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Nano Research 2011, 4(1): 83-91 https://doi.org/10.1007/s12274-010-0051-3
Research Article | Open Access | Issue | Published: 27 October 2010

Synthesis of Pd Nanocrystals Enclosed by {100} Facets and with Sizes < 10 nm for Application in CO Oxidation

Show Author's Information Mingshang Jin1,3,§,  Hongyang Liu2,§,  Hui Zhang1,  Zhaoxiong Xie3,  Jingyue Liu2,4,  Younan Xia1( )
Department of Biomedical EngineeringWashington University, St. LouisMissouri63130USA
Center for NanoscienceUniversity of Missouri, St. LouisMissouri63121USA
State Key Laboratory for Physical Chemistry of Solid SurfacesDepartment of ChemistryXiamen University, XiamenFujian361005China
Department of Physics and Astronomy, and Department of Chemistry and BiochemistryUniversity of Missouri, St. LouisMissouri63121USA

§ These two authors contributed equally to this work.

Keywords:
Palladium, nanocubes, CO oxidation, size-dependence
Cite this article:
Jin M, Liu H, Zhang H, et al. Synthesis of Pd Nanocrystals Enclosed by {100} Facets and with Sizes < 10 nm for Application in CO Oxidation. Nano Research, 2011, 4(1): 83-91. https://doi.org/10.1007/s12274-010-0051-3
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Abstract Full text Electronic supplementary material About this article

The catalytic activity of noble-metal nanocrystals is mainly determined by their sizes and the facets exposed on the surface. For single crystals, it has been demonstrated that the Pd(100) surface is catalytically more active than both Pd(110) and Pd(111) surfaces for the CO oxidation reaction. Here we report the synthesis of Pd nanocrystals enclosed by {100} facets with controllable sizes in the range of 6-18 nm by manipulating the rate of reduction of the precursor. UV-vis spectroscopy studies indicate that the rate of reduction of Na2PdCl4 can be controlled by adjusting the concentrations of Br- and Cl- ions added to the reaction mixture. Pd nanocrystals with different sizes were immobilized on ZnO nanowires and evaluated as catalysts for CO oxidation. We found that the activity of this catalytic system for CO oxidation showed a strong dependence on the nanocrystal size. When the size of the Pd nanocrystals was reduced from 18 nm to 6 nm, the maximum conversion rate was significantly enhanced by a factor of ~10 and the corresponding maximum conversion temperature was lowered by ~80 ℃.


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About this article

Synthesis of Pd Nanocrystals Enclosed by {100} Facets and with Sizes < 10 nm for Application in CO Oxidation

Show Author's information Mingshang Jin1,3,§, Hongyang Liu2,§, Hui Zhang1, Zhaoxiong Xie3, Jingyue Liu2,4, Younan Xia1( )
Department of Biomedical EngineeringWashington University, St. LouisMissouri63130USA
Center for NanoscienceUniversity of Missouri, St. LouisMissouri63121USA
State Key Laboratory for Physical Chemistry of Solid SurfacesDepartment of ChemistryXiamen University, XiamenFujian361005China
Department of Physics and Astronomy, and Department of Chemistry and BiochemistryUniversity of Missouri, St. LouisMissouri63121USA

§ These two authors contributed equally to this work.

Abstract

The catalytic activity of noble-metal nanocrystals is mainly determined by their sizes and the facets exposed on the surface. For single crystals, it has been demonstrated that the Pd(100) surface is catalytically more active than both Pd(110) and Pd(111) surfaces for the CO oxidation reaction. Here we report the synthesis of Pd nanocrystals enclosed by {100} facets with controllable sizes in the range of 6-18 nm by manipulating the rate of reduction of the precursor. UV-vis spectroscopy studies indicate that the rate of reduction of Na2PdCl4 can be controlled by adjusting the concentrations of Br- and Cl- ions added to the reaction mixture. Pd nanocrystals with different sizes were immobilized on ZnO nanowires and evaluated as catalysts for CO oxidation. We found that the activity of this catalytic system for CO oxidation showed a strong dependence on the nanocrystal size. When the size of the Pd nanocrystals was reduced from 18 nm to 6 nm, the maximum conversion rate was significantly enhanced by a factor of ~10 and the corresponding maximum conversion temperature was lowered by ~80 ℃.

