2003) · Journal of Catalysis · doi:10.1016/s0021-9517(02)00115-x · Cited by 167 · see citing works
Menning, C. A., Hwu, H. H., & Chen, J. G. (2006) · The Journal of Physical Chemistry B · doi:10.1021/jp061697z · Cited by 155 · see citing works
Calle‐Vallejo, F., Martínez, J. I., García-Lastra, J. M., Abad, E., & Koper, M. T. M. (2012) · Surface Science · doi:10.1016/j.susc.2012.08.005 · Cited by 147 · see citing works
Bandarenka, A. S., Varela, A. S., Karamad, M., Calle‐Vallejo, F., Bech, L., Pérez-Alonso, F. J., Rossmeisl, J., Stephens, I. E. L., & Chorkendorff, I. (2012) · Angewandte Chemie International Edition · doi:10.1002/anie.201205314 · Cited by 108 · see citing works
Self-citationMonte Carlo simulations of adsorption-induced segregation
Christoffersen, E., Stoltze, P., & Nørskov, J. K. (2002) · Surface Science · doi:10.1016/s0039-6028(02)01158-5 · Cited by 90 · see citing works
Metal Oxide‐Supported Platinum Overlayers as Proton‐Exchange Membrane Fuel Cell Cathodes
Tripković, V., Abild‐Pedersen, F., Studt, F., Cerri, I., Nagami, T., Bligaard, T., & Rossmeisl, J. (2012) · ChemCatChem · doi:10.1002/cctc.201100308 · Cited by 46 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Progress 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
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
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
Hsieh, Y.-C., Senanayake, S. D., Zhang, Y., Xu, W., & Polyansky, D. E. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b01235 · Cited by 396 · 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
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
- Authors
- Karamad, M., Tripkovic, V., & Rossmeisl, J.
- Affiliations
- Technical University of Denmark (DK)
- Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, Fysikvej, Building 311, DK-2800 Kongens Lyngby, Denmark
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-06-13
- Volume
- 4
- Issue
- 7
- Pages
- 2268-2273
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2330796308
- Cited by
- 125
- References
- 50
- Citations by year
- 2026: 5 · 2025: 7 · 2024: 20 · 2023: 16 · 2022: 5 · 2021: 11 · 2020: 7 · 2019: 13 · 2018: 10 · 2017: 8 · 2016: 11 · 2015: 11 · 2014: 1
- FWCI
- 3.41
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Technical University of Denmark, DTU Orbit (Technical University of Denmark, DTU) (submittedVersion)
- 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
- CO electroreduction, intermetallic alloys, hydrogen evolution suppression, methanol selectivity, CO2 reduction, single-site catalysts, electronic structure, geometric structure, 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
