Multimetallic nanoparticles are of interest as functional materials due to their highly tunable properties. However, synthesizing congruent mixtures of immiscible components is limited by the need for high-temperature procedures followed by rapid quenching that lack size and shape control. Here we report a low-temperature (≤80 °C) non-equilibrium synthesis of nanosurface alloys (NSAs) with tunable size, shape and composition regardless of miscibility. We show the generality of our method by producing both bulk miscible and immiscible monodisperse anisotropic Cu-based NSAs of up to three components. We demonstrate our synthesis as a screening platform to investigate the effects of crystal facet and elemental composition by testing tetrahedral, cubic and truncated-octahedral NSAs as catalysts in the electroreduction of CO2. The use of machine learning has enabled the prediction and informed synthesis of both multicarbon-product-selective and phase-stable Cu–Ag–Pd compositions. This combination of non-equilibrium synthesis and theory-guided candidate selection is expected to accelerate test–learn–repeat cycles of structure–performance optimization processes.
This is a preview of subscription content, access via your institution
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Rent or buy this article
Prices vary by article type
Prices may be subject to local taxes which are calculated during checkout
The data generated in this study are provided in supplementary information and source data. Source data are provided with this paper.
DFT simulated atomic structures have been made freely available at https://nano.ku.dk/english/research/theoretical-electrocatalysis/katladb/co2-reduction-on-ag-cu-pd/.
Cui, C., Gan, L., Heggen, M., Rudi, S. & Strasser, P. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat. Mater. 12, 765–771 (2013).
Niu, Z. et al. Anisotropic phase segregation and migration of Pt in nanocrystals en route to nanoframe catalysts. Nat. Mater. 15, 1188–1194 (2016).
Taccardi, N. et al. Gallium-rich Pd–Ga phases as supported liquid metal catalysts. Nat. Chem. 9, 862–867 (2017).
Zhou, L. et al. Quantifying hot carrier and thermal contributions in plasmonic photocatalysis. Science 362, 69–72 (2018).
Batchelor, T. A. A. et al. High-entropy alloys as a discovery platform for electrocatalysis. Joule 3, 834–845 (2019).
Zhang, X. et al. Reversible loss of core–shell structure for Ni–Au bimetallic nanoparticles during CO2 hydrogenation. Nat. Catal. 3, 411–417 (2020).
Xing, F., Nakaya, Y., Yasumura, S., Shimizu, K. & Furukawa, S. Ternary platinum–cobalt–indium nanoalloy on ceria as a highly efficient catalyst for the oxidative dehydrogenation of propane using CO2. Nat. Catal. 5, 55–65 (2022).
Pedersen, J. K., Batchelor, T. A. A., Bagger, A. & Rossmeisl, J. High-entropy alloys as catalysts for the CO2 and CO reduction reactions. ACS Catal. 10, 2169–2176 (2020).
Sankar, M. et al. Designing bimetallic catalysts for a green and sustainable future. Chem. Soc. Rev. 41, 8099–8139 (2012).
Xie, C., Niu, Z., Kim, D., Li, M. & Yang, P. Surface and interface control in nanoparticle catalysis. Chem. Rev. 120, 1184–1249 (2020).
Tabrizi, N. S., Xu, Q., van der Pers, N. M. & Schmidt-Ott, A. Generation of mixed metallic nanoparticles from immiscible metals by spark discharge. J. Nanoparticle Res. 12, 247–259 (2010).
Kane, K. A., Reber, A. C., Khanna, S. N. & Bertino, M. F. Laser synthesized nanoparticle alloys of metals with bulk miscibility gaps. Prog. Nat. Sci. Mater. Int. 28, 456–463 (2018).
Feng, J., Ramlawi, N., Biskos, G. & Schmidt-Ott, A. Internally mixed nanoparticles from oscillatory spark ablation between electrodes of different materials. Aerosol Sci. Technol. 52, 505–514 (2018).
Yao, Y. et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 359, 1489–1494 (2018).
Yang, C. et al. Overcoming immiscibility toward bimetallic catalyst library. Sci. Adv. 6, eaaz6844 (2020).
Guntern, Y. T. et al. Colloidal nanocrystals as electrocatalysts with tunable activity and selectivity. ACS Catal. 11, 1248–1295 (2021).
Hori, Y., Takahashi, I., Koga, O. & Hoshi, N. Selective formation of C2 compounds from electrochemical reduction of CO2 at a series of copper single crystal electrodes. J. Phys. Chem. B 106, 15–17 (2002).