Keywords: Palladium, nanocubes, CO oxidation, size-dependence

References(53)

1

Doyle, A. M.; Shaikhutdinov, S. K.; Freund, H. J.; Freund, J. Surface-bonded precursor determines particle size effects for alkene hydrogenation on palladium. Angew. Chem. Int. Edit. 2005, 44, 629-631.
DOI Google Scholar
2

Doyle, A. M.; Shaikhutdinov, S. K.; Jackson, S. D.; Freund, H. J. Hydrogenation on metal surfaces: Why are nanoparticles more active than single crystals? Angew. Chem. Int. Edit. 2003, 42, 5240-5243.
DOI Google Scholar
3

Shaikhutdinov, S. K.; Heemeier, M.; Baumer, M.; Lear, T.; Lennon, D.; Oldman, R. J.; Jackson, S. D.; Freund, H. J. Structure-reactivity relationships on supported metal model catalysts: Adsorption and reaction of ethene and hydrogen on Pd/Al2O3/NiAl(110). J. Catal. 2001, 220, 330-339.
DOI Google Scholar
4

Wilson, O. M.; Knecht, M. R.; Garcia-Martinez, J. C.; Crooks, R. M. Effect of Pd nanoparticle size on the catalytic hydrogenation of allyl alcohol. J. Am. Chem. Soc. 2006, 128, 4510-4511.
DOI Google Scholar
5

Bhattacharjee, S.; Dotzauer, D. M.; Bruening, M. L. Selectivity as a function of nanoparticle size in the catalytic hydrogenation of unsaturated alcohols. J. Am. Chem. Soc. 2009, 131, 3601-3610.
DOI Google Scholar
6

Chen, J.; Zhang, Q. H.; Wang, Y.; Wan, H. L. Size-dependent catalytic activity of supported palladium nanoparticles for aerobic oxidation of alcohols. Adv. Synth. Catal. 2008, 350, 453-464.
DOI Google Scholar
7

Li, F.; Zhang, Q. H.; Wang, Y. Size dependence in solvent-free aerobic oxidation of alcohols catalyzed by zeolite-supported palladium nanoparticles. Appl. Catal. A 2008, 334, 217-226.
DOI Google Scholar
8

He, F.; Liu, J. C.; Roberts, C. B.; Zhao, D. Y. One-step "green" synthesis of Pd nanoparticles of controlled size and their catalytic activity for trichloroethene hydrodechlorination. Ind. Eng. Chem. Res. 2009, 48, 6550-6557.
DOI Google Scholar
9

Li, Y.; Boone, E.; El-Sayed, M. A. Size effects of PVP-Pd nanoparticles on the catalytic Suzuki reactions in aqueous solution. Langmuir 2002, 18, 4921-4925.
DOI Google Scholar
10

Narayanan, R.; El-Sayed, M. A. Effect of colloidal catalysis on the nanoparticle size distribution: Dendrimer-Pd vs. PVP-Pd nanoparticles catalyzing the Suzuki coupling reaction. J. Phys. Chem. B 2004, 108, 8572-8580.
DOI Google Scholar
11

Le Bars, J.; Specht, U.; Bradley, J. S.; Blackmond, D. G. A catalytic probe of the surface of colloidal palladium particles using Heck coupling reactions. Langmuir 1999, 15, 7621-7625.
DOI Google Scholar
12

Garcia-Martinez, J. C.; Lezutekong, R.; Crooks, R. M. Dendrimer-encapsulated Pd nanoparticles as aqueous, room-temperature catalysts for the Stille reaction. J. Am. Chem. Soc. 2005, 127, 5097-5103.
DOI Google Scholar
13

