Modifying the Reactivity of Single Pd Sites in a Trimetallic Sn‐Pd‐Ag Surface Alloy: Tuning CO Binding Strength

Mohrhusen, Lars; Zhang, Shengjie; Montemore, Matthew M.; Madix, Robert J.

doi:10.1002/smll.202405715

Title: Modifying the Reactivity of Single Pd Sites in a Trimetallic Sn‐Pd‐Ag Surface Alloy: Tuning CO Binding Strength

Journal Article · 06 September 2024 · Small

DOI: https://doi.org/10.1002/smll.202405715 · OSTI ID:2440069

^[1]; Zhang, Shengjie ^[2];

^[2]; Madix, Robert J. ^[3]

Department of Chemistry and Chemical Biology Harvard University Cambridge MA 02138 USA
Department of Chemical and Biomolecular Engineering Tulane University New Orleans LA 70118 USA
John A. Paulson School of Engineering and Applied Sciences Harvard University Cambridge MA 02138 USA

Abstract Improving control over active‐site reactivity is a grand challenge in catalysis. Single‐atom alloys (SAAs) consisting of a reactive component doped as single atoms into a more inert host metal feature localized and well‐defined active sites, but fine tuning their properties is challenging. Here, a framework is developed for tuning single‐atom site reactivity by alloying in an additional inert metal, which this work terms an alloy‐host SAA. Specifically, this work creates about 5% Pd single‐atom sites in a Pd ₃₃ Ag ₆₇ (111) single crystal surface, and then identifies Sn based on computational screening as a suitable third metal to introduce. Subsequent experimental studies show that introducing Sn indeed modifies the electronic structure and chemical reactivity (measured by CO desorption energies) of the Pd sites. The modifications to both the electronic structure and the CO adsorption energies are in close agreement with the calculations. These results indicate that the use of an alloy host environment to modify the reactivity of single‐atom sites can allow fine‐tuning of catalytic performance and boost resistance against strong‐binding adsorbates such as CO.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0012573

OSTI ID:: 2440069

Journal Information:: Small, Journal Name: Small Journal Issue: 48 Vol. 20; ISSN 1613-6810

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (58)

