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Research Article

A library of carbon-supported ultrasmall bimetallic nanoparticles

Shi-Long Xu1, Shan-Cheng Shen1, Ze-Yue Wei2, Shuai Zhao1, Lu-Jie Zuo1, Ming-Xi Chen1, Lei Wang1, Yan-Wei Ding1, Ping Chen3, Sheng-Qi Chu4, Yue Lin1( ), Kun Qian2( ), Hai-Wei Liang1( )
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, CAS Key Laboratory of Materials for Energy Conversion and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
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Abstract

Small-sized bimetallic nanoparticles that possess numerous accessible metal sites and optimal geometric/electronic structures show great promise for advanced synergetic catalysis but remain synthetic challenge so far. Here, an universial synthetic method is developed for building a library of bimetallic nanoparticles on mesoporous sulfur-doped carbon supports, consisting of 24 combinations of 3 noble metals (that is, Pt, Rh, Ir) and 7 other metals, with average particle sizes ranging from 0.7 to 1.4 nm. The synthetic strategy is based on the strong metal-support interaction arising from the metal-sulfur bonding, which suppresses the metal aggregation during the H2-reduction at 700 °C and ensure the formation of small-sized and alloyed bimetallic nanoparticles. The enhanced catalytic properties of the ultrasmall bimetallic nanoparticles are demonstrated in the dehydrogenation of propane at high temperature and oxidative dehydrogenations of N-heterocycles.

Keywords

catalysisbimetallic nanoparticlessulfur doped carbonultrasmallmetal-support interaction