Nishihata, Y.; Mizuki, J.; Akao, T.; Tanaka, H.; Uenishi, M.; Kimura, M.; Okamoto, T.; Hamada, N. Self-regeneration of a Pd-perovskite catalyst for automotive emissions control. Nature 2002, 418, 164-167.
DOI Google Scholar
14

Thomas, J. M.; Johnson, B. F. G.; Raja, R.; Sankar, G.; Midgley, P. A. High-performance nanocatalysts for single-step hydrogenations. Acc. Chem. Res. 2003, 36, 20-30.
DOI Google Scholar
15

Fernandez-Garcia, M.; Martinez-Arias, A.; Salamanca, L. N.; Coronado, J. M.; Anderson, J. A.; Conesa, J. C.; Soria, J. Influence of ceria on Pd activity for the CO + O2 reaction. J. Catal. 1999, 187, 474-485.
DOI Google Scholar
16

Coulston, G. W.; Haller, G. L. The dynamics of Co oxidation on Pd, Rh, and Pt studied by high-resolution infrared chemiluminescence spectroscopy. J. Chem. Phys. 1991, 95, 6932-6944.
DOI Google Scholar
17

Chen, M. S.; Cal, Y.; Yan, Z.; Gath, K. K.; Axnanda, S.; Goodman, D. W. Highly active surfaces for CO oxidation on Rh, Pd, and Pt. Surf. Sci. 2007, 601, 5326-5331.
DOI Google Scholar
18

Nakao, K.; Watanabe, O.; Sasaki, T.; Ito, S.; Tomishige, K.; Kunimori, K. CO oxidation on Pd(111), Pt(111), and Rh(111) surfaces studied by infrared chemiluminescence spectroscopy. Surf. Sci. 2007, 601, 3796-3800.
DOI Google Scholar
19

Huang, X. Q.; Tang, S. H.; Zhang, H. H.; Zhou, Z. Y.; Zheng, N. F. Controlled formation of concave tetrahedral/ trigonal bipyramidal palladium nanocrystals. J. Am. Chem. Soc. 2009, 131, 13916-13917.
DOI Google Scholar
20

Zhou, W. P.; Lewera, A.; Larsen, R.; Masel, R. I.; Bagus, P. S.; Wieckowski, A. Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid. J. Phys. Chem. B 2006, 110, 13393-13398.
DOI Google Scholar
21

Zhou, W. J.; Lee, J. Y. Particle size effects in Pd-catalyzed electrooxidation of formic acid. J. Phys. Chem. C 2008, 112, 3789-3793.
DOI Google Scholar
22

Semagina, N.; Renken, A.; Kiwi-Minsker, L. Palladium nanoparticle size effect in 1-hexyne selective hydrogenation. J. Phys. Chem. C 2007, 111, 13933-13937.
DOI Google Scholar
23

Semagina, N.; Renken, A.; Laub, D.; Kiwi-Minsker, L. Synthesis of monodispersed palladium nanoparticles to study structure sensitivity of solvent-free selective hydrogenation of 2-methyl-3-butyn-2-ol. J. Catal. 2007, 246, 308-314.
DOI Google Scholar
24

Tardy, B.; Noupa, C.; Leclercq, C.; Bertolini, J. C.; Hoareau, A.; Treilleux, M.; Faure, J. P.; Nihoul, G. Catalytic-hydrogenation of 1, 3-butadiene on Pd particles evaporated on carbonaceous supports: Particle size effect. J. Catal. 1991, 129, 1-11.
DOI Google Scholar
25

Silvestre-Albero, J.; Rupprechter, G.; Freund, H. J. Atmospheric pressure studies of selective 1, 3-butadiene hydrogenation on well-defined Pd/Al2O3/NiAl(110) model catalysts: Effect of Pd particle size. J. Catal. 2006, 240, 58-65.
DOI Google Scholar
26

Vasylyev, M. V.; Maayan, G.; Hovav, Y.; Haimov, A.; Neumann, R. Palladium nanoparticles stabilized by alkylated polyethyleneimine as aqueous biphasic catalysts for the chemoselective stereocontrolled hydrogenation of alkenes. Org. Lett. 2006, 8, 5445-5448.
DOI Google Scholar
27

