Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal
Abstract
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.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of California, Riverside, CA (United States)
- Brown Univ., Providence, RI (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1360045
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 10; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wu, Zili, Hu, Guoxiang, Jiang, De-en, Mullins, David R., Zhang, Qianfan, Allard, Jr, Lawrence Frederick, Wang, Laisheng, and Overbury, Steven H. Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal. United States: N. p., 2016.
Web. doi:10.1021/acs.nanolett.6b03221.
Wu, Zili, Hu, Guoxiang, Jiang, De-en, Mullins, David R., Zhang, Qianfan, Allard, Jr, Lawrence Frederick, Wang, Laisheng, & Overbury, Steven H. Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal. United States. https://doi.org/10.1021/acs.nanolett.6b03221
Wu, Zili, Hu, Guoxiang, Jiang, De-en, Mullins, David R., Zhang, Qianfan, Allard, Jr, Lawrence Frederick, Wang, Laisheng, and Overbury, Steven H. Thu .
"Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal". United States. https://doi.org/10.1021/acs.nanolett.6b03221. https://www.osti.gov/servlets/purl/1360045.
@article{osti_1360045,
title = {Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal},
author = {Wu, Zili and Hu, Guoxiang and Jiang, De-en and Mullins, David R. and Zhang, Qianfan and Allard, Jr, Lawrence Frederick and Wang, Laisheng and Overbury, Steven H.},
abstractNote = {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.},
doi = {10.1021/acs.nanolett.6b03221},
journal = {Nano Letters},
number = 10,
volume = 16,
place = {United States},
year = {Thu Sep 29 00:00:00 EDT 2016},
month = {Thu Sep 29 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 70 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Atomically Precise Gold Nanoclusters as New Model Catalysts
journal, March 2013
- Li, Gao; Jin, Rongchao
- Accounts of Chemical Research, Vol. 46, Issue 8
Atomically Dispersed Supported Metal Catalysts
journal, July 2012
- Flytzani-Stephanopoulos, Maria; Gates, Bruce C.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1
Stabilized gold clusters: from isolation toward controlled synthesis
journal, January 2012
- Maity, Prasenjit; Xie, Songhai; Yamauchi, Miho
- Nanoscale, Vol. 4, Issue 14
An Atomic-Level Strategy for Unraveling Gold Nanocatalysis from the Perspective of Aun(SR)m Nanoclusters
journal, August 2010
- Zhu, Yan; Qian, Huifeng; Jin, Rongchao
- Chemistry - A European Journal, Vol. 16, Issue 37
Gold Quantum Boxes: On the Periodicities and the Quantum Confinement in the Au 28 , Au 36 , Au 44 , and Au 52 Magic Series
journal, March 2016
- Zeng, Chenjie; Chen, Yuxiang; Iida, Kenji
- Journal of the American Chemical Society, Vol. 138, Issue 12
Thiolate Ligands as a Double-Edged Sword for CO Oxidation on CeO 2 Supported Au 25 (SCH 2 CH 2 Ph) 18 Nanoclusters
journal, April 2014
- Wu, Zili; Jiang, De-en; Mann, Amanda K. P.
- Journal of the American Chemical Society, Vol. 136, Issue 16
Stabilizing gold clusters by heterostructured transition-metal oxide–mesoporous silica supports for enhanced catalytic activities for CO oxidation
journal, January 2012
- Ma, Guicen; Binder, Andrew; Chi, Miaofang
- Chemical Communications, Vol. 48, Issue 93
Synthesis, characterization, and testing of supported Au catalysts prepared from atomically-tailored Au 38 (SC 12 H 25 ) 24 clusters
journal, January 2012
- Gaur, Sarthak; Miller, Jeffrey T.; Stellwagen, Daniel
- Phys. Chem. Chem. Phys., Vol. 14, Issue 5
Preparation of TiO2-supported Au nanoparticle catalysts from a Au13 cluster precursor: Ligand removal using ozone exposure versus a rapid thermal treatment
journal, October 2006
- Menard, L.; Xu, F.; Nuzzo, R.
- Journal of Catalysis, Vol. 243, Issue 1
Thiolate-Mediated Selectivity Control in Aerobic Alcohol Oxidation by Porous Carbon-Supported Au 25 Clusters
journal, September 2014
- Yoskamtorn, Tatchamapan; Yamazoe, Seiji; Takahata, Ryo
- ACS Catalysis, Vol. 4, Issue 10
Modulation of Active Sites in Supported Au 38 (SC 2 H 4 Ph) 24 Cluster Catalysts: Effect of Atmosphere and Support Material
journal, January 2015
- Zhang, B.; Kaziz, S.; Li, H.