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References

[1]
Alexeev, O. S.; Gates, B. C. Supported bimetallic cluster catalysts. Ind. Eng. Chem. Res. 2003, 42, 1571-1587.
Crossref Google Scholar
[2]
Buchwalter, P.; Rosé, J.; Braunstein, P. Multimetallic catalysis based on heterometallic complexes and clusters. Chem. Rev. 2015, 115, 28-126.
Crossref Google Scholar
[3]
Singh, A. K.; Xu, Q. Synergistic catalysis over bimetallic alloy nanoparticles. ChemCatChem 2013, 5, 652-676.
Crossref Google Scholar
[4]
Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740-1748.
Crossref Google Scholar
[5]
Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981-5079.
Crossref Google Scholar
[6]
Mitchell, S.; Vorobyeva, E.; Pérez-Ramírez, J. Reactivity of single- atom heterogeneous catalysts: Unique and multifaceted. Angew. Chem., Int. Ed. 2018, 57, 15316-15329.
Crossref Google Scholar
[7]
Liu, P. X.; Zhao, Y.; Qin, R. X.; Mo, S. G.; Chen, G. X.; Gu, L.; Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D. D. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 2016, 352, 797-800.
Crossref Google Scholar
[8]
El-Sayed, M. A. Small is different: Shape-, size-, and composition- dependent properties of some colloidal semiconductor nanocrystals. Acc. Chem. Res. 2004, 37, 326-333.
Crossref Google Scholar
[9]
Yao, Y. G.; Huang, Z. N.; Xie, P. F.; Lacey, S. D.; Jacob, R. J.; Xie, H.; Chen, F. J.; Nie, A. M.; Pu, T. C.; Rehwoldt, M. et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 2018, 359, 1489-1494.
Crossref Google Scholar
[10]
Toshima, N. Polymer-protected bimetallic clusters. Preparation and application to catalysis. J. Macromol. Sci. A - Chem. 1990, 27, 1225-1238.
Crossref Google Scholar
[11]
Zhang, H. J.; Watanabe, T.; Okumura, M.; Haruta, M.; Toshima, N. Catalytically highly active top gold atom on palladium nanocluster. Nat. Mater. 2012, 11, 49-52.
Crossref Google Scholar
[12]
Kulkarni, A.; Gates, B. C. Spectroscopic elucidation of first steps of supported bimetallic cluster formation. Angew. Chem., Int. Ed. 2009, 48, 9697-9700.
Crossref Google Scholar
[13]
Chotisuwan, S.; Wittayakun, J.; Lobo-Lapidus, R. J.; Gates, B. C. MGO-supported cluster catalysts with Pt-Ru interactions prepared from Pt3Ru6(CO)21(μ3-H)(μ-h)3. Catal. Lett. 2007, 115, 99-107.
Crossref Google Scholar
[14]
Fung, A. S.; Kelley, M. J.; Koningsberger, D. C.; Gates, B. C. γ-Al2O3- supported Re-Pt cluster catalyst prepared from [Re2Pt(CO)12]: Characterization by extended x-ray absorption fine structure spectroscopy and catalysis of methylcyclohexane dehydrogenation. J. Am. Chem. Soc. 1997, 119, 5877-5887.
Crossref Google Scholar
[15]
Yang, J.; He, D. S.; Chen, W. X.; Zhu, W.; Zhang, H.; Ren, S.; Wang, X.; Yang, Q. H.; Wu, Y. E.; Li, Y. D. Bimetallic Ru-Co clusters derived from a confined alloying process within zeolite-imidazolate frameworks for efficient NH3 decomposition and synthesis. ACS Appl. Mater. Interfaces 2017, 9, 39450-39455.
Crossref Google Scholar
[16]
Iida, T.; Zanchet, D.; Ohara, K.; Wakihara, T.; Román-Leshkov, Y. Concerted bimetallic nanocluster synthesis and encapsulation via induced zeolite framework demetallation for shape and substrate selective heterogeneous catalysis. Angew. Chem., Int. Ed. 2018, 57, 6454-6458.
Crossref Google Scholar
[17]
Mao, J. J.; Li, J.; Pei, J. J.; Liu, Y.; Wang, D. S.; Li, Y. D. Structure regulation of noble-metal-based nanomaterials at an atomic level. Nano Today 2019, 26, 164-175.
Crossref Google Scholar
[18]
Wong, A.; Liu, Q.; Griffin, S.; Nicholls, A.; Regalbuto, J. R. Synthesis of ultrasmall, homogeneously alloyed, bimetallic nanoparticles on silica supports. Science 2017, 358, 1427-1430.
Crossref Google Scholar
[19]
Ding, K. L.; Cullen, D. A.; Zhang, L. B.; Cao, Z.; Roy, A. D.; Ivanov, I. N.; Cao, D. M. A general synthesis approach for supported bimetallic nanoparticles via surface inorganometallic chemistry. Science 2018, 362, 560-564.
Crossref Google Scholar
[20]
Wang, L.; Chen, M. X.; Yan, Q. Q.; Xu, S. L.; Chu, S. Q.; Chen, P.; Lin, Y.; Liang, H. W. A sulfur-tethering synthesis strategy toward high-loading atomically dispersed noble metal catalysts. Sci. Adv. 2019, 5, eaax6322.
Crossref Google Scholar
[21]
Yan, Q. Q.; Wu, D. X.; Chu, S. Q.; Chen, Z. Q.; Lin, Y.; Chen, M. X.; Zhang, J.; Wu, X. J.; Liang, H. W. Reversing the charge transfer between platinum and sulfur-doped carbon support for electrocatalytic hydrogen evolution. Nat. Commun. 2019, 10, 4977.
Crossref Google Scholar
[22]
