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Nano Research 2018, 11(9): 4774-4785 https://doi.org/10.1007/s12274-018-2062-4
Research Article | Issue | Published: 04 April 2018

Sub-nm ruthenium cluster as an efficient and robust catalyst for decomposition and synthesis of ammonia: Break the "size shackles"

Show Author's Information Jinpeng Li1,§,  Weiyang Wang1,§,  Wenxing Chen1,  Qinmei Gong2,  Jun Luo3,  Ruoqian Lin4,  Huolin Xin4,  Hui Zhang2,  Dingsheng Wang1,  Qing Peng1,  Wei Zhu1( ),  Chen Chen1( ),  Yadong Li1
Department of Chemistry Tsinghua UniversityBeijing100084China
The Center of New Energy Materials and Technology College of Chemistry and Chemical Engineering Southwest Petroleum UniversityChengdu610500China
Center for Electron Microscopy Tianjin University of TechnologyTianjin300384China
Center for Functional Nanomaterials Brookhaven National Laboratory UptonNew York11973USA

§Jinpeng Li and Weiyang Wang contributed equally to this work.

Keywords:
metal-organic frameworks, ammonia synthesis, sub-nm Ru cluster, synthesis design, ammonia decomposition
Cite this article:
Li J, Wang W, Chen W, et al. Sub-nm ruthenium cluster as an efficient and robust catalyst for decomposition and synthesis of ammonia: Break the "size shackles". Nano Research, 2018, 11(9): 4774-4785. https://doi.org/10.1007/s12274-018-2062-4
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Abstract Full text Electronic supplementary material About this article

Downsizing to sub-nm is a general strategy to reduce the cost of catalysts. However, theoretical Wulff-constructed model suggests that sub-nm clusters show little activity for various reactions such as ammonia decomposition and ammonia synthesis because of the lack of active sites. As clusters may deviate from the ideal model construction under reaction conditions, a host–guest strategy to synthesize thermally stable 1.0 nm monodispersed Ru clusters by the pyrolysis of MIL-101 hosts is reported here to verify the hypothesis. For ammonia decomposition, the activity of the Ru clusters is 25 times higher than that of commercial Ru/active carbon (AC) at full-conversion temperature, while for ammonia synthesis, the activity of the Ru clusters is 500 times as high as that of promoted Ru NPs counterpart. The catalyst also maintains its activities for 40 h without any increase in the size. This model can be used to develop a host–guest strategy for designing thermally stable sub-nm clusters to atomic–efficiently catalyze reactions.


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Abstract
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Electronic supplementary material
About this article

Sub-nm ruthenium cluster as an efficient and robust catalyst for decomposition and synthesis of ammonia: Break the "size shackles"

Show Author's information Jinpeng Li1,§, Weiyang Wang1,§, Wenxing Chen1, Qinmei Gong2, Jun Luo3, Ruoqian Lin4, Huolin Xin4, Hui Zhang2, Dingsheng Wang1, Qing Peng1, Wei Zhu1( ), Chen Chen1( ), Yadong Li1
Department of Chemistry Tsinghua UniversityBeijing100084China
The Center of New Energy Materials and Technology College of Chemistry and Chemical Engineering Southwest Petroleum UniversityChengdu610500China
Center for Electron Microscopy Tianjin University of TechnologyTianjin300384China
Center for Functional Nanomaterials Brookhaven National Laboratory UptonNew York11973USA

§Jinpeng Li and Weiyang Wang contributed equally to this work.

