Synthesis of Monodisperse Palladium Nanoclusters Using Metal–Organic Frameworks as Sacrificial Templates

Li, Xinle; Goh, Tian Wei; Xiao, Chaoxian; Stanton, Alexandria L. D.; Pei, Yuchen; Jain, Prashant K.; Huang, Wenyu

doi:10.1002/cnma.201600121

Title: Synthesis of Monodisperse Palladium Nanoclusters Using Metal–Organic Frameworks as Sacrificial Templates

Journal Article · Mon Jun 20 00:00:00 EDT 2016 · ChemNanoMat

DOI:https://doi.org/10.1002/cnma.201600121· OSTI ID:1400977

Li, Xinle ^[1]; Goh, Tian Wei ^[1]; Xiao, Chaoxian ^[1]; Stanton, Alexandria L. D. ^[2]; Pei, Yuchen ^[1];

^[2];

^[1]

Department of Chemistry Iowa State University Ames Laboratory U.S. Department of Energy Ames Iowa 50011 United States
Department of Chemistry University of Illinois at Urbana-Champaign Urbana Illinois 61801 United States

Abstract An interfacial etching approach was developed for the synthesis of monodisperse and ultrasmall thiolated palladium nanoclusters (Pd NCs) using Zr‐UiO‐66‐NH ₂ metal–organic frameworks (MOFs) as sacrificial templates. The Pd NCs were originally synthesized inside the cavities of the MOFs (Pd@UiO‐66‐NH ₂ ). The Pd NCs released from the MOFs have a strikingly small size with narrow distribution (1.1±0.1 nm), amounting to a cluster size of ca. 40 Pd atoms. The ¹ H NMR spectrum indicates that thiol is the only capping agent for these Pd NCs. We derived the composition of the thiolated Pd NCs using thermogravimetric analysis (TGA) and inductively coupled plasma mass spectrometry (ICP‐MS) analysis. Moreover, the Pd NCs size can be tuned by using MOF templates with different cavity sizes. The thiolated Pd NCs are catalytically active in a model Suzuki–Miyaura coupling reaction.

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Sponsoring Organization:: USDOE

OSTI ID:: 1400977

Journal Information:: ChemNanoMat, Journal Name: ChemNanoMat Vol. 2 Journal Issue: 8; ISSN 2199-692X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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References (55)

Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration Yang, Qingyuan; Wiersum, Andrew D.; Llewellyn, Philip L. Chemical Communications, Vol. 47, Issue 34 https://doi.org/10.1039/c1cc13543k	journal	January 2011
Controlled Etching of Au:SR Cluster Compounds Schaaff, T. Gregory; Whetten, Robert L. The Journal of Physical Chemistry B, Vol. 103, Issue 44 https://doi.org/10.1021/jp993229d	journal	November 1999
EXAFS study on interfacial structure between Pd cluster and n-octadecanethiolate monolayer: formation of mixed Pd–S interlayer Murayama, Haruno; Ichikuni, Nobuyuki; Negishi, Yuichi Chemical Physics Letters, Vol. 376, Issue 1-2 https://doi.org/10.1016/S0009-2614(03)00911-4	journal	July 2003
Homogeneous Hydrogenation Catalysis with Monodisperse, Dendrimer-Encapsulated Pd and Pt Nanoparticles Zhao, Mingqi; Crooks, Richard M. Angewandte Chemie International Edition, Vol. 38, Issue 3 https://doi.org/10.1002/(SICI)1521-3773(19990201)38:3<364::AID-ANIE364>3.0.CO;2-L	journal	February 1999
Gas storage in porous metal–organic frameworks for clean energy applications Ma, Shengqian; Zhou, Hong-Cai Chem. Commun., Vol. 46, Issue 1 https://doi.org/10.1039/B916295J	journal	January 2010
Size Dependence of Atomically Precise Gold Nanoclusters in Chemoselective Hydrogenation and Active Site Structure Li, Gao; Jiang, De-en; Kumar, Santosh ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500533h	journal	June 2014
Direct Preparation and Size Control of Palladium Nanoparticle Hydrosols by Water-Soluble Isocyanide Ligands Yonezawa, Tetsu; Imamura, Kuniko; Kimizuka, Nobuo Langmuir, Vol. 17, Issue 16 https://doi.org/10.1021/la0101954	journal	August 2001
Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals Schaate, Andreas; Roy, Pascal; Godt, Adelheid Chemistry - A European Journal, Vol. 17, Issue 24 https://doi.org/10.1002/chem.201003211	journal	May 2011
Ordered metal nanostructureself-assembly using metal–organic frameworks as templates Jacobs, Benjamin W.; Houk, Ronald J. T.; Anstey, Mitchell R. Chem. Sci., Vol. 2, Issue 3 https://doi.org/10.1039/C0SC00377H	journal	January 2011
Quantum Sized Gold Nanoclusters with Atomic Precision Qian, Huifeng; Zhu, Manzhou; Wu, Zhikun Accounts of Chemical Research, Vol. 45, Issue 9 https://doi.org/10.1021/ar200331z	journal	June 2012
Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang Nano Letters, Vol. 8, Issue 7 https://doi.org/10.1021/nl801325m	journal	July 2008
Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm Regime Liu, Yongmei; Tsunoyama, Hironori; Akita, Tomoki ACS Catalysis, Vol. 1, Issue 1 https://doi.org/10.1021/cs100043j	journal	December 2010
Facile Preparation of Organic Nanoparticles by Interfacial Cross-Linking of Reverse Micelles and Template Synthesis of Subnanometer Au−Pt Nanoparticles Zhang, Shiyong; Zhao, Yan ACS Nano, Vol. 5, Issue 4 https://doi.org/10.1021/nn102666k	journal	March 2011
Hydrogen Reactivity of Palladium Nanoparticles Coated with Mixed Monolayers of Alkyl Thiols and Alkyl Amines for Sensing and Catalysis Applications Moreno, Monica; Ibañez, Francisco J.; Jasinski, Jacek B. Journal of the American Chemical Society, Vol. 133, Issue 12 https://doi.org/10.1021/ja108378x	journal	March 2011
The Story of a Monodisperse Gold Nanoparticle: Au ₂₅ L ₁₈ Parker, Joseph F.; Fields-Zinna, Christina A.; Murray, Royce W. Accounts of Chemical Research, Vol. 43, Issue 9 https://doi.org/10.1021/ar100048c	journal	September 2010
Metal-Organic Framework Templated Synthesis of Ultrathin, Well-Aligned Metallic Nanowires Volosskiy, Boris; Niwa, Kenta; Chen, Yu ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/nn5072446	journal	February 2015
Preparation of Alkanethiolate-Protected Palladium Nanoparticles and Their Size Dependence on Synthetic Conditions Quiros, Ignacio; Yamada, Mami; Kubo, Kenya Langmuir, Vol. 18, Issue 4 https://doi.org/10.1021/la0114023	journal	February 2002
Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds Miyaura, Norio.; Suzuki, Akira. Chemical Reviews, Vol. 95, Issue 7 https://doi.org/10.1021/cr00039a007	journal	November 1995