Choi, C. H.; Kim, M.; Kwon, H. C.; Cho, S. J.; Yun, S.; Kim, H. T.; Mayrhofer, K. J. J.; Kim, H.; Choi, M. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst. Nat. Commun. 2016, 7, 10922.
Crossref Google Scholar
[23]
Liu, B.; Yao, H. Q.; Song, W. Q.; Jin, L.; Mosa, I. M.; Rusling, J. F.; Suib, S. L.; He, J. Ligand-free noble metal nanocluster catalysts on carbon supports via “soft” nitriding. J. Am. Chem. Soc. 2016, 138, 4718-4721.
Crossref Google Scholar
[24]
Cheng, N. C.; Stambula, S.; Wang, D.; Banis, M. N.; Liu, J.; Riese, A.; Xiao, B. W.; Li, R. Y.; Sham, T. K.; Liu, L. M. et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 2016, 7, 13638.
Crossref Google Scholar
[25]
Wu, Z. Y.; Xu, S. L.; Yan, Q. Q.; Chen, Z. Q.; Ding, Y. W.; Li, C.; Liang, H. W.; Yu, S. H. Transition metal-assisted carbonization of small organic molecules toward functional carbon materials. Sci. Adv. 2018, 4, eaat0788.
Crossref Google Scholar
[26]
Liang, H. W.; Brüller, S.; Dong, R. H.; Zhang, J.; Feng, X. L.; Müllen, K. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution. Nat. Commun. 2015, 6, 7992.
Crossref Google Scholar
[27]
Chen, L.; Cooper, A. C.; Pez, G. P.; Cheng, H. S. Mechanistic study on hydrogen spillover onto graphitic carbon materials. J. Phys. Chem. C 2007, 111, 18995-19000.
Crossref Google Scholar
[28]
Karim, W.; Spreafico, C.; Kleibert, A.; Gobrecht, J.; VandeVondele, J.; Ekinci, Y.; van Bokhoven, J. A. Catalyst support effects on hydrogen spillover. Nature 2017, 541, 68-71.
Crossref Google Scholar
[29]
Zhang, X.; Cui, G. Q.; Feng, H. S.; Chen, L. F.; Wang, H.; Wang, B.; Zhang, X.; Zheng, L. R.; Hong, S.; Wei, M. Platinum-copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis. Nat. Commun. 2019, 10, 5812.
Crossref Google Scholar
[30]
Zhang, B.; Asakura, H.; Zhang, J.; Zhang, J. G.; De, S.; Yan, N. Stabilizing a platinum1 single-atom catalyst on supported phosphomolybdic acid without compromising hydrogenation activity. Angew. Chem., Int. Ed. 2016, 55, 8319-8323.
Crossref Google Scholar
[31]
Takahashi, M.; Koizumi, H.; Chun, W. J.; Kori, M.; Imaoka, T.; Yamamoto, K. Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons. Sci. Adv. 2017, 3, e1700101.
Crossref Google Scholar
[32]
Wang, W. H.; Tian, X. L.; Chen, K.; Cao, G. Y. Synthesis and characterization of Pt-Cu bimetallic alloy nanoparticles by reverse micelles method. Colloids Surf. A 2006, 273, 35-42.
Crossref Google Scholar
[33]
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 2014, 118, 26324-26331.
Crossref Google Scholar
[34]
Akporiaye, D.; Jensen, S.; Olsbye, U.; Rohr, F.; Rytter, E.; Rønnekleiv, M.; Spjelkavik, A. I. A novel, highly efficient catalyst for propane dehydrogenation. Ind. Eng. Chem. Res. 2001, 40, 4741-4748.
Crossref Google Scholar
[35]
Shen, J. Y.; Hill, J. M.; Watwe, R. M.; Spiewak, B. E.; Dumesic, J. A. Microcalorimetric, infrared spectroscopic, and DFT studies of ethylene adsorption on Pt/SiO2 and Pt-Sn/SiO2 catalysts. J. Phys. Chem. B 1999, 103, 3923-3934.
Crossref Google Scholar
[36]
Siri, G. J.; Ramallo-López, J. M.; Casella, M. L.; Fierro, J. L. G.; Requejo, F. G.; Ferretti, O. XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals: Application to the isobutane dehydrogenation. Appl. Catal. A 2005, 278, 239-249.
Crossref Google Scholar
[37]
Cui, X.; Li, Y.; Bachmann, S.; Scalone, M.; Surkus, A. E.; Junge, K.; Topf, C.; Beller, M. Synthesis and characterization of iron-nitrogen- doped graphene/core-shell catalysts: Efficient oxidative dehydrogenation of N-heterocycles. J. Am. Chem. Soc. 2015, 137, 10652-10658.
Crossref Google Scholar
[38]
Chang, J. R.; Chang, S. L.; Lin, T. B. γ-alumina-supported Pt catalysts for aromatics reduction: A structural investigation of sulfur poisoning catalyst deactivation. J. Catal. 1997, 169, 338-346.
Crossref Google Scholar
[39]
Chang, J. R.; Chang, S. L. Catalytic properties of γ-alumina- supported Pt catalysts for tetralin hydrogenation: Effects of sulfur-poisoning and hydrogen reactivation. J. Catal. 1998, 176, 42-51.
Crossref Google Scholar
Nano Research
Volume 13 Issue 10,
October 2020
Pages 2735-2740
DOI: 10.1007/s12274-020-2920-8
Cite this article:
Xu S-L, Shen S-C, Wei Z-Y, et al. A library of carbon-supported ultrasmall bimetallic nanoparticles. Nano Research, 2020, 13(10): 2735-2740. https://doi.org/10.1007/s12274-020-2920-8
Topics:
CarbonMetal nanoparticlesMetalsStructural optimizationSulfur

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Received: 01 January 2020
Revised: 02 June 2020
Accepted: 06 June 2020
Published: 05 October 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
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