Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

Zugic, Branko; van Spronsen, Matthijs A.; Heine, Christian; Montemore, Matthew M.; Li, Yuanyuan; Zakharov, Dmitri N.; Karakalos, Stavros; Lechner, Barbara A. J.; Crumlin, Ethan; Biener, Monika M.; Frenkel, Anatoly I.; Biener, Juergen; Stach, Eric A.; Salmeron, Miquel B.; Kaxiras, Efthimios; Madix, Robert J.; Friend, Cynthia M.

doi:10.1016/j.jcat.2019.08.041

Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97

Journal Article · 22 October 2019 · Journal of Catalysis

DOI: https://doi.org/10.1016/j.jcat.2019.08.041 · OSTI ID:1606185

Zugic, Branko ^[1]; van Spronsen, Matthijs A. ^[2]; Heine, Christian ^[3]; Montemore, Matthew M. ^[4]; Li, Yuanyuan ^[5]; Zakharov, Dmitri N. ^[6];

^[1]; Lechner, Barbara A. J. ^[3]; Crumlin, Ethan ^[7]; Biener, Monika M. ^[8];

^[9]; Biener, Juergen ^[8]; Stach, Eric A. ^[6]; Salmeron, Miquel B. ^[3]; Kaxiras, Efthimios ^[4]; Madix, Robert J. ^[4]; Friend, Cynthia M. ^[10]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Harvard Univ., Cambridge, MA (United States). Paulson School of Engineering and Applied Sciences
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States)
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, Paulson School of Engineering and Applied Sciences

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag_0.03Au_0.97 alloy and their subsequent evolution under steady-state CH₃OH oxidation conditions are investigated. Activation using O₃ results in AgO and Au₂O₃, strongly enriching the near-surface region in Ag. These oxides reduce in the O₂/CH₃OH mixture, yielding CO₂ and producing a highly Ag-enriched surface alloy. At the reaction tem-perature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher tem-peratures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These find-ings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1606185

Report Number(s):: BNL--213755-2020-JAAM

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 380; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

