Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site
Abstract
Abstract Single-atom catalysts are widely investigated heterogeneous catalysts; however, the identification of the local environment of single atoms under experimental conditions, as well as operando characterization of their structural changes during catalytic reactions are still challenging. Here, the preferred local coordination of Rh single atoms is investigated on TiO 2 during calcination in O 2 , reduction in H 2 , CO adsorption, and reverse water gas shift (RWGS) reaction conditions. Theoretical and experimental studies clearly demonstrate that Rh single atoms adapt their local coordination and reactivity in response to various redox conditions. Single-atom catalysts hence do not have static local coordinations, but can switch from inactive to active structure under reaction conditions, hence explaining some conflicting literature accounts. The combination of approaches also elucidates the structure of the catalytic active site during reverse water gas shift. This insight on the real nature of the active site is key for the design of high-performance catalysts.
- Publication Date:
- Research Org.:
- Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); China Scholarship Council; National Science Foundation (NSF); National Natural Science Foundation of China (NNSFC)
- OSTI Identifier:
- 1619720
- Alternate Identifier(s):
- OSTI ID: 1595588
- Grant/Contract Number:
- SC0012573
- Resource Type:
- Published Article
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Name: Nature Communications Journal Volume: 10 Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United Kingdom
- Language:
- English
Citation Formats
Tang, Yan, Asokan, Chithra, Xu, Mingjie, Graham, George W., Pan, Xiaoqing, Christopher, Phillip, Li, Jun, and Sautet, Philippe. Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site. United Kingdom: N. p., 2019.
Web. doi:10.1038/s41467-019-12461-6.
Tang, Yan, Asokan, Chithra, Xu, Mingjie, Graham, George W., Pan, Xiaoqing, Christopher, Phillip, Li, Jun, & Sautet, Philippe. Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site. United Kingdom. doi:10.1038/s41467-019-12461-6.
Tang, Yan, Asokan, Chithra, Xu, Mingjie, Graham, George W., Pan, Xiaoqing, Christopher, Phillip, Li, Jun, and Sautet, Philippe. Thu .
"Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site". United Kingdom. doi:10.1038/s41467-019-12461-6.
@article{osti_1619720,
title = {Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site},
author = {Tang, Yan and Asokan, Chithra and Xu, Mingjie and Graham, George W. and Pan, Xiaoqing and Christopher, Phillip and Li, Jun and Sautet, Philippe},
abstractNote = {Abstract Single-atom catalysts are widely investigated heterogeneous catalysts; however, the identification of the local environment of single atoms under experimental conditions, as well as operando characterization of their structural changes during catalytic reactions are still challenging. Here, the preferred local coordination of Rh single atoms is investigated on TiO 2 during calcination in O 2 , reduction in H 2 , CO adsorption, and reverse water gas shift (RWGS) reaction conditions. Theoretical and experimental studies clearly demonstrate that Rh single atoms adapt their local coordination and reactivity in response to various redox conditions. Single-atom catalysts hence do not have static local coordinations, but can switch from inactive to active structure under reaction conditions, hence explaining some conflicting literature accounts. The combination of approaches also elucidates the structure of the catalytic active site during reverse water gas shift. This insight on the real nature of the active site is key for the design of high-performance catalysts.},
doi = {10.1038/s41467-019-12461-6},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {10}
}
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DOI: 10.1038/s41467-019-12461-6
DOI: 10.1038/s41467-019-12461-6
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
X-ray photoelectron spectroscopy (XPS) studies of clean and hydrated TiO2 (rutile) surfaces
journal, December 1979
- Sham, T. K.; Lazarus, M. S.
- Chemical Physics Letters, Vol. 68, Issue 2-3
Isolated Metal Active Site Concentration and Stability Control Catalytic CO 2 Reduction Selectivity
journal, February 2015
- Matsubu, John C.; Yang, Vanessa N.; Christopher, Phillip
- Journal of the American Chemical Society, Vol. 137, Issue 8
Toward Rational Design of Oxide-Supported Single-Atom Catalysts: Atomic Dispersion of Gold on Ceria
journal, April 2017
- Liu, Jin-Cheng; Wang, Yang-Gang; Li, Jun
- Journal of the American Chemical Society, Vol. 139, Issue 17
A quantum theory of molecular structure and its applications
journal, July 1991
- Bader, Richard F. W.