Atomically Dispersed Copper-Platinum Dual Sites Alloyed with Palladium Nanorings Catalyze the Hydrogen Evolution Reaction Chao, Tingting; Luo, Xuan; Chen, Wenxing Angewandte Chemie International Edition, Vol. 56, Issue 50 https://doi.org/10.1002/anie.201709803	journal	November 2017
Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity Chen, Minda; Yan, Yu; Gebre, Mebatsion Angewandte Chemie International Edition, Vol. 60, Issue 33 https://doi.org/10.1002/anie.202106515	journal	July 2021
Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies Wegener, Evan C.; Bukowski, Brandon C.; Yang, Dali ChemCatChem, Vol. 12, Issue 5 https://doi.org/10.1002/cctc.201901869	journal	January 2020
Calculations of electron inelastic mean free paths. X. Data for 41 elemental solids over the 50 eV to 200 keV range with the relativistic full Penn algorithm: Calculations of electron inelastic mean free paths. X Shinotsuka, H.; Tanuma, S.; Powell, C. J. Surface and Interface Analysis, Vol. 47, Issue 9 https://doi.org/10.1002/sia.5789	journal	July 2015
Investigating the Reactivity of Single Atom Alloys Using Density Functional Theory Thirumalai, Hari; Kitchin, John R. Topics in Catalysis, Vol. 61, Issue 5-6 https://doi.org/10.1007/s11244-018-0899-0	journal	January 2018
Extendable Machine Learning Model for the Stability of Single Atom Alloys Rao, Karun K.; Do, Quan K.; Pham, Khoa Topics in Catalysis, Vol. 63, Issue 7-8 https://doi.org/10.1007/s11244-020-01267-2	journal	April 2020
The structure and activity of supported metal catalysts VII. CO poisoning and metal location in palladium-charcoal catalysts Pope, D. Journal of Catalysis, Vol. 28, Issue 1 https://doi.org/10.1016/0021-9517(73)90177-2	journal	January 1973
Physisorption of CO on Ag(111): investigation of the monolayer and the multilayer through HREELS, ARUPS, and TDS Hansen, W.; Bertolo, M.; Jacobi, K. Surface Science, Vol. 253, Issue 1-3 https://doi.org/10.1016/0039-6028(91)90576-E	journal	August 1991
Influence of alloyed Sn atoms on the chemisorption properties of Ni(111) as probed by RAIRS and TPD studies of CO adsorption Xu, Chen; Koel, Bruce E. Surface Science, Vol. 327, Issue 1-2 https://doi.org/10.1016/0039-6028(94)00816-7	journal	April 1995
Probing the modifier precursor state: adsorption of CO on Sn/Pt(111) surface alloys Xu, Chen; Koel, Bruce E. Surface Science, Vol. 304, Issue 3 https://doi.org/10.1016/0039-6028(94)91335-8	journal	March 1994
A thermodynamic evaluation of the Ag-Sn system Chevalier, Pierre-Yves Thermochimica Acta, Vol. 136 https://doi.org/10.1016/0040-6031(88)87426-4	journal	December 1988
Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 Yeh, J. J.; Lindau, I. Atomic Data and Nuclear Data Tables, Vol. 32, Issue 1 https://doi.org/10.1016/0092-640X(85)90016-6	journal	January 1985
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
Structural and electronic properties of Sn overlayers and surface alloys on Pd(111) Lee, Adam F.; Baddeley, Christopher J.; Tikhov, Mintcho S. Surface Science, Vol. 373, Issue 2-3 https://doi.org/10.1016/S0039-6028(96)01160-0	journal	March 1997
STM study of the (111) and (100) surfaces of PdAg Wouda, P. T.; Schmid, M.; Nieuwenhuys, B. E. Surface Science, Vol. 417, Issue 2-3 https://doi.org/10.1016/S0039-6028(98)00673-6	journal	November 1998
C2H2 semi-hydrogenation on the metal M (M = Cu, Ag, Au) alloyed single-atom Pd catalysts: Effects of Pd coordination number and environment on the catalytic performance Qi, Yamin; Wang, Baojun; Fan, Maohong Chemical Engineering Science, Vol. 243 https://doi.org/10.1016/j.ces.2021.116786	journal	November 2021
Dilute Pd-in-Au alloy RCT-SiO2 catalysts for enhanced oxidative methanol coupling Filie, Amanda; Shirman, Tanya; Foucher, Alexandre C. Journal of Catalysis https://doi.org/10.1016/j.jcat.2021.06.003	journal	June 2021
In situ spectroscopic investigation of CO accumulation and poisoning on Pd black surfaces in concentrated HCOOH Zhang, Han-Xuan; Wang, Shao-Hua; Jiang, Kun Journal of Power Sources, Vol. 199 https://doi.org/10.1016/j.jpowsour.2011.10.033	journal	February 2012
The adsorption of benzene on Pd(111) and ordered Sn/Pd(111) surface alloys Hamm, G.; Schmidt, T.; Breitbach, J. Surface Science, Vol. 562, Issue 1-3 https://doi.org/10.1016/j.susc.2004.05.119	journal	August 2004
