Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys
Abstract
Ni is one of the most extensively utilized metals in industrial catalysis. For example, Ni is the catalyst of choice for the steam reforming of hydrocarbons. However, pure Ni also detrimentally catalyzes the formation of graphitic carbon, which in turn leads to coking and deactivation of the catalyst. It has been shown that alloying small amounts of a less reactive metal like Au into Ni can alleviate this issue by breaking up the larger Ni ensembles that promote coke formation. We are taking the opposite of this approach by alloying very small amounts of Ni into Cu, another catalytically less active host metal to create single Ni atom sites. In this way our single-atom alloy approach has the potential to greatly enhance catalytic selectivity and reduce poisoning, analogous to other single-atom alloys such as PtCu and PdCu. Herein we report the atomic-scale surface structure and local geometry of low coverages of Ni deposited on a Cu(111) single crystal with scanning tunneling microscopy. At 433 K, low concentrations of Ni alloy in the Cu host as a single-atom alloy in Ni-rich brims along ascending step edges. To support our STM assignments of the single atom dispersion of Ni, reflection absorption infraredmore »
- Authors:
-
- Tufts Univ., Medford, MA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1595414
- Grant/Contract Number:
- SC0012573
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 46; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Desorption; Alloys; Catalysts; Deposition; Scanning tunneling microscopy
Citation Formats
Patel, Dipna A., Hannagan, Ryan T., Kress, Paul L., Schilling, Alex C., Çınar, Volkan, and Sykes, E. Charles H. Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcc.9b07513.
Patel, Dipna A., Hannagan, Ryan T., Kress, Paul L., Schilling, Alex C., Çınar, Volkan, & Sykes, E. Charles H. Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys. United States. https://doi.org/10.1021/acs.jpcc.9b07513
Patel, Dipna A., Hannagan, Ryan T., Kress, Paul L., Schilling, Alex C., Çınar, Volkan, and Sykes, E. Charles H. Wed .
"Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys". United States. https://doi.org/10.1021/acs.jpcc.9b07513. https://www.osti.gov/servlets/purl/1595414.
@article{osti_1595414,
title = {Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys},
author = {Patel, Dipna A. and Hannagan, Ryan T. and Kress, Paul L. and Schilling, Alex C. and Çınar, Volkan and Sykes, E. Charles H.},
abstractNote = {Ni is one of the most extensively utilized metals in industrial catalysis. For example, Ni is the catalyst of choice for the steam reforming of hydrocarbons. However, pure Ni also detrimentally catalyzes the formation of graphitic carbon, which in turn leads to coking and deactivation of the catalyst. It has been shown that alloying small amounts of a less reactive metal like Au into Ni can alleviate this issue by breaking up the larger Ni ensembles that promote coke formation. We are taking the opposite of this approach by alloying very small amounts of Ni into Cu, another catalytically less active host metal to create single Ni atom sites. In this way our single-atom alloy approach has the potential to greatly enhance catalytic selectivity and reduce poisoning, analogous to other single-atom alloys such as PtCu and PdCu. Herein we report the atomic-scale surface structure and local geometry of low coverages of Ni deposited on a Cu(111) single crystal with scanning tunneling microscopy. At 433 K, low concentrations of Ni alloy in the Cu host as a single-atom alloy in Ni-rich brims along ascending step edges. To support our STM assignments of the single atom dispersion of Ni, reflection absorption infrared spectroscopy of CO on NiCu was performed. To access the binding strength of CO to isolated Ni sites, we use temperature-programmed desorption studies which reveal that CO binds more weakly to single Ni atoms in Cu compared to Ni(111), indicating that NiCu single-atom alloys are promising for catalytic applications in which CO poisoning is an issue. Altogether, these results provide a guide for the preparation of NiCu single-atom alloy model catalysts that are predicted by theory to be promising for a number of reactions.},
doi = {10.1021/acs.jpcc.9b07513},
journal = {Journal of Physical Chemistry. C},
number = 46,
volume = 123,
place = {United States},
year = {Wed Oct 23 00:00:00 EDT 2019},
month = {Wed Oct 23 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys
journal, September 2018
- Darby, Matthew T.; Stamatakis, Michail; Michaelides, Angelos
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
Behavior of Ni atoms on the Cu(111) surface: A study by high-resolution electron-energy-loss spectroscopy
journal, August 1993
- Tzeng, Yi-Ren; Wu, Hao-tse; Shiang, Keh-Dong
- Physical Review B, Vol. 48, Issue 8
Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra
journal, September 2016
- Hoffman, Adam S.; Fang, Chia-Yu; Gates, Bruce C.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single‐Atom Alloys
journal, November 2019
- Hannagan, Ryan T.; Patel, Dipna A.; Cramer, Laura A.
