Adsorbate-induced adatom formation on Au-Cu bimetallic alloys and its possible consequences for CO2 electroreduction

Xu, Lang; Rebarchik, Michael; Bhandari, Saurabh; Mavrikakis, Manos

doi:10.1016/j.susc.2024.122613

Adsorbate-induced adatom formation on Au-Cu bimetallic alloys and its possible consequences for CO₂ electroreduction

Journal Article · Sat Sep 14 20:00:00 EDT 2024 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2024.122613· OSTI ID:3012296

Xu, Lang ^[1]; Rebarchik, Michael ^[1]; Bhandari, Saurabh ^[1]; ^[1]

University of Wisconsin-Madison, WI (United States)

The adsorbate-induced formation of sub-nanometer clusters on transition-metal single crystals observed in previous high-pressure microscopic studies hinted at the in-situ formation of unique active sites even on large nanoparticle catalysts. We propose that the adatom formation energy can be used as an energetic descriptor for the initial step toward the adsorbate-induced metal-cluster formation process. This descriptor can be efficiently computed using density functional theory (DFT) calculations and applied for screening and identification of metal catalysts where this phenomenon may play an important role in generating active sites in-situ. As a proof of concept, here, we construct an adatom formation energy database for three Au_xCu_y alloys (x:y = 3:1, 1:1, or 1:3) and eighteen adsorbates (H, C, N, O, F, S, Cl, Br, I, CH_x, NH_x (x = 1 – 3), CO, NO, and OH) commonly involved in catalytic reactions. The energetics of adatom formation were examined in all cases where the (111) terrace, (211) step-edge, and (874) kink were the sources of the adatom. We demonstrate that the presence of an adsorbate could alter not only the energetics for adatom formation but also the elemental nature of the preferred adatom being formed. Using our database, we identified promising systems which favor adsorbate-induced adatom formation under near-ambient conditions. Specifically, CO-induced adatom formation on all three Au-Cu alloy surfaces could occur under CO₂ electroreduction (CO₂RR) conditions. This phenomenon offers a qualitative explanation for the experimentally observed CO₂RR activity on Au-Cu alloy catalysts. As a result, our methodology offers an easily expandable and efficient approach for large-scale catalyst screening with regards to adatom/cluster formation under reaction conditions and provides insight into the possible nature of active sites on alloy catalysts from a novel perspective.

View Accepted Manuscript (DOE)

Research Organization:: University of Wisconsin-Madison, WI (United States)