X-ray photoelectron spectroscopic binding energy shifts due to matrix in alloys and small supported metal particles Kim, K. S.; Winograd, N. Chemical Physics Letters, Vol. 30, Issue 1 https://doi.org/10.1016/0009-2614(75)85505-9	journal	January 1975
Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation Personick, Michelle L.; Zugic, Branko; Biener, Monika M. ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00330	journal	June 2015
A Comparison of CO Oxidation by Hydroxyl and Atomic Oxygen from Water on Low-Coordinated Au Atoms van Spronsen, Matthijs A.; Weststrate, Kees-Jan; Juurlink, Ludo B. F. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01720	journal	September 2016
An EXAFS study on the photo-assisted growth of silver nanoparticles on titanium dioxide thin-films and the identification of their photochromic states Kafizas, Andreas; A. Parry, Stephen; Chadwick, Alan V. Physical Chemistry Chemical Physics, Vol. 15, Issue 21 https://doi.org/10.1039/c3cp44513e	journal	January 2013
A near ambient pressure XPS study of Au oxidation Klyushin, Alexander Yu.; Rocha, Tulio C. R.; Hävecker, Michael Physical Chemistry Chemical Physics, Vol. 16, Issue 17 https://doi.org/10.1039/c4cp00308j	journal	January 2014
Mechanism for reversed photoemission core-level shifts of oxidized Ag Grönbeck, Henrik; Klacar, Simon; Martin, Natalia M. Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/physrevb.85.115445	journal	March 2012
A versatile sample-environment cell for non-ambient X-ray scattering experiments Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles Journal of Applied Crystallography, Vol. 41, Issue 4 https://doi.org/10.1107/s0021889808020165	journal	July 2008
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 Shinotsuka, Hiroshi; Tanuma, Shigeo; Powell, Cedric Wiley https://doi.org/10.48505/nims.3043	preprint	January 2015
XPS: binding energy calibration of electron spectrometers 5?re-evaluation of the reference energies Seah, M. P.; Gilmore, I. S.; Beamson, G. Surface and Interface Analysis, Vol. 26, Issue 9 https://doi.org/10.1002/(SICI)1096-9918(199808)26:9<642::AID-SIA408>3.0.CO;2-3	journal	August 1998
On the Role of Residual Ag in Nanoporous Au Catalysts for CO Oxidation: A Combined Microreactor and TAP Reactor Study Wang, L. C.; Zhong, Y.; Widmann, D. ChemCatChem, Vol. 4, Issue 2 https://doi.org/10.1002/cctc.201100297	journal	December 2011
Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface Xu, Bingjun; Siler, Cassandra G. F.; Madix, Robert J. Chemistry - A European Journal, Vol. 20, Issue 16 https://doi.org/10.1002/chem.201304837	journal	March 2014
New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica Shirman, Tanya; Lattimer, Judith; Luneau, Mathilde Chemistry - A European Journal, Vol. 24, Issue 8 https://doi.org/10.1002/chem.201704552	journal	November 2017
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
Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase Dou, Jian; Tang, Yu; Nguyen, Luan Catalysis Letters, Vol. 147, Issue 2 https://doi.org/10.1007/s10562-016-1883-6	journal	December 2016
Oxygen Adsorption and Low-Temperature CO Oxidation on a Nanoporous Au Catalyst: Reaction Mechanism and Foreign Metal Effects Wang, L. C.; Zhong, Y.; Widmann, D. Topics in Catalysis, Vol. 61, Issue 5-6 https://doi.org/10.1007/s11244-017-0881-2	journal	January 2018
Surface Segregation in Au–Ag Alloys Investigated by Atom Probe Tomography Gilis, Natalia; Jacobs, Luc; Barroo, Cédric Topics in Catalysis, Vol. 61, Issue 14 https://doi.org/10.1007/s11244-018-1040-0	journal	August 2018
X-ray photoelectron spectroscopic binding energy shifts due to matrix in alloys and small supported metal particles Kim, K. S.; Winograd, N. Chemical Physics Letters, Vol. 30, Issue 1 https://doi.org/10.1016/0009-2614(75)85505-9	journal	January 1975
Structure-dependent surface core level shifts for the Au(111), (100), and (110) surfaces Heimann, P.; van der Veen, J. F.; Eastman, D. E. Solid State Communications, Vol. 38, Issue 7 https://doi.org/10.1016/0038-1098(81)90947-9	journal	May 1981
Surface core-level shifts at the end and beginning of the transition metal series Erbudak, M.; Kalt, P.; Schlapbach, L. Surface Science, Vol. 126, Issue 1-3 https://doi.org/10.1016/0039-6028(83)90698-2	journal	March 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
The surface energy of metals Vitos, L.; Ruban, A. V.; Skriver, H. L. Surface Science, Vol. 411, Issue 1-2 https://doi.org/10.1016/S0039-6028(98)00363-X	journal	August 1998
Thermally and catalytically induced coarsening of nanoporous Au Pia, Giorgio; Cincotti, Alberto; Delogu, Francesco Materials Letters, Vol. 183 https://doi.org/10.1016/j.matlet.2016.07.051	journal	November 2016
Photoelectron spectroscopy under ambient pressure and temperature conditions Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2 https://doi.org/10.1016/j.nima.2008.12.155	journal	March 2009
Microstructure studies in nanoporous Au: Effects on electro-oxidation Lakshmanan, C.; Behera, A. K.; Viswanath, R. N. Scripta Materialia, Vol. 146 https://doi.org/10.1016/j.scriptamat.2017.11.018	journal	March 2018