- ChemCatChem, Vol. 12, Issue 2
Tackling CO Poisoning with Single-Atom Alloy Catalysts
journal, May 2016
- Liu, Jilei; Lucci, Felicia R.; Yang, Ming
- Journal of the American Chemical Society, Vol. 138, Issue 20
Single-Atom Alloy Pd–Ag Catalyst for Selective Hydrogenation of Acrolein
journal, July 2015
- Aich, Payoli; Wei, Haojuan; Basan, Bridget
- The Journal of Physical Chemistry C, Vol. 119, Issue 32
Extraction of kinetic parameters in temperature programmed desorption: A comparison of methods
journal, December 1987
- Miller, J. B.; Siddiqui, H. R.; Gates, S. M.
- The Journal of Chemical Physics, Vol. 87, Issue 11
Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation
journal, October 2018
- Sun, Guodong; Zhao, Zhi-Jian; Mu, Rentao
- Nature Communications, Vol. 9, Issue 1
Catalytic hydrogenolysis and dehydrogenation over copper-nickel alloys
journal, February 1972
- Sinfelt, J.
- Journal of Catalysis, Vol. 24, Issue 2
The influence of surface defects on the infrared spectra of adsorbed species
journal, January 1992
- Hollins, Peter
- Surface Science Reports, Vol. 16, Issue 2
Spontaneous evolution of the Ni/Cu( 111 ) interface at 300 K
journal, June 2002
- Pons, S.; Mallet, P.; Magaud, L.
- Surface Science, Vol. 511, Issue 1-3
The structure of CO on Ni(111)
journal, January 1982
- Netzer, Falko P.; Madey, Theodore E.
- The Journal of Chemical Physics, Vol. 76, Issue 1
Calculation of the surface segregation of Ni-Cu alloys with the use of the embedded-atom method
journal, December 1985
- Foiles, S. M.
- Physical Review B, Vol. 32, Issue 12
A mixed Cu–Ni bridge site for CO adsorption
journal, May 1989
- Garfunkel, Eric; Yu, Mingren; Yang, Shu
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 7, Issue 3
Polarization-Dependent Infrared Spectroscopy of Adsorbed Carbon Monoxide To Probe the Surface of a Pd/Cu(111) Single-Atom Alloy
journal, April 2017
- Kruppe, Christopher M.; Krooswyk, Joel D.; Trenary, Michael
- The Journal of Physical Chemistry C, Vol. 121, Issue 17
Growth and morphology of Ni films on Cu(111)
journal, January 1998
- Wulfhekel, Wulf; Beckmann, Ingo; Rosenfeld, Georg
- Surface Science, Vol. 395, Issue 2-3
Elucidating the Stability and Reactivity of Surface Intermediates on Single-Atom Alloy Catalysts
journal, April 2018
- Darby, Matthew T.; Réocreux, Romain; Sykes, E. Charles. H.
- ACS Catalysis, Vol. 8, Issue 6
Initial Oxidation of Cu( hkl ) Surfaces Vicinal to Cu(111): A High-Throughput Study of Structure Sensitivity
journal, July 2012
- Lawton, T. J.; Pushkarev, V.; Broitman, E.
- The Journal of Physical Chemistry C, Vol. 116, Issue 30
Significant Quantum Effects in Hydrogen Activation
journal, April 2014
- Kyriakou, Georgios; Davidson, Erlend R. M.; Peng, Guowen
- ACS Nano, Vol. 8, Issue 5
IRAS study of the adsorption of CO on Ni(111): Interrelation between various bonding modes of chemisorbed CO
journal, January 1988
- Surnev, L.; Xu, Z.; Yates, J. T.
- Surface Science, Vol. 201, Issue 1-2
Calculated properties of surface and subsurface nickel monolayers on copper
journal, September 1999
- Pourovskii, L. V.; Skorodumova, N. V.; Vekilov, Yu. Kh.
- Surface Science, Vol. 439, Issue 1-3
H 2 Activation and Spillover on Catalytically Relevant Pt–Cu Single Atom Alloys
journal, August 2015
- Lucci, Felicia R.; Marcinkowski, Matthew D.; Lawton, Timothy J.
- The Journal of Physical Chemistry C, Vol. 119, Issue 43
Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys
journal, January 2018
- Darby, Matthew T.; Sykes, E. Charles H.; Michaelides, Angelos
- Topics in Catalysis, Vol. 61, Issue 5-6
Adsorption and desorption of carbon monoxide from nickel and nickel-copper alloys
journal, April 1977
- Harberts, J.
- Journal of Catalysis, Vol. 47, Issue 1
Sulfur-passivated nickel catalysts for carbon-free steam reforming of methane
journal, January 1984
- Rostrupnielsen, J.
- Journal of Catalysis, Vol. 85, Issue 1
Investigation of the interplay of nickel dissolution and copper segregation in Ni/Cu() system
journal, January 2002
- Erdélyi, Z.; Girardeaux, Ch.; Tôkei, Zs.