Formation, stability and CO adsorption properties of PdAg/Pd(111) surface alloys Ma, Yunsheng; Bansmann, J.; Diemant, T. Surface Science, Vol. 603, Issue 7 https://doi.org/10.1016/j.susc.2009.02.024	journal	April 2009
Comment on “STM study of the (111) and (100) surfaces of PdAg, Surf. Sci. 417 (1998) 292–300″ and references therein Egle, Tobias; Cavanaugh, Timothy J.; Friend, Cynthia M. Surface Science, Vol. 720 https://doi.org/10.1016/j.susc.2022.122048	journal	June 2022
Dilute Pd/Au Alloy Nanoparticles Embedded in Colloid-Templated Porous SiO 2 : Stable Au-Based Oxidation Catalysts Luneau, Mathilde; Shirman, Tanya; Filie, Amanda Chemistry of Materials, Vol. 31, Issue 15 https://doi.org/10.1021/acs.chemmater.9b01779	journal	July 2019
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
Heterogeneous Trimetallic Nanoparticles as Catalysts Crawley, James W. M.; Gow, Isla E.; Lawes, Naomi Chemical Reviews, Vol. 122, Issue 6 https://doi.org/10.1021/acs.chemrev.1c00493	journal	March 2022
Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites Lee, Jennifer D.; Miller, Jeffrey B.; Shneidman, Anna V. Chemical Reviews, Vol. 122, Issue 9 https://doi.org/10.1021/acs.chemrev.1c00967	journal	March 2022
Combined DRIFTS and DFT Study of CO Adsorption and Segregation Modes in Pt–Sn Nanoalloys Wang, Qing; Tichit, Didier; Meunier, Frederic The Journal of Physical Chemistry C, Vol. 124, Issue 18 https://doi.org/10.1021/acs.jpcc.0c01296	journal	April 2020
CO Poisoning and CO Hydrogenation on the Surface of Pd Hydrogen Separation Membranes O’Brien, Casey P.; Lee, Ivan C. The Journal of Physical Chemistry C, Vol. 121, Issue 31 https://doi.org/10.1021/acs.jpcc.7b05046	journal	July 2017
Coverage Effect on the Activity of the Acetylene Semihydrogenation over Pd–Sn Catalysts: A Density Functional Theory Study Zhao, Jiubing; Zha, Shenjun; Mu, Rentao The Journal of Physical Chemistry C, Vol. 122, Issue 11 https://doi.org/10.1021/acs.jpcc.7b11394	journal	March 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
Controlling Hydrogen Activation, Spillover, and Desorption with Pd–Au Single-Atom Alloys Lucci, Felicia R.; Darby, Matthew T.; Mattera, Michael F. G. The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02400	journal	January 2016
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
A Large-Scalable, Surfactant-Free, and Ultrastable Ru-Doped Pt₃Co Oxygen Reduction Catalyst Zhu, Yiming; Peng, Jiaheng; Zhu, Xiaorong Nano Letters, Vol. 21, Issue 15 https://doi.org/10.1021/acs.nanolett.1c02064	journal	July 2021
High-Entropy Alloys as a Platform for Catalysis: Progress, Challenges, and Opportunities Xin, Yue; Li, Shuhui; Qian, Yayang ACS Catalysis, Vol. 10, Issue 19 https://doi.org/10.1021/acscatal.0c03617	journal	September 2020
Entropic Control of HD Exchange Rates over Dilute Pd-in-Au Alloy Nanoparticle Catalysts van der Hoeven, Jessi E. S.; Ngan, Hio Tong; Taylor, Austin ACS Catalysis, Vol. 11, Issue 12 https://doi.org/10.1021/acscatal.1c01400	journal	June 2021
Integrated Catalysis-Surface Science-Theory Approach to Understand Selectivity in the Hydrogenation of 1-Hexyne to 1-Hexene on PdAu Single-Atom Alloy Catalysts Liu, Jilei; Uhlman, Matthew B.; Montemore, Matthew M. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b00491	journal	August 2019
Achieving High Selectivity for Alkyne Hydrogenation at High Conversions with Compositionally Optimized PdAu Nanoparticle Catalysts in Raspberry Colloid-Templated SiO ₂ Luneau, Mathilde; Shirman, Tanya; Foucher, Alexandre C. ACS Catalysis, Vol. 10, Issue 1 https://doi.org/10.1021/acscatal.9b04243	journal	November 2019
A Priori Design of Dual-Atom Alloy Sites and Experimental Demonstration of Ethanol Dehydrogenation and Dehydration on PtCrAg Kress, Paul L.; Zhang, Shengjie; Wang, Yicheng Journal of the American Chemical Society, Vol. 145, Issue 15 https://doi.org/10.1021/jacs.2c13577	journal	March 2023
Probing Single Pt Atoms in Complex Intermetallic Al ₁₃ Fe ₄ Yamada, Tsunetomo; Kojima, Takayuki; Abe, Eiji Journal of the American Chemical Society, Vol. 140, Issue 11 https://doi.org/10.1021/jacs.7b13658	journal	February 2018
Site-Specific Scaling Relations for Hydrocarbon Adsorption on Hexagonal Transition Metal Surfaces Montemore, Matthew M.; Medlin, J. Will The Journal of Physical Chemistry C, Vol. 117, Issue 39 https://doi.org/10.1021/jp4076405	journal	September 2013