Abstract

Downsizing to sub-nm is a general strategy to reduce the cost of catalysts. However, theoretical Wulff-constructed model suggests that sub-nm clusters show little activity for various reactions such as ammonia decomposition and ammonia synthesis because of the lack of active sites. As clusters may deviate from the ideal model construction under reaction conditions, a host–guest strategy to synthesize thermally stable 1.0 nm monodispersed Ru clusters by the pyrolysis of MIL-101 hosts is reported here to verify the hypothesis. For ammonia decomposition, the activity of the Ru clusters is 25 times higher than that of commercial Ru/active carbon (AC) at full-conversion temperature, while for ammonia synthesis, the activity of the Ru clusters is 500 times as high as that of promoted Ru NPs counterpart. The catalyst also maintains its activities for 40 h without any increase in the size. This model can be used to develop a host–guest strategy for designing thermally stable sub-nm clusters to atomic–efficiently catalyze reactions.

Keywords: metal-organic frameworks, ammonia synthesis, sub-nm Ru cluster, synthesis design, ammonia decomposition

References(52)

1

Spencer, N. D.; Schoonmaker, R. C.; Somorjai, G. A. Structure sensitivity in the iron single-crystal catalysed synthesis of ammonia. Nature 1981, 294, 643-644.
DOI Google Scholar
2

Rodriguez, J. A.; Goodman, D. W. High-pressure catalytic reactions over single-crystal metal surfaces. Surf. Sci. Rep. 1991, 14, 1-107.
DOI Google Scholar
3

Liu, J. X.; Su, H. Y.; Sun, D. P.; Zhang, B. Y.; Li, W. X. Crystallographic dependence of CO activation on cobalt catalysts: HCP versus FCC. J. Am. Chem. Soc. 2013, 135, 16284-16287.
DOI Google Scholar
4

Li, W. Z.; Liu, J. X.; Gu, J.; Zhou, W.; Yao, S. Y.; Si, R.; Guo, Y.; Su, H. Y.; Yan, C. H.; Li, W. X. et al. Chemical insights into the design and development of face-centered cubic ruthenium catalysts for Fischer-Tropsch synthesis. J. Am. Chem. Soc. 2017, 139, 2267-2276.
DOI Google Scholar
5

Marks, L. D. Experimental studies of small particle structures. Rep. Prog. Phys. 1994, 57, 603-649.
DOI Google Scholar
6

Honkala, K.; Hellman, A.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Nørskov, J. K. Ammonia synthesis from first-principles calculations. Science 2005, 307, 555-558.
DOI Google Scholar
7

Dahl, S.; Logadottir, A.; Egeberg, R. C.; Larsen, J. H.; Chorkendorff, I.; Törnqvist, E.; Nørskov, J. K. Role of steps in N2 activation on Ru(0001). Phys. Rev. Lett. 1999, 83, 1814-1817.
DOI Google Scholar
8

Vajda, S.; Pellin, M. J.; Greeley, J. P.; Marshall, C. L.; Curtiss, L. A.; Ballentine, G. A.; Elam, J. W.; Catillon-Mucherie, S.; Redfern, P. C.; Mehmood, F. et al. Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane. Nat. Mater. 2009, 8, 213-216.
DOI Google Scholar
9

Oliver-Meseguer, J.; Cabrero-Antonino, J. R.; Domínguez, I.; Leyva-Pérez, A.; Corma, A. Small gold clusters formed in solution give reaction turnover numbers of 107 at room temperature. Science 2012, 338, 1452-1455.
DOI Google Scholar
10

Wei, H. S.; Liu, X. Y.; Wang, A. Q.; Zhang, L. L.; Qiao, B. T.; Yang, X. F.; Huang, Y. Q.; Miao, S.; Liu, J. Y.; Zhang, T. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 2014, 5, 5634.
DOI Google Scholar
11

Tyo, E. C.; Vajda, S. Catalysis by clusters with precise numbers of atoms. Nat. Nanotechnol. 2015, 10, 577-588.
DOI Google Scholar
12

Meek, S. T.; Greathouse, J. A.; Allendorf, M. D. Metal-organic frameworks: A rapidly growing class of versatile nanoporous materials. Adv. Mater. 2011, 23, 249-267.
DOI Google Scholar
13