- Surface Science, Vol. 496, Issue 1-2
Structural and Energetic Properties of Ni−Cu Bimetallic Clusters
journal, August 2008
- Hristova, Elisaveta; Dong, Yi; Grigoryan, Valeri G.
- The Journal of Physical Chemistry A, Vol. 112, Issue 34
Partial oxidation of methane to synthesis gas using carbon dioxide
journal, July 1991
- Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.
- Nature, Vol. 352, Issue 6332
Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations
journal, March 2012
- Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D.
- Science, Vol. 335, Issue 6073
Nickel monolayers on copper surfaces: CO adsorption and ni diffusion
journal, October 1988
- Yang, Shu; Yu, Mingren; Meigs, George
- Surface Science, Vol. 205, Issue 1-2
Modification of the surface electronic structure of Cu(111) by monolayer Ni adsorption and the effects on chemisorption
journal, January 1989
- Frank, K. H.; Dudde, R.; Sagner, H. J.
- Physical Review B, Vol. 39, Issue 2
The surface composition of the nickel-copper alloy system as determined by Auger electron spectroscopy
journal, November 1977
- Kuijers, F. J.; Ponec, V.
- Surface Science, Vol. 68
NiCu single atom alloys catalyze the C H bond activation in the selective non- oxidative ethanol dehydrogenation reaction
journal, June 2018
- Shan, Junjun; Liu, Jilei; Li, Mengwei
- Applied Catalysis B: Environmental, Vol. 226
Tailoring Bimetallic Alloy Surface Properties by Kinetic Control of Self-Diffusion Processes at the Nanoscale
journal, September 2012
- Rizzi, Michele; Furlan, Sara; Peressi, Maria
- Journal of the American Chemical Society, Vol. 134, Issue 40
Investigating the Reactivity of Single Atom Alloys Using Density Functional Theory
journal, January 2018
- Thirumalai, Hari; Kitchin, John R.
- Topics in Catalysis, Vol. 61, Issue 5-6
Deactivation dynamics of a Ni supported catalyst during the steam reforming of volatiles from waste polyethylene pyrolysis
journal, July 2017
- Ochoa, Aitor; Barbarias, Itsaso; Artetxe, Maite
- Applied Catalysis B: Environmental, Vol. 209
Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys
journal, January 2014
- Lucci, Felicia R.; Lawton, Timothy J.; Pronschinske, Alex
- The Journal of Physical Chemistry C, Vol. 118, Issue 6
Atomic-Scale Imaging and Electronic Structure Determination of Catalytic Sites on Pd/Cu Near Surface Alloys
journal, March 2009
- Tierney, Heather L.; Baber, Ashleigh E.; Sykes, E. Charles H.
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Industrial relevance of coking
journal, August 1997
- Rostrup-Nielsen, Jens R.
- Catalysis Today, Vol. 37, Issue 3
Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts
journal, December 2018
- Giannakakis, Georgios; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.
- Accounts of Chemical Research, Vol. 52, Issue 1
CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study
journal, March 2019
- Papanikolaou, Konstantinos G.; Darby, Matthew T.; Stamatakis, Michail
- The Journal of Physical Chemistry C, Vol. 123, Issue 14
In situ IR spectroscopic studies of Ni surface segregation induced by CO adsorption on Cu–Ni/SiO2 bimetallic catalysts
journal, January 2014
- Yao, Yunxi; Goodman, D. Wayne
- Physical Chemistry Chemical Physics, Vol. 16, Issue 8
Design of a Surface Alloy Catalyst for Steam Reforming
journal, March 1998
- Besenbacher, F.
- Science, Vol. 279, Issue 5358
Structural and electronic properties of thin Ni layers on Cu(111) as investigated by ARPES, STM and GIXD
journal, September 2006
- Mulazzi, M.; Stanescu, S.; Fujii, J.
- Surface Science, Vol. 600, Issue 18
Steam reforming of methane over Ni/SiO2 catalyst with enhanced coke resistance at low steam to methane ratio
journal, November 2015
- Zhang, Yao; Wang, Wei; Wang, Zongyuan
- Catalysis Today, Vol. 256
Free-atom-like d states in single-atom alloy catalysts
journal, August 2018
- Greiner, M. T.; Jones, T. E.; Beeg, S.
- Nature Chemistry, Vol. 10, Issue 10
Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation
journal, January 2018
- Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei
- Nature Chemistry, Vol. 10, Issue 3
Controlling Hydrogen Activation, Spillover, and Desorption with Pd–Au Single-Atom Alloys
journal, January 2016
- Lucci, Felicia R.; Darby, Matthew T.; Mattera, Michael F. G.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
FT-rairs, eels and leed studies of the adsorption of carbon monoxide on Cu(111)
journal, September 1988
- Raval, R.; Parker, S. F.; Pemble, M. E.
- Surface Science, Vol. 203, Issue 3
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