Formation of a Ti–Cu(111) single atom alloy: Structure and CO binding

Shi, Junjie; Owen, Cameron J.; Ngan, Hio Tong; Qin, Siyu; Mehar, Vikram; Sautet, Philippe; Weaver, Jason F.

doi:10.1063/5.0050800

Formation of a Ti–Cu(111) single atom alloy: Structure and CO binding

Journal Article · Wed Jun 16 00:00:00 EDT 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0050800· OSTI ID:1851693

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Univ. of Florida, Gainesville, FL (United States); Univ. of Florida, Gainesville, FL (United States)
Harvard Univ., Cambridge, MA (United States)
Univ. of California, Los Angeles, CA (United States)
Univ. of Florida, Gainesville, FL (United States)

A single atom Ti–Cu(111) surface alloy can be generated by depositing small amounts of Ti onto Cu(111) at slightly elevated surface temperatures (~500 to 600 K). Here, scanning tunneling microscopy shows that small Ti-rich islands covered by a Cu single layer form preferentially on ascending step edges of Cu(111) during Ti deposition below about 400 K but that a Ti–Cu(111) alloy replaces these small islands during deposition between 500 and 600 K, producing an alloy in the brims of the steps. Larger partially Cu-covered Ti-containing islands also form on the Cu(111) terraces at temperatures between 300 and 700 K. After surface exposure to CO at low temperatures, reflection absorption infrared spectroscopy (RAIRS) reveals distinct C–O stretch bands at 2102 and 2050 cm^–1 attributed to CO adsorbed on Cu-covered Ti-containing domains vs sites in the Ti–Cu(111) surface alloy. Calculations using density functional theory (DFT) suggest that the lower frequency C–O stretch band originates specifically from CO adsorbed on isolated Ti atoms in the Ti–Cu(111) surface alloy and predicts a higher C–O stretch frequency for CO adsorbed on Cu above subsurface Ti ensembles. DFT further predicts that CO preferentially adsorbs in flat-lying configurations on contiguous Ti surface structures with more than one Ti atom and thus that CO adsorbed on such structures should not be observed with RAIRS. The ability to generate a single atom Ti–Cu(111) alloy will provide future opportunities to investigate the surface chemistry promoted by a representative early transition metal dopant on a Cu(111) host surface.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012573