Tao, F.; Dag, S.; Wang, L. W.; Liu, Z.; Butcher, D. R.; Bluhm, H.; Salmeron, M.; Somorjai, G. A. Break-up of stepped platinum catalyst surfaces by high CO coverage. Science 2010, 327, 850-853.
DOI Google Scholar
14

Tao, F.; Grass, M. E.; Zhang, Y. W.; Butcher, D. R.; Renzas, J. R.; Liu, Z.; Chung, J. Y.; Mun, B. S.; Salmeron, M.; Somorjai, G. A. Reaction-driven restructuring of Rh-Pd and Pt-Pd core-shell nanoparticles. Science 2008, 322, 932-934.
DOI Google Scholar
15

Jacobsen, C. J. H.; Dahl, S.; Hansen, P. L.; Tornqvist, E.; Jensen, L.; Topsøe, H.; Prip, D. V.; Møenshaug, P. B.; Chorkendorff, I. Structure sensitivity of supported ruthenium catalysts for ammonia synthesis. J. Mol. Catal. A: Chem. 2000, 163, 19-26.
DOI Google Scholar
16

Kalamaras, C. M.; Americanou, S.; Efstathiou, A. M. "Redox" vs. "associative formate with -OH group regeneration" WGS reaction mechanism on Pt/CeO2: Effect of platinum particle size. J. Catal. 2011, 279, 287-300.
DOI Google Scholar
17

Corma, A. From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem. Rev. 1997, 97, 2373-2420.
DOI Google Scholar
18

Goel, S.; Wu, Z. J.; Zones, S. I.; Iglesia, E. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites. J. Am. Chem. Soc. 2012, 134, 17688-17695.
DOI Google Scholar
19

Liu, Y. L.; Tang, Z. Y. Multifunctional Nanoparticle@MOF core-shell nanostructures. Adv. Mater. 2013, 25, 5819-5825.
DOI Google Scholar
20

Guan, B. Y.; Yu, X. Y.; Wu, H. B.; Lou, X. W. Complex nanostructures from materials based on metal-organic frameworks for electrochemical energy storage and conversion. Adv. Mater., 2017, 29, 1703614.
DOI Google Scholar
21

Pan, X. L.; Fan, Z. L.; Chen, W.; Ding, Y. J.; Luo, H. Y.; Bao, X. H. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles. Nat. Mater. 2007, 6, 507-511.
DOI Google Scholar
22

Volosskiy, B.; Niwa, K.; Chen, Y.; Zhao, Z. P.; Weiss, N. O.; Zhong, X.; Ding, M. N.; Lee, C.; Huang, Y.; Duan, X. F. Metal-organic framework templated synthesis of ultrathin, well-aligned metallic nanowires. ACS Nano 2015, 9, 3044-3049.
DOI Google Scholar
23

Chen, Y. Z.; Zhou, Y. X.; Wang, H. W.; Lu, J. L.; Uchida, T.; Xu, Q.; Yu, S. H.; Jiang, H. L. Multifunctional PdAg@MIL-101 for one-pot cascade reactions: Combination of host-guest cooperation and bimetallic synergy in catalysis. ACS Catal. 2015, 5, 2062-2069.
DOI Google Scholar
24

Wu, S. S.; Zhu, Y. G.; Huo, Y. F.; Luo, Y. C.; Zhang, L. H.; Wan, Y.; Nan, B.; Cao, L. J.; Wang, Z. Y.; Li, M. C. et al. Bimetallic organic frameworks derived CuNi/carbon nanocomposites as efficient electrocatalysts for oxygen reduction reaction. Sci. China Mater. 2017, 60, 654-663.
DOI Google Scholar
25

Wang, B. Q.; Liu, W. X.; Zhang, W. N.; Liu, J. F. Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size-and shape-selective reactions. Nano Res. 2017, 10, 3826-3835.
DOI Google Scholar
26