Lim, B.; Jiang, M. J.; Tao, J.; Camargo, P. H. C.; Zhu, Y. M.; Xia, Y. N. Shape-controlled synthesis of Pd nanocrystals in aqueous solutions. Adv. Funct. Mater. 2009, 19, 189-200.
DOI Google Scholar
28

Niu, W. X.; Li, Z. Y.; Shi, L. H.; Liu, X. Q.; Li, H. J.; Han, S.; Chen, J.; Xu, G. B. Seed-mediated growth of nearly monodisperse palladium nanocubes with controllable sizes. Cryst. Growth Des. 2008, 8, 4440-4444.
DOI Google Scholar
29

Lim, B.; Kobayashi, H.; Camargo, P. H. C.; Allard, L. F.; Liu, J. Y.; Xia, Y. N. New insights into the growth mechanism and surface structure of palladium nanocrystals. Nano Res. 2010, 3, 180-188.
DOI Google Scholar
30

Lim, B.; Xiong, Y. J.; Xia, Y. N. A water-based synthesis of octahedral, decahedral, and icosahedral Pd nanocrystals. Angew. Chem. Int. Ed. 2007, 46, 9279-9282.
DOI Google Scholar
31

Xia, Y.; Xiong, Y. J.; Lim, B.; Skrabalak, S. E. Shape-controlled synthesis of metal nanocrystals: Simple chemistry meets complex physics? Angew. Chem. Int. Ed. 2009, 48, 60-103.
DOI Google Scholar
32

Xiong, Y. J.; Cai, H. G.; Wiley, B. J.; Wang, J. G.; Kim, M. J.; Xia, Y. N. Synthesis and mechanistic study of palladium nanobars and nanorods. J. Am. Chem. Soc. 2007, 129, 3665-3675.
DOI Google Scholar
33

Xiong, Y. J.; Cai, H. G.; Yin, Y. D.; Xia, Y. N. Synthesis and characterization of fivefold twinned nanorods and right bipyramids of palladium. Chem. Phys. Lett. 2007, 440, 273-278.
DOI Google Scholar
34

Chen, Y. H.; Hung, H. H.; Huang, M. H. Seed-mediated synthesis of palladium nanorods and branched nanocrystals and their use as recyclable Suzuki coupling reaction catalysts. J. Am. Chem. Soc. 2009, 131, 9114-9121.
DOI Google Scholar
35

Tian, N.; Zhou, Z. Y.; Sun, S. G. Electrochemical preparation of Pd nanorods with high-index facets. Chem. Commun. 2009, 1502-1504.
DOI Google Scholar
36

Yu, Y. C.; Zhao, Y. X.; Huang, T.; Liu, H. F. Microwave-assisted synthesis of palladium nanocubes and nanobars. Mater. Res. Bull. 2010, 45, 159-164.
DOI Google Scholar
37

Chang, G.; Oyama, M.; Hirao, K. Facile synthesis of monodisperse palladium nanocubes and the characteristics of self-assembly. Acta Mater. 2007, 55, 3453-3456.
DOI Google Scholar
38

Shen, X. S.; Wang, G. Z.; Hong, X.; Zhu, W. Simple-cubic microcubes assembled by palladium nanocubes. CrystEngComm 2009, 11, 753-755.
DOI Google Scholar
39

Zhang, C. J.; Hu, P. CO oxidation on Pd(100) and Pd(111): A comparative study of reaction pathways and reactivity at low and medium coverages. J. Am. Chem. Soc. 2001, 123, 1166-1172.
DOI Google Scholar
40

Nakao, K.; Ito, S.; Tomishige, K.; Kunimori, K. Structure of activated complex of CO2 formation in a CO + O2 reaction on Pd(110) and Pd(111). J. Phys. Chem. B 2005, 109, 17553-17559.
DOI Google Scholar
41