OSTI ID:: 1851693

Alternate ID(s):: OSTI ID: 1797322

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 154; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single‐Atom Alloys Hannagan, Ryan T.; Patel, Dipna A.; Cramer, Laura A. ChemCatChem, Vol. 12, Issue 2 https://doi.org/10.1002/cctc.201901488	journal	November 2019
Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys Darby, Matthew T.; Sykes, E. Charles H.; Michaelides, Angelos Topics in Catalysis, Vol. 61, Issue 5-6 https://doi.org/10.1007/s11244-017-0882-1	journal	January 2018
Phase Equilibria of the Cu-Ti-Er System at 773 K (500 °C) and Stability of the CuTi3 Phase Zhan, Yongzhong; Peng, Dan; She, Jia Metallurgical and Materials Transactions A, Vol. 43, Issue 11 https://doi.org/10.1007/s11661-012-1226-1	journal	August 2012
Ab initio Hellmann-Feynman molecular dynamics for liquid metals Kresse, G.; Hafner, J. Journal of Non-Crystalline Solids, Vol. 156-158 https://doi.org/10.1016/0022-3093(93)90104-6	journal	May 1993
Surface free energies of solid metals: Estimation from liquid surface tension measurements Tyson, W. R.; Miller, W. A. Surface Science, Vol. 62, Issue 1 https://doi.org/10.1016/0039-6028(77)90442-3	journal	January 1977
Interactions of CO molecules adsorbed on Cu(111) Hollins, P.; Pritchard, J. Surface Science, Vol. 89, Issue 1-3 https://doi.org/10.1016/0039-6028(79)90633-2	journal	January 1979
Fourier transform reflection-absorption infrared spectroscopy of adsorbates on Cu(100) and Cu(111) Chesters, M. A.; Parker, S. F.; Raval, R. Surface Science, Vol. 165, Issue 1 https://doi.org/10.1016/0039-6028(86)90668-0	journal	January 1986
FT-rairs, eels and leed studies of the adsorption of carbon monoxide on Cu(111) Raval, R.; Parker, S. F.; Pemble, M. E. Surface Science, Vol. 203, Issue 3 https://doi.org/10.1016/0039-6028(88)90088-x	journal	September 1988
Infrared reflection-absorption spectroscopy of adsorbed molecules Hoffmann, F. Surface Science Reports, Vol. 3, Issue 2-3 https://doi.org/10.1016/0167-5729(83)90001-8	journal	January 1983
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
First-principles investigation of structural, mechanical and electronic properties for Cu–Ti intermetallics Zhu, Y. D.; Yan, M. F.; Zhang, Y. X. Computational Materials Science, Vol. 123 https://doi.org/10.1016/j.commatsci.2016.06.015	journal	October 2016
CO induced surface segregation as a means of improving surface composition and enhancing performance of CuPd bimetallic catalysts McCue, Alan J.; Anderson, James A. Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.06.002	journal	September 2015
Submonolayer growth of Pd on Cu(111) studied by scanning tunneling microscopy Bach Aaen, A.; Lægsgaard, E.; Ruban, A. V. Surface Science, Vol. 408, Issue 1-3 https://doi.org/10.1016/s0039-6028(98)00124-1	journal	June 1998
Theoretical surface science and catalysis—calculations and concepts Hammer, B.; Nørskov, J. K. Impact of Surface Science on Catalysis, p. 71-129 https://doi.org/10.1016/s0360-0564(02)45013-4	book	January 2000
Adsorption of carbon monoxide on Ti(0001) Kuznetsov, M. V.; Frickel, D. P.; Shalaeva, E. V. Journal of Electron Spectroscopy and Related Phenomena, Vol. 96, Issue 1-3 https://doi.org/10.1016/s0368-2048(98)00219-9	journal	November 1998
Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts Giannakakis, Georgios; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H. Accounts of Chemical Research, Vol. 52, Issue 1 https://doi.org/10.1021/acs.accounts.8b00490	journal	December 2018
Single-Atom Alloy Catalysis Hannagan, Ryan T.; Giannakakis, Georgios; Flytzani-Stephanopoulos, Maria Chemical Reviews https://doi.org/10.1021/acs.chemrev.0c00078	journal	June 2020
Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review Luneau, Mathilde; Lim, Jin Soo; Patel, Dipna A. Chemical Reviews, Vol. 120, Issue 23 https://doi.org/10.1021/acs.chemrev.0c00582	journal	October 2020