Li, X. L.; Zhang, B. Y.; Tang, L. L.; Goh, T. W.; Qi, S. Y.; Volkov, A.; Pei, Y. C.; Qi, Z. Y.; Tsung, C. -K.; Stanley, L. et al. Cooperative multifunctional catalysts for nitrone synthesis: Platinum nanoclusters in amine-functionalized metal-organic frameworks. Angew. Chem., Int. Ed. 2017, 56, 16371-16375.
DOI Google Scholar
27

Li, X. L.; Goh, T. W.; Li, L.; Xiao, C. X.; Guo, Z. Y.; Zeng, X. C.; Huang, W. Y. Controlling catalytic properties of Pd nanoclusters through their chemical environment at the atomic level using isoreticular metal-organic frameworks. ACS Catal. 2016, 6, 3461-3468.
DOI Google Scholar
28

Li, X. L.; Guo, Z. Y.; Xiao, C. X.; Goh, T. W.; Tesfagaber, D.; Huang, W. Y. Tandem catalysis by palladium nanoclusters encapsulated in metal-organic frameworks. ACS Catal. 2014, 4, 3490-3497.
DOI Google Scholar
29

Guo, Z. Y.; Xiao, C. X.; Maligal-Ganesh, R. V.; Zhou, L.; Goh, T. W.; Li, X. L.; Tesfagaber, D.; Thiel, A.; Huang, W. Y. Pt Nanoclusters confined within metal-organic framework cavities for chemoselective cinnamaldehyde hydrogenation. ACS Catal. 2014, 4, 1340-1348.
DOI Google Scholar
30

Boisen, A.; Dahl, S.; Nørskov, J. K.; Christensen, C. H. Why the optimal ammonia synthesis catalyst is not the optimal ammonia decomposition catalyst. J. Catal. 2005, 230, 309-312.
DOI Google Scholar
31

Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 2005, 309, 2040-2042.
DOI Google Scholar
32

Yin, S. F.; Xu, B. Q.; Zhou, X. P.; Au, C. T. A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications. Appl. Catal. A: Gen. 2004, 277, 1-9.
DOI Google Scholar
33

Aika, K.; Ohya, A.; Ozaki, A.; Inoue, Y.; Yasumori, I. Support and promoter effect of ruthenium catalyst: Ⅱ. Ruthenium/alkaline earth catalyst for activation of dinitrogen. J. Catal. 1985, 92, 305-311.
DOI Google Scholar
34

Aika, K.; Takano, T.; Murata, S. Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesis: 3. A magnesia-supported ruthenium catalyst. J. Catal. 1992, 136, 126-140.
DOI Google Scholar
35

Kubota, J.; Aika, K. Infrared studies of adsorbed dinitrogen on supported ruthenium catalysts for ammonia synthesis: Effects of the alumina and magnesia supports and the cesium compound promoter. J. Phys. Chem. 1994, 98, 11293-11300.
DOI Google Scholar
36

Larichev, Y. V. Valence state study of supported ruthenium Ru/MgO catalysts. J. Phys. Chem. C 2008, 112, 14776-14780.
DOI Google Scholar
37

Ge, J. J.; He, D. S.; Chen, W. X.; Ju, H. X.; Zhang, H.; Chao, T. T.; Wang, X. Q.; You, R.; Lin, Y.; Wang, Y. et al. Atomically dispersed Ru on ultrathin Pd nanoribbons. J. Am. Chem. Soc. 2016, 138, 13850-13853.
DOI Google Scholar
38

Kitano, M.; Inoue, Y.; Yamazaki, Y.; Hayashi, F.; Kanbara, S.; Matsuishi, S.; Yokoyama, T.; Kim, S. W.; Hara, M.; Hosono, H. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem. 2012, 4, 934-940.
DOI Google Scholar
39

Kitano, M.; Kanbara, S.; Inoue, Y.; Kuganathan, N.; Sushko, P. V.; Yokoyama, T.; Hara, M.; Hosono, H. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis. Nat. Commun. 2015, 6, 6731.
DOI Google Scholar
40