Large-Scale Synthesis of Thiolated Au ₂₅ Clusters via Ligand Exchange Reactions of Phosphine-Stabilized Au ₁₁ Clusters Shichibu, Yukatsu; Negishi, Yuichi; Tsukuda, Tatsuya Journal of the American Chemical Society, Vol. 127, Issue 39 https://doi.org/10.1021/ja053915s	journal	October 2005
Formation of Pdn(SR)m clusters (n<60) in the reactions of PdCl2 and RSH (R=n-C18H37, n-C12H25) Negishi, Yuichi; Murayama, Haruno; Tsukuda, Tatsuya Chemical Physics Letters, Vol. 366, Issue 5-6 https://doi.org/10.1016/S0009-2614(02)01643-3	journal	December 2002
Biomedical Applications of Metal Organic Frameworks Keskin, Seda; Kızılel, Seda Industrial & Engineering Chemistry Research, Vol. 50, Issue 4 https://doi.org/10.1021/ie101312k	journal	February 2011
Facile, Large-Scale Synthesis of Dodecanethiol-Stabilized Au ₃₈ Clusters ^† Qian, Huifeng; Zhu, Manzhou; Andersen, Ulla N. The Journal of Physical Chemistry A, Vol. 113, Issue 16 https://doi.org/10.1021/jp810893w	journal	April 2009
Functional materials derived from open framework templates/precursors: synthesis and applications Sun, Jian-Ke; Xu, Qiang Energy & Environmental Science, Vol. 7, Issue 7 https://doi.org/10.1039/c4ee00517a	journal	January 2014
Precursor engineering and controlled conversion for the synthesis of monodisperse thiolate-protected metal nanoclusters Yu, Yong; Yao, Qiaofeng; Luo, Zhentao Nanoscale, Vol. 5, Issue 11 https://doi.org/10.1039/c3nr00464c	journal	January 2013
Catalysis by metal nanoparticles embedded on metal–organic frameworks Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo Chemical Society Reviews, Vol. 41, Issue 15 https://doi.org/10.1039/c2cs35047e	journal	January 2012
Synthesis and Characterization of a New Tiara Pd(II) Thiolate Complex, [Pd(SC ₁₂ H ₂₅ ) ₂ ] ₆ , and Its Solution-Phase Thermolysis to Prepare Nearly Monodisperse Palladium Sulfide Nanoparticles Yang, Zhiqiang; Smetana, Alexander B.; Sorensen, Christopher M. Inorganic Chemistry, Vol. 46, Issue 7 https://doi.org/10.1021/ic061242o	journal	April 2007
Dendrimer-Encapsulated Nanoparticle Precursors to Supported Platinum Catalysts Lang, Huifang; May, R. Alan; Iversen, Brianna L. Journal of the American Chemical Society, Vol. 125, Issue 48 https://doi.org/10.1021/ja0364120	journal	December 2003
Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries Lu, Yizhong; Chen, Wei Chemical Society Reviews, Vol. 41, Issue 9 https://doi.org/10.1039/c2cs15325d	journal	January 2012
Homogene katalytische Hydrierung mit monodispersen, dendrimerumhüllten Pd- und Pt-Nanopartikeln Zhao, Mingqi; Crooks, Richard M. Angewandte Chemie, Vol. 111, Issue 3 https://doi.org/10.1002/(SICI)1521-3757(19990201)111:3<375::AID-ANGE375>3.0.CO;2-E	journal	February 1999
Reinvestigation of the structure of PdS Brese, N. E.; Squattrito, P. J.; Ibers, J. A. Acta Crystallographica Section C Crystal Structure Communications, Vol. 41, Issue 12 https://doi.org/10.1107/S0108270185009623	journal	December 1985
Alkanethiolate-Protected Palladium Nanoparticles Chen, Shaowei; Huang, Kui; Stearns, Jaime A. Chemistry of Materials, Vol. 12, Issue 2 https://doi.org/10.1021/cm9906203	journal	February 2000
Artificial metalloenzymes via encapsulation of hydrophobic transition-metal catalysts in surface-crosslinked micelles (SCMs) Zhang, Shiyong; Zhao, Yan Chemical Communications, Vol. 48, Issue 80 https://doi.org/10.1039/c2cc33012a	journal	January 2012
Atomically Precise Gold Nanoclusters as New Model Catalysts Li, Gao; Jin, Rongchao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300213z	journal	March 2013
Heat-treatment of metal–organic frameworks for green energy applications Lux, Lacey; Williams, Kia; Ma, Shengqian CrystEngComm, Vol. 17, Issue 1 https://doi.org/10.1039/C4CE01499E	journal	January 2015
Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal–Organic Frameworks Li, Xinle; Goh, Tian Wei; Li, Lei ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00397	journal	April 2016
