Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal

Wu, Zili; Hu, Guoxiang; Jiang, De-en; Mullins, David R.; Zhang, Qianfan; Allard, Jr, Lawrence Frederick; Wang, Laisheng; Overbury, Steven H.

doi:10.1021/acs.nanolett.6b03221

Diphosphine-Protected Au₂₂ Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal

Journal Article · Thu Sep 29 00:00:00 EDT 2016 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.6b03221· OSTI ID:1360045

Wu, Zili ^[1]; Hu, Guoxiang ^[2]; Jiang, De-en ^[2]; Mullins, David R. ^[1]; Zhang, Qianfan ^[3]; Allard, Jr, Lawrence Frederick ^[1]; Wang, Laisheng ^[3]; Overbury, Steven H. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Brown Univ., Providence, RI (United States)

Investigation of monodispersed and atomically-precise Au nanoclusters provides a route to understand the roles of coordination, size, and ligand effects in Au catalysis. We have explored the catalytic behavior of a newly-synthesized Au₂₂(L⁸)₆ nanocluster (L = 1,8-bis(diphenylphosphino) octane) with in situ uncoordinated Au sites supported on TiO₂, CeO₂ and Al₂O₃. Stability of the supported Au₂₂ nanoclusters was probed structurally by EXAFS and HAADF-STEM, and their adsorption and reactivity for CO oxidation were investigated by IR absorption spectroscopy and temperature programed flow reaction. Low temperature CO oxidation activity was observed for the supported pristine Au₂₂(L⁸)₆ nanoclusters without ligand removal. Isotopically labeled O₂ was used to demonstrate that the reaction pathway occurs through a redox mechanism, consistent with the observed support-dependent activity trend: CeO₂ > TiO₂ > Al₂O₃. Substantiated by density functional theory (DFT) calculations, we conclude that the uncoordinated Au sites in the intact Au₂₂(L⁸)₆ nanoclusters are capable of adsorbing CO, activating O2 and promoting CO oxidation reaction. Thanks to the presence of the in situ coordination unsaturated Au atoms, this work is the first clear demonstration of a ligand-protected Au nanocluster that are active for gas phase catalysis without the need of ligand removal.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1360045

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 10 Vol. 16; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

