Oxidation-induced phase separation of carbon-supported CuAu nanoparticles for electrochemical reduction of CO2
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Langli Luo1,2(
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Alloy nanostructures have been extensively exploited in both thermal and electrochemical catalysis due to their beneficial “synergetic effects” and being cost-effective. Understandings of the alloy nanostructures including phases, interfaces, and chemical composition are prerequisites for utilizing them as efficient electrocatalysts. Here, we use carbon-supported CuAu nanoparticles as a model catalyst to demonstrate the phase-separation induced variation of electrochemical performance for the CO2 reduction reaction. Driven by thermal oxidation, the CuOx phase gradually separates from the original CuAu nanoparticles, and different carbon supports, i.e., graphene vs. carbon nanotube lead to a reversed trend in the selectivity towards CO production. Through detailed structural and chemical analysis, we find the extent of phase separation holds the key to this variation and could be used as an effective method to tune the electrochemical properties of the alloy phase.
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Oxidation-induced phase separation of carbon-supported CuAu nanoparticles for electrochemical reduction of CO2
), Langli Luo1,2(
)
Abstract
Alloy nanostructures have been extensively exploited in both thermal and electrochemical catalysis due to their beneficial “synergetic effects” and being cost-effective. Understandings of the alloy nanostructures including phases, interfaces, and chemical composition are prerequisites for utilizing them as efficient electrocatalysts. Here, we use carbon-supported CuAu nanoparticles as a model catalyst to demonstrate the phase-separation induced variation of electrochemical performance for the CO2 reduction reaction. Driven by thermal oxidation, the CuOx phase gradually separates from the original CuAu nanoparticles, and different carbon supports, i.e., graphene vs. carbon nanotube lead to a reversed trend in the selectivity towards CO production. Through detailed structural and chemical analysis, we find the extent of phase separation holds the key to this variation and could be used as an effective method to tune the electrochemical properties of the alloy phase.
References(29)
Wei, Z. H.; Sun, J. M.; Li, Y.; Datye, A. K.; Wang, Y. Bimetallic catalysts for hydrogen generation. Chem. Soc. Rev. 2012, 41, 7994–8008.
Fang, H.; Yang, J. H.; Wen, M.; Wu, Q. S. Nanoalloy materials for chemical catalysis. Adv. Mater. 2018, 30, 1705698.
Sankar, M.; Dimitratos, N.; Miedziak, P. J.; Wells, P. P.; Kiely, C. J.; Hutchings, G. J. Designing bimetallic catalysts for a green and sustainable future. Chem. Soc. Rev. 2012, 41, 8099–8139.
Tao, F. Synthesis, catalysis, surface chemistry and structure of bimetallic nanocatalysts. Chem. Soc. Rev. 2012, 41, 7977–7979.
Zhang, X. B.; Han, S. B.; Zhu, B. E.; Zhang, G. H.; Li, X. Y.; Gao, Y.; Wu, Z. X.; Yang, B.; Liu, Y. F.; Baaziz, W. et al. Reversible loss of core–shell structure for Ni-Au bimetallic nanoparticles during CO2 hydrogenation. Nat. Catal. 2020, 3, 411–417.
van der Hoeven, J. E. S.; Jelic, J.; Olthof, L. A.; Totarella, G.; van Dijk-Moes, R. J. A.; Krafft, J. M.; Louis, C.; Studt, F.; van Blaaderen, A.; de Jongh, P. E. Unlocking synergy in bimetallic catalysts by core–shell design. Nat. Mater. 2021, 20, 1216–1220.
Watanabe, M.; Shibata, M.; Kato, A.; Azuma, M.; Sakata, T. Design of alloy electrocatalysts for CO2 reduction: III. The selective and reversible reduction of CO2 on Cu alloy electrodes.
Watanabe, M.; Shibata, M.; Katoh, A.; Sakata, T.; Azuma, M. Design of alloy electrocatalysts for CO2 reduction: Improved energy efficiency, selectivity, and reaction rate for the CO2 electroreduction on Cu alloy electrodes. J. Electroanal. Chem. Interfacial Electrochem. 1991, 305, 319–328.
Friebel, D.; Mbuga, F.; Rajasekaran, S.; Miller, D. J.; Ogasawara, H.; Alonso-Mori, R.; Sokaras, D.; Nordlund, D.; Weng, T. C.; Nilsson, A. Structure, redox chemistry, and interfacial alloy formation in monolayer and multilayer Cu/Au(111) model catalysts for CO2 electroreduction. J. Phys. Chem. C 2014, 118, 7954–7961.
Chen, C. B.; Li, Y. F.; Yu, S.; Louisia, S.; Jin, J. B.; Li, M. F.; Ross, M. B.; Yang, P. D. Cu-Ag tandem catalysts for high-rate CO2 electrolysis toward multicarbons. Joule 2020, 4, 1688–1699.
Lv, X. M.; Shang, L. M.; Zhou, S.; Li, S.; Wang, Y. H.; Wang, Z. Q.; Sham, T. K.; Peng, C.; Zheng, G. F. Electron-deficient Cu sites on Cu3Ag1 catalyst promoting CO2 electroreduction to alcohols. Adv. Energy Mater. 2020, 10, 2001987.