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

Grant/Contract Number:: FG02-05ER15731; AC02-05CH11231; AC02-06CH11357

OSTI ID:: 3012296

Journal Information:: Surface Science, Journal Name: Surface Science Vol. 751; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Catalytic ethylene oxidation by Cu–Au core–shell nanoclusters: a computational study Tseng, Jo-Yi; Chen, Hsin-Tsung Theoretical Chemistry Accounts, Vol. 139, Issue 3 https://doi.org/10.1007/s00214-020-2575-2	journal	March 2020
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
Dense structures formed by CO on Rh(111) studied by scanning tunneling microscopy Cernota, Paul; Rider, Keith; Yoon, H. Alex Surface Science, Vol. 445, Issue 2-3 https://doi.org/10.1016/S0039-6028(99)01073-0	journal	January 2000
Silica-supported Au–Cu alloy nanoparticles as an efficient catalyst for selective oxidation of alcohols Li, Wanjun; Wang, Aiqin; Liu, Xiaoyan Applied Catalysis A: General, Vol. 433-434 https://doi.org/10.1016/j.apcata.2012.05.014	journal	August 2012
Directly growing hierarchical nickel-copper hydroxide nanowires on carbon fibre cloth for efficient electrooxidation of ammonia Xu, Wei; Lan, Rong; Du, Dongwei Applied Catalysis B: Environmental, Vol. 218 https://doi.org/10.1016/j.apcatb.2017.07.005	journal	December 2017
Au–Cu alloy nanoparticles supported on silica gel as catalyst for CO oxidation: Effects of Au/Cu ratios Liu, Xiaoyan; Wang, Aiqin; Zhang, Tao Catalysis Today, Vol. 160, Issue 1 https://doi.org/10.1016/j.cattod.2010.05.019	journal	February 2011
CO activation pathways and the mechanism of Fischer–Tropsch synthesis Ojeda, Manuel; Nabar, Rahul; Nilekar, Anand U. Journal of Catalysis, Vol. 272, Issue 2 https://doi.org/10.1016/j.jcat.2010.04.012	journal	June 2010
Structure sensitivity in adsorbate-induced adatom formation on FCC transition-metal surfaces Xu, Lang; Mavrikakis, Manos Journal of Catalysis, Vol. 431 https://doi.org/10.1016/j.jcat.2024.115373	journal	March 2024
Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis Bhandari, Saurabh; Rangarajan, Srinivas; Mavrikakis, Manos Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00340	journal	September 2020
Computational Methods in Heterogeneous Catalysis Chen, Benjamin W. J.; Xu, Lang; Mavrikakis, Manos Chemical Reviews, Vol. 121, Issue 2 https://doi.org/10.1021/acs.chemrev.0c01060	journal	December 2020
Selective Catalytic Ammonia Oxidation to Nitrogen by Atomic Oxygen Species on Ag(111) Karatok, Mustafa; Vovk, Evgeny I.; Koc, Ali Vala The Journal of Physical Chemistry C, Vol. 121, Issue 41 https://doi.org/10.1021/acs.jpcc.7b08291	journal	October 2017
Predicting Surface Clustering at Ambient Conditions from Thermodynamic Data Eren, Baran; Salmeron, Miquel The Journal of Physical Chemistry C, Vol. 123, Issue 13 https://doi.org/10.1021/acs.jpcc.8b08287	journal	October 2018
Understanding Trends in Ethylene Epoxidation on Group IB Metals Li, Hao; Cao, Ang; Nørskov, Jens K. ACS Catalysis, Vol. 11, Issue 19 https://doi.org/10.1021/acscatal.1c03094	journal	September 2021
Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation Grabow, L. C.; Mavrikakis, M. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs200055d	journal	February 2011
CO Oxidation on Au _n /TiO ₂ Catalysts Produced by Size-Selected Cluster Deposition Lee, Sungsik; Fan, Chaoyang; Wu, Tianpin Journal of the American Chemical Society, Vol. 126, Issue 18 https://doi.org/10.1021/ja049436v	journal	May 2004
Selective Catalytic Oxidation of Ammonia to Nitrogen on Atomic Oxygen Precovered Au(111) Gong, Jinlong; Ojifinni, Rotimi A.; Kim, Tae S. Journal of the American Chemical Society, Vol. 128, Issue 28 https://doi.org/10.1021/ja062624w	journal	July 2006
Predicted Oxidation of CO Catalyzed by Au Nanoclusters on a Thin Defect-Free MgO Film Supported on a Mo(100) Surface Zhang, Chun; Yoon, Bokwon; Landman, Uzi Journal of the American Chemical Society, Vol. 129, Issue 8 https://doi.org/10.1021/ja0684545	journal	February 2007
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 130, Issue 4 https://doi.org/10.1021/ja0768237	journal	January 2008
Oxidation State and Surface Reconstruction of Cu under CO ₂ Reduction Conditions from In Situ X-ray Characterization Lee, Soo Hong; Lin, John C.; Farmand, Maryam Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c10017	journal	December 2020
Structure of Copper–Cobalt Surface Alloys in Equilibrium with Carbon Monoxide Gas Eren, Baran; Torres, Daniel; Karslıoğlu, Osman Journal of the American Chemical Society, Vol. 140, Issue 21 https://doi.org/10.1021/jacs.7b13621	journal	May 2018
Dynamic Atom Clusters on AuCu Nanoparticle Surface during CO Oxidation Luo, Langli; Chen, Shuyue; Xu, Qian Journal of the American Chemical Society, Vol. 142, Issue 8 https://doi.org/10.1021/jacs.9b13901	journal	February 2020
Adsorbate-Induced Adatom Formation on Lithium, Iron, Cobalt, Ruthenium, and Rhenium Surfaces Xu, Lang; Mavrikakis, Manos JACS Au, Vol. 3, Issue 8 https://doi.org/10.1021/jacsau.3c00256	journal	July 2023
Effect of Particle Size on the Oxidizability of Platinum Clusters Xu, Ye; Shelton, William A.; Schneider, William F. The Journal of Physical Chemistry A, Vol. 110, Issue 17 https://doi.org/10.1021/jp0547111	journal	May 2006
High Water−Gas Shift Activity in TiO ₂ (110) Supported Cu and Au Nanoparticles: Role of the Oxide and Metal Particle Size Rodríguez, José A.; Evans, Jaime; Graciani, Jesús The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp900483u	journal	April 2009
Investigation of Catalytic Finite-Size-Effects of Platinum Metal Clusters Li, Lin; Larsen, Ask H.; Romero, Nichols A. The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz3018286	journal	December 2012
Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14881	journal	March 2017
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles Kim, Dohyung; Resasco, Joaquin; Yu, Yi Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5948	journal	September 2014
The most active Cu facet for low-temperature water gas shift reaction Zhang, Zhenhua; Wang, Sha-Sha; Song, Rui Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00620-6	journal	September 2017
The active sites of Cu–ZnO catalysts for water gas shift and CO hydrogenation reactions Zhang, Zhenhua; Chen, Xuanye; Kang, Jincan Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24621-8	journal	July 2021
Operando studies reveal active Cu nanograins for CO2 electroreduction Yang, Yao; Louisia, Sheena; Yu, Sunmoon Nature, Vol. 614, Issue 7947 https://doi.org/10.1038/s41586-022-05540-0	journal	February 2023
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
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
Dipole correction for surface supercell calculations Bengtsson, Lennart Physical Review B, Vol. 59, Issue 19 https://doi.org/10.1103/PhysRevB.59.12301	journal	May 1999
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
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
The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering Campbell, C. T. Science, Vol. 298, Issue 5594 https://doi.org/10.1126/science.1075094	journal	October 2002
Break-Up of Stepped Platinum Catalyst Surfaces by High CO Coverage Tao, F.; Dag, S.; Wang, L. -W. Science, Vol. 327, Issue 5967 https://doi.org/10.1126/science.1182122	journal	February 2010
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014
Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption Eren, B.; Zherebetskyy, D.; Patera, L. L. Science, Vol. 351, Issue 6272 https://doi.org/10.1126/science.aad8868	journal	January 2016
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis Kuld, S.; Thorhauge, M.; Falsig, H. Science, Vol. 352, Issue 6288 https://doi.org/10.1126/science.aaf0718	journal	May 2016
Formation of active sites on transition metals through reaction-driven migration of surface atoms Xu, Lang; Papanikolaou, Konstantinos G.; Lechner, Barbara A. J. Science, Vol. 380, Issue 6640 https://doi.org/10.1126/science.add0089	journal	April 2023
The Superlattice Formation and Lattice Spacing Changes in Copper-Gold Alloys No authors listed Acta Physica Sinica, Vol. 22, Issue 6 https://doi.org/10.7498/aps.22.669	journal	January 1966

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