Structural Changes of Cu(110) and Cu(110)-(2 × 1)-O Surfaces under Carbon Monoxide in the Torr Pressure Range Studied with Scanning Tunneling Microscopy and Infrared Reflection Absorption Spectroscopy Eren, Baran; Liu, Zongyuan; Stacchiola, Dario The Journal of Physical Chemistry C, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcc.6b02143	journal	April 2016
Polarization-Dependent Infrared Spectroscopy of Adsorbed Carbon Monoxide To Probe the Surface of a Pd/Cu(111) Single-Atom Alloy Kruppe, Christopher M.; Krooswyk, Joel D.; Trenary, Michael The Journal of Physical Chemistry C, Vol. 121, Issue 17 https://doi.org/10.1021/acs.jpcc.7b01227	journal	April 2017
Roughening of Copper (100) at Elevated CO Pressure: Cu Adatom and Cluster Formation Enable CO Dissociation Roiaz, Matteo; Falivene, Laura; Rameshan, Christoph The Journal of Physical Chemistry C, Vol. 123, Issue 13 https://doi.org/10.1021/acs.jpcc.8b07668	journal	October 2018
Dynamics of Surface Alloys: Rearrangement of Pd/Ag(111) Induced by CO and O ₂ van Spronsen, Matthijs A.; Daunmu, Kaining; O’Connor, Christopher R. The Journal of Physical Chemistry C, Vol. 123, Issue 13 https://doi.org/10.1021/acs.jpcc.8b08849	journal	October 2018
CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study Papanikolaou, Konstantinos G.; Darby, Matthew T.; Stamatakis, Michail The Journal of Physical Chemistry C, Vol. 123, Issue 14 https://doi.org/10.1021/acs.jpcc.9b00649	journal	March 2019
Atomic-Scale Surface Structure and CO Tolerance of NiCu Single-Atom Alloys Patel, Dipna A.; Hannagan, Ryan T.; Kress, Paul L. The Journal of Physical Chemistry C, Vol. 123, Issue 46 https://doi.org/10.1021/acs.jpcc.9b07513	journal	October 2019
Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys Darby, Matthew T.; Stamatakis, Michail; Michaelides, Angelos The Journal of Physical Chemistry Letters, Vol. 9, Issue 18 https://doi.org/10.1021/acs.jpclett.8b01888	journal	September 2018
Optimal Packing of CO at a High Coverage on Pt(100) and Pt(111) Surfaces Sumaria, Vaidish; Nguyen, Luan; Tao, Franklin Feng ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c01971	journal	July 2020
Comprehensive Benchmarking of a Density-Dependent Dispersion Correction Steinmann, Stephan N.; Corminboeuf, Clemence Journal of Chemical Theory and Computation, Vol. 7, Issue 11 https://doi.org/10.1021/ct200602x	journal	October 2011
Structural, chemical and electronic properties of copper/tantalum (110) Kuhn, W. Kevin; Campbell, Robert A.; Goodman, D. Wayne The Journal of Physical Chemistry, Vol. 97, Issue 2 https://doi.org/10.1021/j100104a029	journal	January 1993
Extensive ab Initio Study of the C ₂ O ₂ , C ₂ S ₂ , and C ₂ OS Systems: Stabilities and Singlet−Triplet Energy Gaps Talbi, D.; Chandler, G. S. The Journal of Physical Chemistry A, Vol. 104, Issue 24 https://doi.org/10.1021/jp000732d	journal	June 2000
The CO/Pt(111) Puzzle ^† Feibelman, Peter J.; Hammer, B.; Nørskov, J. K. The Journal of Physical Chemistry B, Vol. 105, Issue 18 https://doi.org/10.1021/jp002302t	journal	May 2001
Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys Lucci, Felicia R.; Lawton, Timothy J.; Pronschinske, Alex The Journal of Physical Chemistry C, Vol. 118, Issue 6 https://doi.org/10.1021/jp405254z	journal	January 2014
Dehydrogenation of Propane to Propylene by a Pd/Cu Single-Atom Catalyst: Insight from First-Principles Calculations Cao, Xinrui; Ji, Yongfei; Luo, Yi The Journal of Physical Chemistry C, Vol. 119, Issue 2 https://doi.org/10.1021/jp508625b	journal	December 2014
CO Oxidation on PdO(101) during Temperature-Programmed Reaction Spectroscopy: Role of Oxygen Vacancies Zhang, Feng; Pan, Li; Li, Tao The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp509383v	journal	November 2014
Importance of Kinetics in Surface Alloying: A Comparison of the Diffusion Pathways of Pd and Ag Atoms on Cu(111) Bellisario, Darin O.; Han, Jeong Woo; Tierney, Heather L. The Journal of Physical Chemistry C, Vol. 113, Issue 29 https://doi.org/10.1021/jp903541k	journal	June 2009
Determination of Site Specific Adsorption Energies of CO on Copper Vollmer, Stefan; Witte, Gregor; Wöll, Christof Catalysis Letters, Vol. 77, Issue 1/3, p. 97-101 https://doi.org/10.1023/a:1012755616064	journal	January 2001
Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei Nature Chemistry, Vol. 10, Issue 3 https://doi.org/10.1038/nchem.2915	journal	January 2018
Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9550	journal	October 2015
Accurate surface and adsorption energies from many-body perturbation theory Schimka, L.; Harl, J.; Stroppa, A. Nature Materials, Vol. 9, Issue 9 https://doi.org/10.1038/nmat2806	journal	July 2010
Free-atom-like d states in single-atom alloy catalysts Greiner, M. T.; Jones, T. E.; Beeg, S. Nature Chemistry, Vol. 10, Issue 10 https://doi.org/10.1038/s41557-018-0125-5	journal	August 2018
An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation Therrien, Andrew J.; Hensley, Alyssa J. R.; Marcinkowski, Matthew D. Nature Catalysis, Vol. 1, Issue 3 https://doi.org/10.1038/s41929-018-0028-2	journal	March 2018
Adsorbate-driven morphological changes on Cu(111) nano-pits Mudiyanselage, K.; Xu, F.; Hoffmann, F. M. Physical Chemistry Chemical Physics, Vol. 17, Issue 5 https://doi.org/10.1039/c4cp05088f	journal	January 2015
Growth and auto-oxidation of Pd on single-layer AgO _x /Ag(111) Mehar, Vikram; O’Connor, Christopher R.; Egle, Tobias Physical Chemistry Chemical Physics, Vol. 22, Issue 11 https://doi.org/10.1039/c9cp06973a	journal	January 2020
Electronic band contraction induced low temperature methane activation on metal alloys Fung, Victor; Hu, Guoxiang; Sumpter, Bobby Journal of Materials Chemistry A, Vol. 8, Issue 12 https://doi.org/10.1039/d0ta00375a	journal	January 2020
Exchange-hole dipole moment and the dispersion interaction Becke, Axel D.; Johnson, Erin R. The Journal of Chemical Physics, Vol. 122, Issue 15 https://doi.org/10.1063/1.1884601	journal	April 2005
A generalized-gradient approximation exchange hole model for dispersion coefficients Steinmann, Stephan N.; Corminboeuf, Clemence The Journal of Chemical Physics, Vol. 134, Issue 4 https://doi.org/10.1063/1.3545985	journal	January 2011
Elucidating the composition of PtAg surface alloys with atomic-scale imaging and spectroscopy Patel, Dipna A.; Kress, Paul L.; Cramer, Laura A. The Journal of Chemical Physics, Vol. 151, Issue 16 https://doi.org/10.1063/1.5124687	journal	October 2019
Surface facet dependence of competing alloying mechanisms Wang, Yicheng; Papanikolaou, Konstantinos G.; Hannagan, Ryan T. The Journal of Chemical Physics, Vol. 153, Issue 24 https://doi.org/10.1063/5.0034520	journal	December 2020
Surface states in the epitaxial growth of titanium on copper (111) Vahakangas, Jouko; Williams, Ellen D.; Park, Robert L. Physical Review B, Vol. 33, Issue 4 https://doi.org/10.1103/physrevb.33.2281	journal	February 1986
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/physrevb.40.3616	journal	August 1989
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/physrevb.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/physrevb.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/physrevb.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/physrevb.59.1758	journal	January 1999
Significance of single-electron energies for the description of CO on Pt(111) Kresse, G.; Gil, A.; Sautet, P. Physical Review B, Vol. 68, Issue 7 https://doi.org/10.1103/physrevb.68.073401	journal	August 2003
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces Mason, Sara E.; Grinberg, Ilya; Rappe, Andrew M. Physical Review B, Vol. 69, Issue 16 https://doi.org/10.1103/physrevb.69.161401	journal	April 2004
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/physrevlett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/s0021889811038970	journal	October 2011
Adsorption-Induced Segregation as a Method for the Target-Oriented Modification of the Surface of a Bimetallic Pd–Ag Catalyst Stakheev, A. Yu.; Smirnova, N. S.; Markov, P. V. Kinetics and Catalysis, Vol. 59, Issue 5 https://doi.org/10.1134/s0023158418050154	journal	September 2018

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Formation of a Ti–Cu(111) single atom alloy: Structure and CO binding

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