An Atomic-Level Strategy for Unraveling Gold Nanocatalysis from the Perspective of Aun(SR)m Nanoclusters Zhu, Yan; Qian, Huifeng; Jin, Rongchao Chemistry - A European Journal, Vol. 16, Issue 37 https://doi.org/10.1002/chem.201001086	journal	August 2010
Au20: A Tetrahedral Cluster. Li, Jun; Li, Xi; Zhai, Hua-Jin ChemInform, Vol. 34, Issue 20 https://doi.org/10.1002/chin.200320001	journal	May 2003
Au/TiO2 Nanosized Samples: A Catalytic, TEM, and FTIR Study of the Effect of Calcination Temperature on the CO Oxidation Boccuzzi, Flora; Chiorino, Anna; Manzoli, Maela Journal of Catalysis, Vol. 202, Issue 2 https://doi.org/10.1006/jcat.2001.3290	journal	September 2001
Electronic and optical properties of the Au22[1,8-bis(diphenylphosphino) octane]6 nanoclusters disclosed by DFT and TD-DFT calculations Muniz-Miranda, Francesco; Presti, Davide; Menziani, Maria Cristina Theoretical Chemistry Accounts, Vol. 135, Issue 1 https://doi.org/10.1007/s00214-015-1764-x	journal	December 2015
On the potential role of hydroxyl groups in CO oxidation over Au/Al2O3 Costello, C. K.; Yang, J. H.; Law, H. Y. Applied Catalysis A: General, Vol. 243, Issue 1 https://doi.org/10.1016/S0926-860X(02)00533-1	journal	March 2003
Evidence of active species in CO oxidation catalyzed by highly dispersed supported gold Fierro-Gonzalez, Juan C.; Gates, Bruce C. Catalysis Today, Vol. 122, Issue 3-4, p. 201-210 https://doi.org/10.1016/j.cattod.2007.01.020	journal	April 2007
Preparation of TiO2-supported Au nanoparticle catalysts from a Au13 cluster precursor: Ligand removal using ozone exposure versus a rapid thermal treatment Menard, L.; Xu, F.; Nuzzo, R. Journal of Catalysis, Vol. 243, Issue 1 https://doi.org/10.1016/j.jcat.2006.07.006	journal	October 2006
New insight on the nature of catalytically active gold sites: Quantitative CO chemisorption data and analysis of FTIR spectra of adsorbed CO and of isotopic mixtures Chiorino, Anna; Manzoli, Maela; Menegazzo, Federica Journal of Catalysis, Vol. 262, Issue 1 https://doi.org/10.1016/j.jcat.2008.12.017	journal	February 2009
CO oxidation on Au/FePO4 catalyst: Reaction pathways and nature of Au sites Li, Meijun; Wu, Zili; Ma, Zhen Journal of Catalysis, Vol. 266, Issue 1 https://doi.org/10.1016/j.jcat.2009.05.019	journal	August 2009
Support effects in the Au-catalyzed CO oxidation – Correlation between activity, oxygen storage capacity, and support reducibility Widmann, D.; Liu, Y.; Schüth, F. Journal of Catalysis, Vol. 276, Issue 2 https://doi.org/10.1016/j.jcat.2010.09.023	journal	December 2010
CO oxidation on phosphate-supported Au catalysts: Effect of support reducibility on surface reactions Li, Meijun; Wu, Zili; Overbury, S. H. Journal of Catalysis, Vol. 278, Issue 1 https://doi.org/10.1016/j.jcat.2010.11.019	journal	February 2011
Oxide-supported atomically precise gold nanocluster for catalyzing Sonogashira cross-coupling Li, Gao; Jiang, De-en; Liu, Chao Journal of Catalysis, Vol. 306 https://doi.org/10.1016/j.jcat.2013.06.017	journal	October 2013
Catalysis by gold: New insights into the support effect Liu, Xiao Yan; Wang, Aiqin; Zhang, Tao Nano Today, Vol. 8, Issue 4 https://doi.org/10.1016/j.nantod.2013.07.005	journal	August 2013
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
Thiolate-Mediated Selectivity Control in Aerobic Alcohol Oxidation by Porous Carbon-Supported Au ₂₅ Clusters Yoskamtorn, Tatchamapan; Yamazoe, Seiji; Takahata, Ryo ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs501010x	journal	September 2014
Inhibition at Perimeter Sites of Au/TiO ₂ Oxidation Catalyst by Reactant Oxygen Green, Isabel Xiaoye; Tang, Wenjie; McEntee, Monica Journal of the American Chemical Society, Vol. 134, Issue 30 https://doi.org/10.1021/ja304426b	journal	July 2012
Controlling Gold Nanoclusters by Diphospine Ligands Chen, Jing; Zhang, Qian-Fan; Bonaccorso, Timary A. Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja411061e	journal	December 2013
Thiolate Ligands as a Double-Edged Sword for CO Oxidation on CeO ₂ Supported Au ₂₅ (SCH ₂ CH ₂ Ph) ₁₈ Nanoclusters Wu, Zili; Jiang, De-en; Mann, Amanda K. P. Journal of the American Chemical Society, Vol. 136, Issue 16 https://doi.org/10.1021/ja5018706	journal	April 2014
Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles Wang, Yu; Wan, Xian-Kai; Ren, Liting Journal of the American Chemical Society, Vol. 138, Issue 10 https://doi.org/10.1021/jacs.5b12730	journal	March 2016
Gold Quantum Boxes: On the Periodicities and the Quantum Confinement in the Au ₂₈ , Au ₃₆ , Au ₄₄ , and Au ₅₂ Magic Series Zeng, Chenjie; Chen, Yuxiang; Iida, Kenji Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.5b12747	journal	March 2016
Preparation and Comparison of Supported Gold Nanocatalysts on Anatase, Brookite, Rutile, and P25 Polymorphs of TiO ₂ for Catalytic Oxidation of CO Yan, Wenfu; Chen, Bei; Mahurin, S. M. The Journal of Physical Chemistry B, Vol. 109, Issue 21 https://doi.org/10.1021/jp044091o	journal	June 2005
Toward the Solution Synthesis of the Tetrahedral Au ₂₀ Cluster Zhang, Hai-Feng; Stender, Matthias; Zhang, Rui The Journal of Physical Chemistry B, Vol. 108, Issue 33 https://doi.org/10.1021/jp048636q	journal	August 2004
Facile Syntheses of Monodisperse Ultrasmall Au Clusters Bertino, Massimo F.; Sun, Zhong-Ming; Zhang, Rui The Journal of Physical Chemistry B, Vol. 110, Issue 43 https://doi.org/10.1021/jp065227g	journal	November 2006
Modulation of Active Sites in Supported Au ₃₈ (SC ₂ H ₄ Ph) ₂₄ Cluster Catalysts: Effect of Atmosphere and Support Material Zhang, B.; Kaziz, S.; Li, H. The Journal of Physical Chemistry C, Vol. 119, Issue 20 https://doi.org/10.1021/jp512022v	journal	January 2015
DRIFTS-QMS Study of Room Temperature CO Oxidation on Au/SiO ₂ Catalyst: Nature and Role of Different Au Species Wu, Zili; Zhou, Shenghu; Zhu, Haoguo The Journal of Physical Chemistry C, Vol. 113, Issue 9 https://doi.org/10.1021/jp809220z	journal	February 2009
CO Oxidation at the Interface of Au Nanoclusters and the Stepped-CeO ₂ (111) Surface by the Mars–van Krevelen Mechanism Kim, Hyun You; Henkelman, Graeme The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz301778b	journal	December 2012
Probing Defect Sites on CeO ₂ Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O ₂ Adsorption ^† Wu, Zili; Li, Meijun; Howe, Jane Langmuir, Vol. 26, Issue 21 https://doi.org/10.1021/la101723w	journal	November 2010
CO Oxidation Catalyzed by Oxide-Supported Au ₂₅ (SR) ₁₈ Nanoclusters and Identification of Perimeter Sites as Active Centers Nie, Xiaotao; Qian, Huifeng; Ge, Qingjie ACS Nano, Vol. 6, Issue 7 https://doi.org/10.1021/nn301019f	journal	June 2012
Synthesis, characterization, and testing of supported Au catalysts prepared from atomically-tailored Au ₃₈ (SC ₁₂ H ₂₅ ) ₂₄ clusters Gaur, Sarthak; Miller, Jeffrey T.; Stellwagen, Daniel Phys. Chem. Chem. Phys., Vol. 14, Issue 5 https://doi.org/10.1039/C1CP22438G	journal	January 2012
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
The support effect on the size and catalytic activity of thiolated Au ₂₅ nanoclusters as precatalysts Fang, Jun; Li, Jingguo; Zhang, Bin Nanoscale, Vol. 7, Issue 14 https://doi.org/10.1039/C5NR00549C	journal	January 2015
Mild activation of CeO ₂ -supported gold nanoclusters and insight into the catalytic behavior in CO oxidation Li, Weili; Ge, Qingjie; Ma, Xiangang Nanoscale, Vol. 8, Issue 4 https://doi.org/10.1039/C5NR07498C	journal	January 2016
Oxygen-assisted reduction of Au species on Au/SiO2 catalyst in room temperature CO oxidation Wu, Zili; Zhou, Shenghu; Zhu, Haoguo Chemical Communications, Issue 28 https://doi.org/10.1039/b803834a	journal	January 2008
Spiers Memorial Lecture : Role of perimeter interfaces in catalysis by gold nanoparticles Haruta, Masatake Faraday Discussions, Vol. 152 https://doi.org/10.1039/c1fd00107h	journal	January 2011
Stabilizing gold clusters by heterostructured transition-metal oxide–mesoporous silica supports for enhanced catalytic activities for CO oxidation Ma, Guicen; Binder, Andrew; Chi, Miaofang Chemical Communications, Vol. 48, Issue 93 https://doi.org/10.1039/c2cc35787a	journal	January 2012
Stabilized gold clusters: from isolation toward controlled synthesis Maity, Prasenjit; Xie, Songhai; Yamauchi, Miho Nanoscale, Vol. 4, Issue 14 https://doi.org/10.1039/c2nr30900a	journal	January 2012
Spectroscopic Observation of Dual Catalytic Sites During Oxidation of CO on a Au/TiO2 Catalyst Green, I. X.; Tang, W.; Neurock, M. Science, Vol. 333, Issue 6043 https://doi.org/10.1126/science.1207272	journal	August 2011
Atomically Dispersed Supported Metal Catalysts Flytzani-Stephanopoulos, Maria; Gates, Bruce C. Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1 https://doi.org/10.1146/annurev-chembioeng-062011-080939	journal	July 2012