Pardo Pérez, L. C.; Arndt, A.; Stojkovikj, S.; Ahmet, I. Y.; Arens, J. T.; Dattila, F.; Wendt, R.; Guilherme Buzanich, A.; Radtke, M.; Davies, V. et al. Determining structure-activity relationships in oxide derived Cu-Sn catalysts during CO2 electroreduction using X-ray spectroscopy. Adv. Energy Mater. 2022, 12, 2103328.
Hoang, T. T. H.; Verma, S.; Ma, S. C.; Fister, T. T.; Timoshenko, J.; Frenkel, A. I.; Kenis, P. J. A.; Gewirth, A. A. Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 2018, 140, 5791–5797.
Kim, D.; Resasco, J.; Yu, Y.; Asiri, A. M.; Yang, P. D. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles. Nat. Commun. 2014, 5, 4948.
He, J. F.; Johnson, N. J. J.; Huang, A. X.; Berlinguette, C. P. Electrocatalytic alloys for CO2 reduction. ChemSusChem 2018, 11, 48–57.
Lee, S.; Park, G.; Lee, J. Importance of Ag-Cu biphasic boundaries for selective electrochemical reduction of CO2 to ethanol. ACS Catal. 2017, 7, 8594–8604.
Wang, Y.; Wang, D. G.; Dares, C. J.; Marquard, S. L.; Sheridan, M. V.; Meyer, T. J. CO2 reduction to acetate in mixtures of ultrasmall (Cu)n,(Ag)m bimetallic nanoparticles. Proc. Natl. Acad. Sci. USA 2018, 115, 278–283.
Huang, J. F.; 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. 2019, 141, 2490–2499.
Tao, Z. X.; Wu, Z. S.; Yuan, X. L.; Wu, Y. S.; Wang, H. L. Copper-gold interactions enhancing formate production from electrochemical CO2 reduction. ACS Catal. 2019, 9, 10894–10898.
Wang, L.; Higgins, D. C.; Ji, Y. F.; Morales-Guio, C. G.; Chan, K.; Hahn, C.; Jaramillo, T. F. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. Proc. Natl. Sci. USA 2020, 117, 12572–12575.
Ren, D.; Ang, B. S. H.; Yeo, B. S. Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts. ACS Catal. 2016, 6, 8239–8247.
Kim, D.; Xie, C. L.; Becknell, N.; Yu, Y.; Karamad, M.; Chan, K.; Crumlin, E. J.; Nørskov, J. K.; Yang, P. D. Electrochemical activation of CO2 through atomic ordering transformations of AuCu nanoparticles. J. Amer. Chem. Soc. 2017, 139, 8329–8336.
Chang, C. J.; Hung, S. F.; Hsu, C. S.; Chen, H. C.; Lin, S. C.; Liao, Y. F.; Chen, H. M. Quantitatively unraveling the redox shuttle of spontaneous oxidation/electroreduction of CuOx on silver nanowires using in situ X-ray absorption spectroscopy. ACS Cent. Sci. 2019, 5, 1998–2009.
Zhang, L. J.; Li, M.; Zhang, S. B.; Cao, X. R.; Bo, J. X.; Zhu, X. L.; Han, J. Y.; Ge, Q. F.; Wang, H. Promoting carbon dioxide electroreduction toward ethanol through loading Au nanoparticles on hollow Cu2O nanospheres. Catal. Today 2021, 365, 348–356.
Lee, C. W.; Yang, K. D.; Nam, D. H.; Jang, J. H.; Cho, N. H.; Im, S. W.; Nam, K. T. Defining a materials database for the design of copper binary alloy catalysts for electrochemical CO2 conversion. Adv. Mater. 2018, 30, 1704717.
Jeon, H. S.; Timoshenko, J.; Scholten, F.; Sinev, I.; Herzog, A.; Haase, F. T.; Roldan Cuenya, B. Operando insight into the correlation between the structure and composition of CuZn nanoparticles and their selectivity for the electrochemical CO2 reduction. J. Am. Chem. Soc. 2019, 141, 19879–19887.
Chang, C. J.; Lin, S. C.; Chen, H. C.; Wang, J. L.; Zheng, K. J.; Zhu, Y. P.; Chen, H. M. Dynamic reoxidation/reduction-driven atomic interdiffusion for highly selective CO2 reduction toward methane. J. Am. Chem. Soc. 2020, 142, 12119–12132.
Ye, K.; Zhou, Z. W.; Shao, J. Q.; Lin, L.; Gao, D. F.; Ta, N.; Si, R.; Wang, G. X.; Bao, X. H. In situ reconstruction of a hierarchical Sn-Cu/SnOx core/shell catalyst for high-performance CO2 electroreduction. Angew. Chem., Int. Ed. 2020, 59, 4814–4821.
Zhan, W. C.; Wang, J. L.; Wang, H. F.; Zhang, J. S.; Liu, X. F.; Zhang, P. F.; Chi, M. F.; Guo, Y. L.; Guo, Y.; Lu, G. Z. et al. Crystal structural effect of AuCu alloy nanoparticles on catalytic CO oxidation. J. Am. Chem. Soc. 2017, 139, 8846–8854.
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Acknowledgements
The authors appreciate the support from the National Natural Science Foundation of China (No. 22172110). We thank the Haihe Laboratory of Sustainable Chemical Transformations for financial support. We thank the facility Center at the Institute of Molecular Plus at Tianjin University to use the transmission electron microscopes.
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