DFT study of the Au(321) surface reconstruction by consecutive deposition of oxygen atoms Fajín, José L. C.; Cordeiro, M. Natália D. S.; Gomes, José R. B. Surface Science, Vol. 602, Issue 2 https://doi.org/10.1016/j.susc.2007.10.037	journal	January 2008
The creation of microscopic surface structures by interfacial diffusion of Au and Ag on Ag(110): A XPS and STM study Schmid, Martin; Madix, Robert J.; Friend, C. M. Surface Science, Vol. 643 https://doi.org/10.1016/j.susc.2015.08.023	journal	January 2016
Atomic-scale electron microscopy at ambient pressure Creemer, J. F.; Helveg, S.; Hoveling, G. H. Ultramicroscopy, Vol. 108, Issue 9 https://doi.org/10.1016/j.ultramic.2008.04.014	journal	August 2008
Hydrophilic Interaction Between Low-Coordinated Au and Water: H ₂ O/Au(310) Studied with TPD and XPS van Spronsen, Matthijs A.; Weststrate, Kees-Jan; den Dunnen, Angela The Journal of Physical Chemistry C, Vol. 120, Issue 16 https://doi.org/10.1021/acs.jpcc.6b00912	journal	April 2016
How Does Nanoporous Gold Dissociate Molecular Oxygen? Montemore, Matthew M.; Madix, Robert J.; Kaxiras, Efthimios The Journal of Physical Chemistry C, Vol. 120, Issue 30 https://doi.org/10.1021/acs.jpcc.6b03371	journal	July 2016
Macroscopic 3D Nanoporosity Formation by Dry Oxidation of AgAu Alloys Barroo, Cédric; Montemore, Matthew M.; Janvelyan, Nare The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b12847	journal	February 2017
Oxygen-Driven Surface Evolution of Nanoporous Gold: Insights from Ab Initio Molecular Dynamics and Auger Electron Spectroscopy Li, Yong; Dononelli, Wilke; Moreira, Raphaell The Journal of Physical Chemistry C, Vol. 122, Issue 10 https://doi.org/10.1021/acs.jpcc.7b08873	journal	November 2017
Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation Personick, Michelle L.; Zugic, Branko; Biener, Monika M. ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00330	journal	June 2015
A Comparison of CO Oxidation by Hydroxyl and Atomic Oxygen from Water on Low-Coordinated Au Atoms van Spronsen, Matthijs A.; Weststrate, Kees-Jan; Juurlink, Ludo B. F. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01720	journal	September 2016
Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches Liu, Deyu; Li, Yuanyuan; Kottwitz, Matthew ACS Catalysis, Vol. 8, Issue 5 https://doi.org/10.1021/acscatal.8b00706	journal	April 2018
Toward Controlled Modification of Nanoporous Gold. A Detailed Surface Science Study on Cleaning and Oxidation Schaefer, A.; Ragazzon, D.; Wittstock, A. The Journal of Physical Chemistry C, Vol. 116, Issue 7 https://doi.org/10.1021/jp207638t	journal	February 2012
Chemisorbed Oxygen on the Au(321) Surface Alloyed with Silver: A First-Principles Investigation Moskaleva, Lyudmila V.; Weiss, Theodor; Klüner, Thorsten The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/jp511884k	journal	April 2015
Dynamic Structure of a Working Methanol Steam Reforming Catalyst: In Situ Quick-EXAFS on Pd/ZnO Nanoparticles Föttinger, Karin; van Bokhoven, Jeroen A.; Nachtegaal, Maarten The Journal of Physical Chemistry Letters, Vol. 2, Issue 5 https://doi.org/10.1021/jz101751s	journal	February 2011
Atomic Observation of Catalysis-Induced Nanopore Coarsening of Nanoporous Gold Fujita, Takeshi; Tokunaga, Tomoharu; Zhang, Ling Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl403895s	journal	February 2014
Correlating Catalytic Activity of Ag–Au Nanoparticles with 3D Compositional Variations Slater, Thomas J. A.; Macedo, Alexandra; Schroeder, Sven L. M. Nano Letters, Vol. 14, Issue 4 https://doi.org/10.1021/nl4047448	journal	March 2014
Revealing the Atomic Restructuring of Pt–Co Nanoparticles Xin, Huolin L.; Alayoglu, Selim; Tao, Runzhe Nano Letters, Vol. 14, Issue 6 https://doi.org/10.1021/nl500553a	journal	May 2014
Atomic origins of the high catalytic activity of nanoporous gold Fujita, Takeshi; Guan, Pengfei; McKenna, Keith Nature Materials, Vol. 11, Issue 9 https://doi.org/10.1038/nmat3391	journal	August 2012
Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts Zugic, Branko; Wang, Lucun; Heine, Christian Nature Materials, Vol. 16, Issue 5 https://doi.org/10.1038/nmat4824	journal	December 2016
Self-activated surface dynamics in gold catalysts under reaction environments Kamiuchi, Naoto; Sun, Keju; Aso, Ryotaro Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04412-4	journal	May 2018
Ag surface segregation in nanoporous Au catalysts during CO oxidation Pia, Giorgio; Sogne, Elisa; Falqui, Andrea Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-33631-4	journal	October 2018
The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen Baker, Thomas A.; Liu, Xiaoying; Friend, Cynthia M. Phys. Chem. Chem. Phys., Vol. 13, Issue 1 https://doi.org/10.1039/C0CP01514H	journal	January 2011
On the theoretical understanding of the unexpected O ₂ activation by nanoporous gold Fajín, José L. C.; Cordeiro, M. Natália D. S.; Gomes, José R. B. Chem. Commun., Vol. 47, Issue 29 https://doi.org/10.1039/C1CC12166A	journal	January 2011