- The Journal of Physical Chemistry C, Vol. 119, Issue 20
The support effect on the size and catalytic activity of thiolated Au 25 nanoclusters as precatalysts
journal, January 2015
- Fang, Jun; Li, Jingguo; Zhang, Bin
- Nanoscale, Vol. 7, Issue 14
CO Oxidation Catalyzed by Oxide-Supported Au 25 (SR) 18 Nanoclusters and Identification of Perimeter Sites as Active Centers
journal, June 2012
- Nie, Xiaotao; Qian, Huifeng; Ge, Qingjie
- ACS Nano, Vol. 6, Issue 7
Oxide-supported atomically precise gold nanocluster for catalyzing Sonogashira cross-coupling
journal, October 2013
- Li, Gao; Jiang, De-en; Liu, Chao
- Journal of Catalysis, Vol. 306
Mild activation of CeO 2 -supported gold nanoclusters and insight into the catalytic behavior in CO oxidation
journal, January 2016
- Li, Weili; Ge, Qingjie; Ma, Xiangang
- Nanoscale, Vol. 8, Issue 4
Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles
journal, March 2016
- Wang, Yu; Wan, Xian-Kai; Ren, Liting
- Journal of the American Chemical Society, Vol. 138, Issue 10
Au20: A Tetrahedral Cluster.
journal, May 2003
- Li, Jun; Li, Xi; Zhai, Hua-Jin
- ChemInform, Vol. 34, Issue 20
Toward the Solution Synthesis of the Tetrahedral Au 20 Cluster
journal, August 2004
- Zhang, Hai-Feng; Stender, Matthias; Zhang, Rui
- The Journal of Physical Chemistry B, Vol. 108, Issue 33
Facile Syntheses of Monodisperse Ultrasmall Au Clusters
journal, November 2006
- Bertino, Massimo F.; Sun, Zhong-Ming; Zhang, Rui
- The Journal of Physical Chemistry B, Vol. 110, Issue 43
Controlling Gold Nanoclusters by Diphospine Ligands
journal, December 2013
- Chen, Jing; Zhang, Qian-Fan; Bonaccorso, Timary A.
- Journal of the American Chemical Society, Vol. 136, Issue 1
Electronic and optical properties of the Au22[1,8-bis(diphenylphosphino) octane]6 nanoclusters disclosed by DFT and TD-DFT calculations
journal, December 2015
- Muniz-Miranda, Francesco; Presti, Davide; Menziani, Maria Cristina
- Theoretical Chemistry Accounts, Vol. 135, Issue 1
Preparation and Comparison of Supported Gold Nanocatalysts on Anatase, Brookite, Rutile, and P25 Polymorphs of TiO 2 for Catalytic Oxidation of CO
journal, June 2005
- Yan, Wenfu; Chen, Bei; Mahurin, S. M.
- The Journal of Physical Chemistry B, Vol. 109, Issue 21
Support effects in the Au-catalyzed CO oxidation – Correlation between activity, oxygen storage capacity, and support reducibility
journal, December 2010
- Widmann, D.; Liu, Y.; Schüth, F.
- Journal of Catalysis, Vol. 276, Issue 2
Spiers Memorial Lecture : Role of perimeter interfaces in catalysis by gold nanoparticles
journal, January 2011
- Haruta, Masatake
- Faraday Discussions, Vol. 152
Catalysis by gold: New insights into the support effect
journal, August 2013
- Liu, Xiao Yan; Wang, Aiqin; Zhang, Tao
- Nano Today, Vol. 8, Issue 4
DRIFTS-QMS Study of Room Temperature CO Oxidation on Au/SiO 2 Catalyst: Nature and Role of Different Au Species
journal, February 2009
- Wu, Zili; Zhou, Shenghu; Zhu, Haoguo
- The Journal of Physical Chemistry C, Vol. 113, Issue 9
Oxygen-assisted reduction of Au species on Au/SiO2 catalyst in room temperature CO oxidation
journal, January 2008
- Wu, Zili; Zhou, Shenghu; Zhu, Haoguo
- Chemical Communications, Issue 28
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
journal, February 2009
- Chiorino, Anna; Manzoli, Maela; Menegazzo, Federica
- Journal of Catalysis, Vol. 262, Issue 1
Inhibition at Perimeter Sites of Au/TiO 2 Oxidation Catalyst by Reactant Oxygen
journal, July 2012
- Green, Isabel Xiaoye; Tang, Wenjie; McEntee, Monica
- Journal of the American Chemical Society, Vol. 134, Issue 30
Au/TiO2 Nanosized Samples: A Catalytic, TEM, and FTIR Study of the Effect of Calcination Temperature on the CO Oxidation
journal, September 2001
- Boccuzzi, Flora; Chiorino, Anna; Manzoli, Maela
- Journal of Catalysis, Vol. 202, Issue 2
Spectroscopic Observation of Dual Catalytic Sites During Oxidation of CO on a Au/TiO2 Catalyst
journal, August 2011
- Green, I. X.; Tang, W.; Neurock, M.
- Science, Vol. 333, Issue 6043
Evidence of active species in CO oxidation catalyzed by highly dispersed supported gold
journal, April 2007
- Fierro-Gonzalez, Juan C.; Gates, Bruce C.