Loiudice, A. et al. Tailoring copper nanocrystals towards C2 products in electrochemical CO2 reduction. Angew. Chem. Int. Ed. 55, 5789–5792 (2016).
Iyengar, P., Huang, J., Gregorio, G. L. D., Gadiyar, C. & Buonsanti, R. Size dependent selectivity of Cu nano-octahedra catalysts for the electrochemical reduction of CO2 to CH4. Chem. Commun. 55, 8796–8799 (2019).
Schouten, K. J. P., Pérez Gallent, E. & Koper, M. T. M. Structure sensitivity of the electrochemical reduction of carbon monoxide on copper single crystals. ACS Catal. 3, 1292–1295 (2013).
Clark, E. L., Hahn, C., Jaramillo, T. F. & Bell, A. T. Electrochemical CO2 reduction over compressively strained CuAg surface alloys with enhanced multi-carbon oxygenate selectivity. J. Am. Chem. Soc. 139, 15848–15857 (2017).
Higgins, D. et al. Guiding electrochemical carbon dioxide reduction toward carbonyls using copper silver thin films with interphase miscibility. ACS Energy Lett. 3, 2947–2955 (2018).
Wang, X. et al. Efficient electrosynthesis of n-propanol from carbon monoxide using a Ag–Ru–Cu catalyst. Nat. Energy 7, 170–176 (2022).
Xia, X., Wang, Y., Ruditskiy, A. & Xia, Y. 25th anniversary article: galvanic replacement: a simple and versatile route to hollow nanostructures with tunable and well-controlled properties. Adv. Mater. 25, 6313–6333 (2013).
Subramanian, P. R. & Perepezko, J. H. The Ag–Cu (silver–copper) system. J. Phase Equilibria 14, 62–75 (1993).
Kim, N. R., Shin, K., Jung, I., Shim, M. & Lee, H. M. Ag–Cu bimetallic nanoparticles with enhanced resistance to oxidation: a combined experimental and theoretical study. J. Phys. Chem. C 118, 26324–26331 (2014).
Lee, C., Kim, N. R., Koo, J., Lee, Y. J. & Lee, H. M. Cu–Ag core–shell nanoparticles with enhanced oxidation stability for printed electronics. Nanotechnology 26, 455601 (2015).
Osowiecki, W. T. et al. Tailoring morphology of Cu–Ag nanocrescents and core–shell nanocrystals guided by a thermodynamic model. J. Am. Chem. Soc. 140, 8569–8577 (2018).
Huang, J., Mensi, M., Oveisi, E., Mantella, V. & Buonsanti, R. Structural sensitivities in bimetallic catalysts for electrochemical CO2 reduction revealed by Ag–Cu nanodimers. J. Am. Chem. Soc. 141, 2490–2499 (2019).
Hoang, T. T. H. et al. Nanoporous copper–silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791–5797 (2018).
Dettelbach, K. E. et al. Kinetic phases of Ag–Cu alloy films are accessible through photodeposition. J. Mater. Chem. A 7, 711–715 (2019).
Ruban, A. V., Skriver, H. L. & Nørskov, J. K. Surface segregation energies in transition-metal alloys. Phys. Rev. B 59, 15990–16000 (1999).
Koolen, C. D. et al. High-throughput sizing, counting, and elemental analysis of anisotropic multimetallic nanoparticles with single-particle inductively coupled plasma mass spectrometry. ACS Nano 16, 11968–11978 (2022).
Tran, R. et al. Surface energies of elemental crystals. Sci. Data 3, 160080 (2016).
Koolen, C. D., Luo, W. & Züttel, A. From single crystal to single atom catalysts: structural factors influencing the performance of metal catalysts for CO2 electroreduction. ACS Catal. 13, 948–973 (2022).
Sprunger, P. T., Lægsgaard, E. & Besenbacher, F. Growth of Ag on Cu(100) studied by STM: from surface alloying to Ag superstructures. Phys. Rev. B 54, 8163–8171 (1996).
Berakdar, J. & Kirschner, J. Many-Particle Spectroscopy of Atoms, Molecules, Clusters, and Surfaces (Springer, 2001).
Kim, D., Resasco, J., Yu, Y., Asiri, A. M. & Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat. Commun. 5, 1–8 (2014).
Frenkel, A. I., Yevick, A., Cooper, C. & Vasic, R. Modeling the structure and composition of nanoparticles by extended X-ray absorption fine-structure spectroscopy. Annu. Rev. Anal. Chem. 4, 23–39 (2011).
Sun, D. T. et al. Rapid, selective heavy metal removal from water by a metal–organic framework/polydopamine composite. ACS Cent. Sci. 4, 349–356 (2018).