Controlling O coverage and stability by alloying Au and Ag Montemore, Matthew M.; Cubuk, Ekin D.; Klobas, J. Eric Physical Chemistry Chemical Physics, Vol. 18, Issue 38 https://doi.org/10.1039/C6CP05611C	journal	January 2016
Silver residues as a possible key to a remarkable oxidative catalytic activity of nanoporous gold Moskaleva, Lyudmila V.; Röhe, Sarah; Wittstock, Arne Physical Chemistry Chemical Physics, Vol. 13, Issue 10 https://doi.org/10.1039/c0cp02372h	journal	January 2011
Applications of extended X-ray absorption fine-structure spectroscopy to studies of bimetallic nanoparticle catalysts Frenkel, Anatoly I. Chemical Society Reviews, Vol. 41, Issue 24 https://doi.org/10.1039/c2cs35174a	journal	January 2012
An EXAFS study on the photo-assisted growth of silver nanoparticles on titanium dioxide thin-films and the identification of their photochromic states Kafizas, Andreas; A. Parry, Stephen; Chadwick, Alan V. Physical Chemistry Chemical Physics, Vol. 15, Issue 21 https://doi.org/10.1039/c3cp44513e	journal	January 2013
A near ambient pressure XPS study of Au oxidation Klyushin, Alexander Yu.; Rocha, Tulio C. R.; Hävecker, Michael Physical Chemistry Chemical Physics, Vol. 16, Issue 17 https://doi.org/10.1039/c4cp00308j	journal	January 2014
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2 Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda Review of Scientific Instruments, Vol. 81, Issue 5 https://doi.org/10.1063/1.3427218	journal	May 2010
Short range order in bimetallic nanoalloys: An extended X-ray absorption fine structure study Frenkel, Anatoly I.; Wang, Qi; Sanchez, Sergio I. The Journal of Chemical Physics, Vol. 138, Issue 6 https://doi.org/10.1063/1.4790509	journal	February 2013
The ReactorSTM: Atomically resolved scanning tunneling microscopy under high-pressure, high-temperature catalytic reaction conditions Herbschleb, C. T.; van der Tuijn, P. C.; Roobol, S. B. Review of Scientific Instruments, Vol. 85, Issue 8 https://doi.org/10.1063/1.4891811	journal	August 2014
The ReactorAFM : Non-contact atomic force microscope operating under high-pressure and high-temperature catalytic conditions Roobol, S. B.; Cañas-Ventura, M. E.; Bergman, M. Review of Scientific Instruments, Vol. 86, Issue 3 https://doi.org/10.1063/1.4916194	journal	March 2015
Charge Flow and d Compensation in Gold Alloys Watson, R. E.; Hudis, J.; Perlman, M. L. Physical Review B, Vol. 4, Issue 12 https://doi.org/10.1103/PhysRevB.4.4139	journal	December 1971
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
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
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
Surface characterization study of Ag, AgO, and Ag 2 O using x-ray photoelectron spectroscopy and electron energy-loss spectroscopy Hoflund, Gar B.; Hazos, Zoltan F.; Salaita, Ghaleb N. Physical Review B, Vol. 62, Issue 16 https://doi.org/10.1103/PhysRevB.62.11126	journal	October 2000
First-principles investigations of the structure and stability of oxygen adsorption and surface oxide formation at Au(111) Shi, Hongqing; Stampfl, Catherine Physical Review B, Vol. 76, Issue 7 https://doi.org/10.1103/PhysRevB.76.075327	journal	August 2007
A versatile sample-environment cell for non-ambient X-ray scattering experiments Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles Journal of Applied Crystallography, Vol. 41, Issue 4 https://doi.org/10.1107/S0021889808020165	journal	July 2008
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
AgO XPS Spectra Hoflund, Gar B.; Weaver, Jason F.; Epling, William S. Surface Science Spectra, Vol. 3, Issue 2 https://doi.org/10.1116/1.1247779	journal	April 1994
The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts Behrens, M.; Studt, F.; Kasatkin, I. Science, Vol. 336, Issue 6083, p. 893-897 https://doi.org/10.1126/science.1219831	journal	April 2012

Similar Records

Nanoporous Gold: Understanding the Origin of the Reactivity of a 21st Century Catalyst Made by Pre-Columbian Technology

Journal Article · 2015 · ACS Catalysis · OSTI ID:1386056

Biener, Juergen; Biener, Monika M.; Madix, Robert J.; +1 more

Insights into the Surface Electronic Structure and Catalytic Activity of InO_x/Au(111) Inverse Catalysts for CO₂ Hydrogenation to Methanol

Journal Article · 2024 · ACS Catalysis · OSTI ID:2477565

Prabhakar Reddy, Kasala; Tian, Yi; Ramírez, Pedro J.; +7 more

Enhanced kinetics of Al{sub 0.97}Ga{sub 0.03}As wet oxidation through the use of hydrogenation

Journal Article · 2006 · Applied Physics Letters · OSTI ID:20883222

Le Du, M; Sagnes, I; Beaudoin, G; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Diluted alloys
In situ/operando multimodal approach
Metastability
Nanoporous Au
Selective oxidation of CH3OH

Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

Citation Formats

References (65)

Similar Records

Related Subjects

Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97