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
Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis Yao, Yancai; Hu, Sulei; Chen, Wenxing Nature Catalysis, Vol. 2, Issue 4 https://doi.org/10.1038/s41929-019-0246-2	journal	March 2019
Author Correction: Enhancing catalytic performance of dilute metal alloy nanomaterials Luneau, Mathilde; Guan, Erjia; Chen, Wei Communications Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/s42004-020-0310-5	journal	May 2020
Direct evidence by in situ IR CO monitoring of the formation and the surface segregation of a Pt–Sn alloy Moscu, Alina; Schuurman, Yves; Veyre, Laurent Chemical Communications, Vol. 50, Issue 62 https://doi.org/10.1039/C4CC03208J	journal	January 2014
Scaling relations between adsorption energies for computational screening and design of catalysts Montemore, Matthew M.; Medlin, J. Will Catal. Sci. Technol., Vol. 4, Issue 11 https://doi.org/10.1039/C4CY00335G	journal	January 2014
Palladium–gold single atom alloy catalysts for liquid phase selective hydrogenation of 1-hexyne Liu, Jilei; Shan, Junjun; Lucci, Felicia R. Catalysis Science & Technology, Vol. 7, Issue 19 https://doi.org/10.1039/C7CY00794A	journal	January 2017
Atomically dispersed Ru in Pt₃Sn intermetallic alloy as an efficient methanol oxidation electrocatalyst Yang, Tianyi; Qin, Fengjuan; Zhang, Shuping Chemical Communications, Vol. 57, Issue 17 https://doi.org/10.1039/D0CC08210D	journal	January 2021
Factors controlling oxophilicity and carbophilicity of transition metals and main group metals Kayode, Gbolade O.; Montemore, Matthew M. Journal of Materials Chemistry A, Vol. 9, Issue 39 https://doi.org/10.1039/D1TA06453C	journal	January 2021
Tuning reactivity in trimetallic dual-atom alloys: molecular-like electronic states and ensemble effects Zhang, Shengjie; Sykes, E. Charles H.; Montemore, Matthew M. Chemical Science, Vol. 13, Issue 47 https://doi.org/10.1039/D2SC03650A	journal	January 2022
The interaction of CO with PdAg/Pd(111) surface alloys—A case study of ensemble effects on a bimetallic surface Ma, Yunsheng; Diemant, T.; Bansmann, J. Physical Chemistry Chemical Physics, Vol. 13, Issue 22 https://doi.org/10.1039/c1cp00009h	journal	January 2011
Facilitating hydrogen atom migration via a dense phase on palladium islands to a surrounding silver surface O’Connor, Christopher R.; Duanmu, Kaining; Patel, Dipna A. Proceedings of the National Academy of Sciences, Vol. 117, Issue 37 https://doi.org/10.1073/pnas.2010413117	journal	September 2020
The poisoning of a palladium catalyst by carbon monoxide Burrows, M. G. T.; Stockmayer, W. H.; Chapman, David Leonard Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 176, Issue 967, p. 474-483 https://doi.org/10.1098/rspa.1940.0101	journal	November 1940
Proof that ∂ E ∂ n i = ε in density-functional theory Janak, J. F. Physical Review B, Vol. 18, Issue 12 https://doi.org/10.1103/PhysRevB.18.7165	journal	December 1978
Theory of the scanning tunneling microscope Tersoff, J.; Hamann, D. R. Physical Review B, Vol. 31, Issue 2 https://doi.org/10.1103/PhysRevB.31.805	journal	January 1985
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold Shirley, D. A. Physical Review B, Vol. 5, Issue 12 https://doi.org/10.1103/PhysRevB.5.4709	journal	June 1972
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data Tkatchenko, Alexandre; Scheffler, Matthias Physical Review Letters, Vol. 102, Issue 7 https://doi.org/10.1103/PhysRevLett.102.073005	journal	February 2009
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

Similar Records

Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites

Journal Article · 2021 · Journal of Physical Chemistry Letters · OSTI ID:1844969

Schumann, Julia; Bao, Yutian; Hannagan, Ryan T.; +3 more

Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion

Journal Article · 2024 · ACS Catalysis · OSTI ID:2480017

Yang, Weiwei; Song, Haohong; Zhang, Lihua; +7 more

Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia

Journal Article · 2023 · Nature Synthesis · OSTI ID:1974184

Gao, Qiang; Yao, Bingqing; Pillai, Hemanth Somarajan; +12 more

Title: Modifying the Reactivity of Single Pd Sites in a Trimetallic Sn‐Pd‐Ag Surface Alloy: Tuning CO Binding Strength

Citation Formats

References (58)

Similar Records

Related Subjects