- Catalysis Today, Vol. 122, Issue 3-4, p. 201-210
CO oxidation on phosphate-supported Au catalysts: Effect of support reducibility on surface reactions
journal, February 2011
- Li, Meijun; Wu, Zili; Overbury, S. H.
- Journal of Catalysis, Vol. 278, Issue 1
CO oxidation on Au/FePO4 catalyst: Reaction pathways and nature of Au sites
journal, August 2009
- Li, Meijun; Wu, Zili; Ma, Zhen
- Journal of Catalysis, Vol. 266, Issue 1
Probing Defect Sites on CeO 2 Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O 2 Adsorption †
journal, November 2010
- Wu, Zili; Li, Meijun; Howe, Jane
- Langmuir, Vol. 26, Issue 21
CO Oxidation at the Interface of Au Nanoclusters and the Stepped-CeO 2 (111) Surface by the Mars–van Krevelen Mechanism
journal, December 2012
- Kim, Hyun You; Henkelman, Graeme
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 1
On the potential role of hydroxyl groups in CO oxidation over Au/Al2O3
journal, March 2003
- Costello, C. K.; Yang, J. H.; Law, H. Y.
- Applied Catalysis A: General, Vol. 243, Issue 1
Works referencing / citing this record:
The Evolution in Catalytic Activity Driven by Periodic Transformation in the Inner Sites of Gold Clusters
journal, July 2019
- Sun, Yongnan; Wang, Endong; Ren, Yujing
- Advanced Functional Materials, Vol. 29, Issue 38
Multi-ligand-directed synthesis of chiral silver nanoclusters
journal, January 2017
- Zou, Xuejuan; Jin, Shan; Du, Wenjun
- Nanoscale, Vol. 9, Issue 43
An Au 22 (L 8 ) 6 nanocluster with in situ uncoordinated Au as a highly active catalyst for O 2 activation and CO oxidation
journal, January 2019
- Li, Fuhua; Tang, Qing
- Physical Chemistry Chemical Physics, Vol. 21, Issue 36
Activation of atom-precise clusters for catalysis
journal, January 2020
- Sudheeshkumar, V.; Sulaiman, Kazeem O.; Scott, Robert W. J.
- Nanoscale Advances, Vol. 2, Issue 1
Motif-mediated Au25(SPh)5(PPh3)10X2 nanorods with conjugated electron delocalization
journal, August 2018
- Zheng, Kai; Zhang, Jiangwei; Zhao, Dan
- Nano Research, Vol. 12, Issue 3
Preparation of gas phase naked silver cluster cations outside a mass spectrometer from ligand protected clusters in solution
journal, January 2018
- Jash, Madhuri; Reber, Arthur C.; Ghosh, Atanu
- Nanoscale, Vol. 10, Issue 33
Stronger-than-Pt hydrogen adsorption in a Au 22 nanocluster for the hydrogen evolution reaction
journal, January 2018
- Hu, Guoxiang; Wu, Zili; Jiang, De-en
- Journal of Materials Chemistry A, Vol. 6, Issue 17
Design of atomically precise Au 2 Pd 6 nanoclusters for boosting electrocatalytic hydrogen evolution on MoS 2
journal, January 2018
- Du, Yuanxin; Xiang, Ji; Ni, Kun
- Inorganic Chemistry Frontiers, Vol. 5, Issue 11
Dual effects of water vapor on ceria-supported gold clusters
journal, January 2018
- Li, Zhimin; Li, Weili; Abroshan, Hadi
- Nanoscale, Vol. 10, Issue 14
Triple 1D1D superatomic bonding. Au 22 (dppo) 6 as a Π 4 - and Δ 2 -triply bonded cluster based on Au 11 assembled units
journal, January 2020
- Muñoz-Castro, Alvaro
- Physical Chemistry Chemical Physics, Vol. 22, Issue 3
Ligand-protected atomically precise gold nanoclusters as model catalysts for oxidation reactions
journal, January 2020
- Tian, Shubo; Cao, Yitao; Chen, Tiankai
- Chemical Communications, Vol. 56, Issue 8
Heterogeneous gold catalysts for selective hydrogenation: from nanoparticles to atomically precise nanoclusters
journal, January 2019
- Zhao, Jianbo; Ge, Liming; Yuan, Haifeng
- Nanoscale, Vol. 11, Issue 24
Structure and reactivity of gold cluster protected by triphosphine ligands: DFT study
journal, February 2019
- Golosnaya, M. N.; Pichugina, D. A.; Kuz’menko, N. E.
- Structural Chemistry, Vol. 30, Issue 2
Size‐dependent electrophoretic migration and separation of water‐soluble gold nanoclusters by capillary electrophoresis
journal, February 2019
- Wan, Ting; Tang, Fenglin; Yin, Yanru
- ELECTROPHORESIS, Vol. 40, Issue 9