- Chemical Reviews, Vol. 91, Issue 5
Size-dependent dynamic structures of supported gold nanoparticles in CO oxidation reaction condition
journal, July 2018
- He, Yang; Liu, Jin-Cheng; Luo, Langli
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 30
Catalysis by Supported Single Metal Atoms
journal, November 2016
- Liu, Jingyue
- ACS Catalysis, Vol. 7, Issue 1
Catalysis on singly dispersed bimetallic sites
journal, August 2015
- Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia
- Nature Communications, Vol. 6, Issue 1
Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support
journal, December 2017
- Zhang, Shiran; Tang, Yan; Nguyen, Luan
- ACS Catalysis, Vol. 8, Issue 1
On the Nature of Support Effects of Metal Dioxides MO 2 (M = Ti, Zr, Hf, Ce, Th) in Single-Atom Gold Catalysts: Importance of Quantum Primogenic Effect
journal, July 2016
- Tang, Yan; Zhao, Shu; Long, Bo
- The Journal of Physical Chemistry C, Vol. 120, Issue 31
Ménage-à-trois: single-atom catalysis, mass spectrometry, and computational chemistry
journal, January 2017
- Schwarz, Helmut
- Catalysis Science & Technology, Vol. 7, Issue 19
Distribution of Ti 3+ Surface Sites in Reduced TiO 2
journal, March 2011
- Deskins, N. Aaron; Rousseau, Roger; Dupuis, Michel
- The Journal of Physical Chemistry C, Vol. 115, Issue 15
X-ray photoelectron spectroscopy (XPS) studies of hydrogen reduced rutile (TiO2-x) surfaces
journal, November 1982
- Lazarus, M. S.; Sham, T. K.
- Chemical Physics Letters, Vol. 92, Issue 6
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles
journal, March 2015
- Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra
- Nature Communications, Vol. 6, Issue 1
Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts
journal, September 2016
- Matsubu, John C.; Zhang, Shuyi; DeRita, Leo
- Nature Chemistry, Vol. 9, Issue 2
Theoretical understanding of the stability of single-atom catalysts
journal, September 2018
- Liu, Jin-Cheng; Tang, Yan; Wang, Yang-Gang
- National Science Review, Vol. 5, Issue 5
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Heterogeneous single-atom catalysis
journal, May 2018
- Wang, Aiqin; Li, Jun; Zhang, Tao
- Nature Reviews Chemistry, Vol. 2, Issue 6
CO Oxidation on Au/TiO 2 : Condition-Dependent Active Sites and Mechanistic Pathways
journal, August 2016
- Wang, Yang-Gang; Cantu, David C.; Lee, Mal-Soon
- Journal of the American Chemical Society, Vol. 138, Issue 33
Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit
journal, October 2015
- Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.
- Nature Communications, Vol. 6, Issue 1
Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013
- Flytzani-Stephanopoulos, Maria
- Accounts of Chemical Research, Vol. 47, Issue 3
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997
- Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013
- Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
- Accounts of Chemical Research, Vol. 46, Issue 8
A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction
journal, March 2015
- Yang, Ming; Liu, Jilei; Lee, Sungsik
- Journal of the American Chemical Society, Vol. 137, Issue 10
Reaction Mechanisms for the CO Oxidation on Au/CeO 2 Catalysts: Activity of Substitutional Au 3+ /Au + Cations and Deactivation of Supported Au + Adatoms
journal, August 2009
- Camellone, Matteo Farnesi; Fabris, Stefano
- Journal of the American Chemical Society, Vol. 131, Issue 30
Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011
- Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
- Nature Chemistry, Vol. 3, Issue 8
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 111, Issue 15
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping
journal, July 2016
- Jones, J.; Xiong, H.; DeLaRiva, A. T.