Bencan, A. et al. Atomic scale symmetry and polar nanoclusters in the paraelectric phase of ferroelectric materials. Nat. Commun. 12, 3509 (2021).
Hansen, M. & Anderko, K. Constitution of Binary Alloys 2nd edn (McGraw Hill Book Company, 1958).
Tsaur, B. Y., Lau, S. S. & Mayer, J. W. Continuous series of metastable Ag–Cu solid solutions formed by ion‐beam mixing. Appl. Phys. Lett. 36, 823–826 (1980).
Cheng, H., Wang, C., Qin, D. & Xia, Y. Galvanic replacement synthesis of metal nanostructures: bridging the gap between chemical and electrochemical approaches. Acc. Chem. Res. 56, 900–909 (2023).
Bratsch, S. G. Standard electrode potentials and temperature coefficients in water at 298.15 K. J. Phys. Chem. Ref. Data 18, 1–21 (1989).
Hori, Y., Takahashi, I., Koga, O. & Hoshi, N. Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes. J. Mol. Catal. Chem. 199, 39–47 (2003).
Wu, Z.-Z. et al. Identification of Cu(100)/Cu(111) interfaces as superior active sites for CO dimerization during CO2 electroreduction. J. Am. Chem. Soc. 144, 259–269 (2022).
Salehi-Khojin, A. et al. Nanoparticle silver catalysts that show enhanced activity for carbon dioxide electrolysis. J. Phys. Chem. C 117, 1627–1632 (2013).
Wang, L. et al. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. Proc. Natl Acad. Sci. USA 117, 12572–12575 (2020).
Nitopi, S. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev 119, 7610–7672 (2019).
Iyengar, P., Kolb, M. J., Pankhurst, J. R., Calle-Vallejo, F. & Buonsanti, R. Elucidating the facet-dependent selectivity for CO2 electroreduction to ethanol of Cu–Ag tandem catalysts. ACS Catal. 11, 4456–4463 (2021).
Iyengar, P., Kolb, M. J., Pankhurst, J., Calle-Vallejo, F. & Buonsanti, R. Theory-guided enhancement of CO2 reduction to ethanol on Ag–Cu tandem catalysts via particle-size effects. ACS Catal. 11, 13330–13336 (2021).
Yu, J. et al. Recent progresses in electrochemical carbon dioxide reduction on copper-based catalysts toward multicarbon products. Adv. Funct. Mater. 31, 2102151 (2021).
Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).
Zhou, Y. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat. Chem. 10, 974–980 (2018).
Lum, Y. & Ager, J. W. Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. Energy Environ. Sci. 11, 2935–2944 (2018).
Subramanian, P. R. & Laughlin, D. E. Cu–Pd (copper–palladium). J. Phase Equilibria 12, 231–243 (1991).
Bagger, A., Ju, W., Varela, A. S., Strasser, P. & Rossmeisl, J. Electrochemical CO2 reduction: a classification problem. Chem. Phys. Chem. 18, 3266–3273 (2017).
Clausen, C. M., Pedersen, J. K., Batchelor, T. A. A. & Rossmeisl, J. Lattice distortion releasing local surface strain on high-entropy alloys. Nano Res. 15, 4775–4779 (2022).
Mortensen, J. J., Hansen, L. B. & Jacobsen, K. W. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B 71, 035109 (2005).
Enkovaara, J. et al. Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method. J. Phys. Condens. Matter 22, 253202 (2010).
Larsen, A. H. et al. The atomic simulation environment—a Python library for working with atoms. J. Phys. Condens. Matter 29, 273002 (2017).
Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).
This research was supported by Swiss National Science Foundation (Ambizione Project PZ00P2_179989). M.L. acknowledges the financial support from China Scholarship Council (grant no. 201506060156). J.K.P. and J.R. acknowledge support from the Danish National Research Foundation Center for High Entropy Alloy Catalysis (CHEAC) DNRF-149. L. Menin and N. Gasilova of the Mass Spectrometry and Elemental Analysis Platform (MSEAP), Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École Polytechnique Fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland, are acknowledged for their facilitation of the ICP–MS/OES measurements. S. Phadke is acknowledged for his assistance in the preparation of the capillaries.
The authors declare no competing interests.
Peer review information
Nature Synthesis thanks Joel Ager III and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Koolen, C.D., Oveisi, E., Zhang, J. et al. Low-temperature non-equilibrium synthesis of anisotropic multimetallic nanosurface alloys for electrochemical CO2 reduction. Nat. Synth (2023). https://doi.org/10.1038/s44160-023-00387-3
This article is cited by
Nature Synthesis (2023)