Wang, P. K.; Chang, F.; Gao, W. B.; Guo, J. P.; Wu, G. T.; He, T.; Chen, P. Breaking scaling relations to achieve low-temperature ammonia synthesis through LiH-mediated nitrogen transfer and hydrogenation. Nat. Chem. 2017, 9, 64-70.
DOI Google Scholar
41

Rosowski, F.; Hornung, A.; Hinrichsen, O.; Herein, D.; Muhler, M.; Ertl, G. Ruthenium catalysts for ammonia synthesis at high pressures: Preparation, characterization, and power-law kinetics. Appl. Catal. A: Gen. 1997, 151, 443-460.
DOI Google Scholar
42

Rossetti, I.; Sordelli, L.; Ghigna, P.; Pin, S.; Scavini, M.; Forni, L. EXAFS-XANES evidence of in situ cesium reduction in Cs-Ru/C catalysts for ammonia synthesis. Inorg. Chem. 2011, 50, 3757-3765.
DOI Google Scholar
43

Larichev, Y. V. Effect of Cs+ promoter in Ru/MgO catalysts. J. Phys. Chem. C 2011, 115, 631-635.
DOI Google Scholar
44

Gao, Y.; Bai, G.; Liang, Y.; Dunham, G. C.; Chambers, S. A. Structure and surface morphology of highly conductive RuO2 films grown on MgO by oxygen-plasma-assisted molecular beam epitaxy. J. Mater. Res. 1997, 12, 1844-1849.
DOI Google Scholar
45

Schlögl, R. Catalytic synthesis of ammonia—A "never-ending story"? Angew. Chem., Int. Ed. 2003, 42, 2004-2008.
DOI Google Scholar
46

Liu, H. Z. Ammonia synthesis catalyst 100 years: Practice, enlightenment and challenge. Chinese J. Catal. 2014, 35, 1619-1640.
DOI Google Scholar
47

Choudhary, T. V.; Sivadinarayana, C.; Goodman, D. W. Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications. Catal. Lett. 2001, 72, 197-201.
DOI Google Scholar
48

Klerke, A.; Christensen, C. H.; Nørskov, J. K.; Vegge, T. Ammonia for hydrogen storage: Challenges and opportunities. J. Mater. Chem. 2008, 18, 2304-2310.
DOI Google Scholar
49

Hayashi, F.; Toda, Y.; Kanie, Y.; Kitano, M.; Inoue, Y.; Yokoyama, T.; Hara, M.; Hosono, H. Ammonia decomposition by ruthenium nanoparticles loaded on inorganic electride C12A7: e-. Chem. Sci. 2013, 4, 3124-3130.
DOI Google Scholar
50

García-Bordejé, E.; Armenise, S.; Roldán, L. Toward practical application of H2 generation from ammonia decomposition guided by rational catalyst design. Catal. Rev. 2014, 56, 220-237.
DOI Google Scholar
51

Guo, J. P.; Wang, P. K.; Wu, G. T.; Wu, A. A.; Hu, D. Q.; Xiong, Z. T.; Wang, J. H.; Yu, P.; Chang, F.; Chen, Z. et al. Lithium imide synergy with 3d transition-metal nitrides leading to unprecedented catalytic activities for ammonia decomposition. Angew. Chem., Int. Ed. 2015, 54, 2950-2954.
DOI Google Scholar
52

Kowalczyk, Z.; Sentek, J.; Jodzis, S.; Mizera, E.; Góralski, J.; Paryjczak, T.; Diduszko, R. An alkali-promoted ruthenium catalyst for the synthesis of ammonia, supported on thermally modified active carbon. Catal. Lett. 1997, 45, 65-72.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 08 February 2018
Revised: 20 March 2018
Accepted: 21 March 2018
Published: 04 April 2018
Issue date: September 2018

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21521091, 21131004, 21390393, U1463202, 21573119, 21590792, and 21406184). We also thank the Shanghai Synchrotron Radiation Facility (No. BL14W1) for providing beam time.

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