- Science, Vol. 353, Issue 6295
Maximum Noble-Metal Efficiency in Catalytic Materials: Atomically Dispersed Surface Platinum
journal, June 2014
- Bruix, Albert; Lykhach, Yaroslava; Matolínová, Iva
- Angewandte Chemie International Edition, Vol. 53, Issue 39
Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation
journal, December 2017
- Nie, Lei; Mei, Donghai; Xiong, Haifeng
- Science, Vol. 358, Issue 6369
Scanning Tunneling Microscopy Study of the CO-Induced Structural Changes of Rh Crystallites Supported by TiO 2 (110)
journal, January 1996
- Berkó, A.; Ménesi, G.; Solymosi, F.
- The Journal of Physical Chemistry, Vol. 100, Issue 45
Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015
- Ding, K.; Gulec, A.; Johnson, A. M.
- Science, Vol. 350, Issue 6257
Rhodium geminal dicarbonyl on TiO2(110)
journal, August 1992
- Evans, John; Hayden, Brian; Mosselmans, Frederick
- Journal of the American Chemical Society, Vol. 114, Issue 17
Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO 2
journal, September 2017
- DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly
- Journal of the American Chemical Society, Vol. 139, Issue 40
Mechanism of CO2 reduction by H2 on Ru(0 0 0 1) and general selectivity descriptors for late-transition metal catalysts
journal, November 2016
- Avanesian, Talin; Gusmão, Gabriel S.; Christopher, Phillip
- Journal of Catalysis, Vol. 343
Direct observation of noble metal nanoparticles transforming to thermally stable single atoms
journal, July 2018
- Wei, Shengjie; Li, Ang; Liu, Jin-Cheng
- Nature Nanotechnology, Vol. 13, Issue 9
Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst
journal, December 2016
- Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng
- Nature Communications, Vol. 7, Issue 1
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Maximizing the Number of Interfacial Sites in Single-Atom Catalysts for the Highly Selective, Solvent-Free Oxidation of Primary Alcohols
journal, May 2018
- Li, Tianbo; Liu, Fei; Tang, Yan
- Angewandte Chemie International Edition, Vol. 57, Issue 26
How to Conceptualize Catalytic Cycles? The Energetic Span Model
journal, February 2011
- Kozuch, Sebastian; Shaik, Sason
- Accounts of Chemical Research, Vol. 44, Issue 2
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
Dynamical Observation and Detailed Description of Catalysts under Strong Metal–Support Interaction
journal, June 2016
- Zhang, Shuyi; Plessow, Philipp N.; Willis, Joshua J.
- Nano Letters, Vol. 16, Issue 7
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Stability investigation of a high number density Pt 1 /Fe 2 O 3 single-atom catalyst under different gas environments by HAADF-STEM
journal, March 2018
- Duan, Sibin; Wang, Rongming; Liu, Jingyue
- Nanotechnology, Vol. 29, Issue 20
Adsorption-Induced Structural Changes of Rh Supported by TiO2(110)-(1×2): An STM Study
journal, April 1999
- Berkó, A.; Solymosi, F.
- Journal of Catalysis, Vol. 183, Issue 1
Single-Site Heterogeneous Catalysts
journal, October 2005
- Thomas, John Meurig; Raja, Robert; Lewis, Dewi W.
- Angewandte Chemie International Edition, Vol. 44, Issue 40, p. 6456-6482
CO Oxidation at Rutile TiO 2 (110): Role of Oxygen Vacancies and Titanium Interstitials
journal, February 2015
- Yu, Yan-Yan; Gong, Xue-Qing
- ACS Catalysis, Vol. 5, Issue 4
Surface Single-Cluster Catalyst for N 2 -to-NH 3 Thermal Conversion
journal, December 2017
- Ma, Xue-Lu; Liu, Jin-Cheng; Xiao, Hai
- Journal of the American Chemical Society, Vol. 140, Issue 1
Using probe molecule FTIR spectroscopy to identify and characterize Pt-group metal based single atom catalysts
journal, September 2017
- Asokan, Chithra; DeRita, Leo; Christopher, Phillip
- Chinese Journal of Catalysis, Vol. 38, Issue 9