Catalysis by Palladium Nanoparticles in Microemulsions de Jesus, Dionísia M.; Spiro, Michael Langmuir, Vol. 16, Issue 11 https://doi.org/10.1021/la9915668	journal	May 2000
Metal-Organic Framework as a Template for Porous Carbon Synthesis Liu, Bo; Shioyama, Hiroshi; Akita, Tomoki Journal of the American Chemical Society, Vol. 130, Issue 16 https://doi.org/10.1021/ja7106146	journal	April 2008
Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation Guo, Zhiyong; Xiao, Chaoxian; Maligal-Ganesh, Raghu V. ACS Catalysis, Vol. 4, Issue 5, p. 1340-1348 https://doi.org/10.1021/cs400982n	journal	April 2014
Synthesis, Characterization, Reactivity, and Electrochemistry of Palladium Monolayer Protected Clusters Zamborini, Francis P.; Gross, Stephen M.; Murray, Royce W. Langmuir, Vol. 17, Issue 2 https://doi.org/10.1021/la0010525	journal	January 2001
A Versatile Approach to the Synthesis of Functionalized Thiol-Protected Palladium Nanoparticles Cargnello, Matteo; Wieder, Noah L.; Canton, Patrizia Chemistry of Materials, Vol. 23, Issue 17 https://doi.org/10.1021/cm2014658	journal	September 2011
Ultraviolet–visible absorption spectra of the colloidal metallic elements Creighton, J. Alan; Eadon, Desmond G. J. Chem. Soc., Faraday Trans., Vol. 87, Issue 24 https://doi.org/10.1039/FT9918703881	journal	January 1991
A new synthesis strategy for chiral CdS nanotubes based on a homochiral MOF template Kuang, Xuan; Ma, Yu; Zhang, Caiyun Chemical Communications, Vol. 51, Issue 27 https://doi.org/10.1039/C5CC00733J	journal	January 2015
Metal/metal oxide nanostructures derived from metal–organic frameworks Song, Yonghai; Li, Xia; Sun, Lanlan RSC Advances, Vol. 5, Issue 10 https://doi.org/10.1039/C4RA12273A	journal	January 2015
Atomically precise metal nanoclusters: stable sizes and optical properties Jin, Rongchao Nanoscale, Vol. 7, Issue 5 https://doi.org/10.1039/C4NR05794E	journal	January 2015
Au ₉₉ (SPh) ₄₂ Nanomolecules: Aromatic Thiolate Ligand Induced Conversion of Au ₁₄₄ (SCH ₂ CH ₂ Ph) ₆₀ Nimmala, Praneeth Reddy; Dass, Amala Journal of the American Chemical Society, Vol. 136, Issue 49 https://doi.org/10.1021/ja5103025	journal	November 2014
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953	journal	October 2008
Metal–Organic Framework Materials as Chemical Sensors Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K. Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125 https://doi.org/10.1021/cr200324t	journal	September 2011
Gold Nanocluster-Based Fluorescent Probes for Near-Infrared and Turn-On Sensing of Glutathione in Living Cells Tian, Dahui; Qian, Zhangsheng; Xia, Yunsheng Langmuir, Vol. 28, Issue 8 https://doi.org/10.1021/la204380a	journal	February 2012
Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters Chen, Jishi; Liu, Liren; Weng, Linhong Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep16628	journal	November 2015
The crystal structures of Pd ₄ Se and Pd ₄ S Grønvold, F.; Røst, E. Acta Crystallographica, Vol. 15, Issue 1 https://doi.org/10.1107/S0365110X62000031	journal	January 1962
New Insights into Brust−Schiffrin Metal Nanoparticle Synthesis Goulet, Paul J. G.; Lennox, R. Bruce Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja104011b	journal	July 2010
Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5006635	journal	September 2014
Anion Stripping as a General Method to Create Cationic Porous Framework with Mobile Anions Mao, Chengyu; Kudla, Ryan A.; Zuo, Fan Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja5030723	journal	May 2014
Ultra-large-scale syntheses of monodisperse nanocrystals Park, Jongnam; An, Kwangjin; Hwang, Yosun Nature Materials, Vol. 3, Issue 12 https://doi.org/10.1038/nmat1251	journal	November 2004
Size Dependent Study of MeOH Decomposition Over Size-selected Pt Nanoparticles Synthesized via Micelle Encapsulation Croy, Jason R.; Mostafa, Simon; Liu, Jing Catalysis Letters, Vol. 118, Issue 1-2 https://doi.org/10.1007/s10562-007-9162-1	journal	July 2007

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