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Size‐dependent electrophoretic migration and separation of water‐soluble gold nanoclusters by capillary electrophoresis Wan, Ting; Tang, Fenglin; Yin, Yanru ELECTROPHORESIS, Vol. 40, Issue 9 https://doi.org/10.1002/elps.201800347	journal	February 2019
Structure and reactivity of gold cluster protected by triphosphine ligands: DFT study Golosnaya, M. N.; Pichugina, D. A.; Kuz’menko, N. E. Structural Chemistry, Vol. 30, Issue 2 https://doi.org/10.1007/s11224-019-01292-2	journal	February 2019
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Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia Physical Chemistry Chemical Physics, Vol. 19, Issue 26 https://doi.org/10.1039/c7cp01402c	journal	January 2017
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Preparation of gas phase naked silver cluster cations outside a mass spectrometer from ligand protected clusters in solution Jash, Madhuri; Reber, Arthur C.; Ghosh, Atanu Nanoscale, Vol. 10, Issue 33 https://doi.org/10.1039/c8nr04146f	journal	January 2018
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Ligand-protected atomically precise gold nanoclusters as model catalysts for oxidation reactions Tian, Shubo; Cao, Yitao; Chen, Tiankai Chemical Communications, Vol. 56, Issue 8 https://doi.org/10.1039/c9cc08215h	journal	January 2020
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