Nakao, K.; Ito, S. I.; Tomishige, K.; Kunimori, K. Reaction mechanism and structure of activated complex of CO2 formation in CO oxidation on Pd(110) and Pd(111) surfaces. Catal. Today 2006, 111, 316-321.
DOI Google Scholar
42

Nakao, K.; Ito, S.; Tomishige, K.; Kunimori, K. Infrared chemiluminescence study of CO + O2 reaction on Pd(110): Activated complex of CO2 formation at high CO coverage. Chem. Phys. Lett. 2005, 410, 86-89.
DOI Google Scholar
43

Nakao, K.; Ito, S.; Tomishige, K.; Kunimori, K. Infrared chemiluminescence study of CO2 formation in CO plus NO reaction on Pd(110) and Pd(111) surfaces. J. Phys. Chem. B 2005, 109, 17579-17586.
DOI Google Scholar
44

Uetsuka, H.; Watanabe, K.; Ohnuma, H.; Kunimori, K. Structure sensitivity of the dynamics of CO oxidation on Pd(111), Pd(110) and polycrystalline Pd surfaces: Infrared chemiluminescence study of the product CO2. Chem. Lett. 1996, 25, 227-228.
DOI Google Scholar
45

Uetsuka, H.; Watanabe, K.; Ohnuma, H.; Kunimori, K. Structure-sensitivity in the dynamics of CO oxidation over Pd surfaces: Infrared chemiluminescence of the product CO2. Surf. Rev. Lett. 1997, 4, 1359-1363.
DOI Google Scholar
46

Srivastava, S. C.; Newman, L. Mixed ligand complexes of palladium(Ⅱ) with chloride and bromide. Inorg. Chem. 1966, 5, 1506-1510.
DOI Google Scholar
47

Feldberg, S.; Klotz, P.; Newman, L. Computer evaluation of equilibrium constants from spectrophotometric data. Inorg. Chem. 1972, 11, 2860-2865.
DOI Google Scholar
48

Wang, Z. F.; Shen, B.; He, N. Y. The synthesis of Pd nanoparticles by combination of the stabilizer of CNCH2COOK with its reduction. Mater. Lett. 2004, 58, 3652-3655.
DOI Google Scholar
49

Xiong, Y. J.; Chen, J. Y.; Wiley, B.; Xia, Y. N. Understanding the role of oxidative etching in the polyol synthesis of Pd nanoparticles with uniform shape and size. J. Am. Chem. Soc. 2005, 127, 7332-7333.
DOI Google Scholar
50

Kuhn, J. N.; Tsung, C. K.; Huang, W.; Somorjai, G. A. Effect of organic capping layers over monodisperse platinum nanoparticles upon activity for ethylene hydrogenation and carbon monoxide oxidation. J. Catal. 2009, 265, 209-215.
DOI Google Scholar
51

Becker, C.; Henry, C. R. Cluster size dependent kinetics for the oxidation of CO on a Pd/MgO(100) model catalyst. Surf. Sci. 1996, 352, 457-462.
DOI Google Scholar
52

Pan, Z. W.; Dai, Z. R.; Wang, Z. L. Nanobelts of semiconducting oxides. Science 2001, 291, 1947-1949.
DOI Google Scholar
53

Liu, H.Y.; Liu, J. Faceted ZnO nanowire supported Pd catalyst for the methanol steam reforming. Microsc. Microanal. 2010, 16, 1206-1207.
DOI Google Scholar
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Publication history

Received: 23 August 2010
Revised: 20 September 2010
Accepted: 21 September 2010
Published: 27 October 2010
Issue date: January 2011

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© The Author(s) 2010

Acknowledgements

Acknowledgements

This work was supported in part by the NSF (DMR-0804088) and startup funds from Washington University in St. Louis. As a visiting student from Xiamen University, M. J. was also partially supported by the China Scholarship Council (CSC). Part of the work was performed at the Nano Research Facility (NRF), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the NSF under award no. ECS-0335765. H. L. and J. L. were supported by the University of Missouri-St. Louis.

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