On the nature of active sites for formic acid decomposition on gold catalysts

Li, Sha; Singh, Suyash; Dumesic, James A.; Mavrikakis, Manos

doi:10.1039/c9cy00410f

Title: On the nature of active sites for formic acid decomposition on gold catalysts

Abstract

Formic acid decomposition has been studied experimentally on supported gold nanoparticles with strong evidence showing the critical role of gold clusters in the subnanometer range in catalyzing the reaction. However, there is a lack of theoretical studies capable of explaining these experimental observations. In this work, without accounting for support effects, vapor phase formic acid decomposition was studied systematically on sub-nanometric gold clusters from Au₄ to Au₂₅, among which several candidate Au clusters were identified as a promising active site model for the Au/SiC catalysts. Combining theoretical and experimental results suggested that the active site on Au/SiC catalysts could be represented by an Au₁₈ cluster, on which the reaction rates calculated from the microkinetic model closely match the experimentally measured rates. On Au₁₈, formic acid decomposition proceeds through the same formate mediated pathway as that on extended Au surfaces (HCOOH → HCOO + H → CO₂ + 2H → CO₂ + H₂), with the reaction taking place on a triangular Au₃ site where the reactive Au atoms have a coordination number of 5. Despite the fact that other Au clusters among those studied, including Au17 and Au19 which also expose the same triangular Au₃ site, they were not found tomore »« less

Authors:

^[1]; Singh, Suyash ^[1];

^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)

Publication Date:: Wed May 08 00:00:00 EDT 2019

Research Org.:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1570852

Alternate Identifier(s):: OSTI ID: 1511504

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

Resource Type:: Accepted Manuscript

Journal Name:: Catalysis Science and Technology

Additional Journal Information:: Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2044-4753

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Li, Sha, Singh, Suyash, Dumesic, James A., and Mavrikakis, Manos. On the nature of active sites for formic acid decomposition on gold catalysts.  United States: N. p., 2019. 
Web.  doi:10.1039/c9cy00410f.

Copy to clipboard


                    Li, Sha, Singh, Suyash, Dumesic, James A., & Mavrikakis, Manos. On the nature of active sites for formic acid decomposition on gold catalysts.  United States.  https://doi.org/10.1039/c9cy00410f

Copy to clipboard


                    Li, Sha, Singh, Suyash, Dumesic, James A., and Mavrikakis, Manos. Wed .  
"On the nature of active sites for formic acid decomposition on gold catalysts".  United States.  https://doi.org/10.1039/c9cy00410f.  https://www.osti.gov/servlets/purl/1570852.

Copy to clipboard


                    
@article{osti_1570852,

  title        = {On the nature of active sites for formic acid decomposition on gold catalysts},

  author       = {Li, Sha and Singh, Suyash and Dumesic, James A. and Mavrikakis, Manos},

  abstractNote = {Formic acid decomposition has been studied experimentally on supported gold nanoparticles with strong evidence showing the critical role of gold clusters in the subnanometer range in catalyzing the reaction. However, there is a lack of theoretical studies capable of explaining these experimental observations. In this work, without accounting for support effects, vapor phase formic acid decomposition was studied systematically on sub-nanometric gold clusters from Au4 to Au25, among which several candidate Au clusters were identified as a promising active site model for the Au/SiC catalysts. Combining theoretical and experimental results suggested that the active site on Au/SiC catalysts could be represented by an Au18 cluster, on which the reaction rates calculated from the microkinetic model closely match the experimentally measured rates. On Au18, formic acid decomposition proceeds through the same formate mediated pathway as that on extended Au surfaces (HCOOH → HCOO + H → CO2 + 2H → CO2 + H2), with the reaction taking place on a triangular Au3 site where the reactive Au atoms have a coordination number of 5. Despite the fact that other Au clusters among those studied, including Au17 and Au19 which also expose the same triangular Au3 site, they were not found to be an accurate representation of the active sites, suggesting an atom-specific activity of gold clusters for formic acid decomposition.},

  doi          = {10.1039/c9cy00410f},

  journal      = {Catalysis Science and Technology},

  number       = 11,

  volume       = 9,

  place        = {United States},

  year         = {Wed May 08 00:00:00 EDT 2019},

  month        = {Wed May 08 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1039/c9cy00410f

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 19 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Production of CO-free H2 from formic acid. A comparative study of the catalytic behavior of Pt metals on a carbon support
journal, April 2011

Solymosi, F.; Koós, Á.; Liliom, N.
Journal of Catalysis, Vol. 279, Issue 1
DOI: 10.1016/j.jcat.2011.01.023

On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation
journal, April 2004

Lopez, N.
Journal of Catalysis, Vol. 223, Issue 1
DOI: 10.1016/j.jcat.2004.01.001

Shells of electrons in metal doped simple metal clusters
journal, June 2004

Janssens, Ewald; Neukermans, Sven; Lievens, Peter
Current Opinion in Solid State and Materials Science, Vol. 8, Issue 3-4
DOI: 10.1016/j.cossms.2004.09.002

Structure determination of gold clusters by trapped ion electron diffraction: Au14−–Au19−
journal, January 2009

Lechtken, Anne; Neiss, Christian; Kappes, Manfred M.
Physical Chemistry Chemical Physics, Vol. 11, Issue 21
DOI: 10.1039/b821036e

Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H₂
journal, July 2011

Gazsi, A.; Bánsági, T.; Solymosi, F.
The Journal of Physical Chemistry C, Vol. 115, Issue 31, p. 15459-15466
DOI: 10.1021/jp203751w

Al ₁₂ X (X = Ni, Pd, Pt, Ti, and Zr) Clusters: Promising Low-Cost and High-Activity Catalysts for CO Oxidation
journal, December 2013

Guo, Ling; Zhang, Xiao
The Journal of Physical Chemistry C, Vol. 118, Issue 1
DOI: 10.1021/jp4107074

Characterization of copper clusters through the use of density functional theory reactivity descriptors
journal, August 2002

Jaque, Pablo; Toro-Labbé, Alejandro
The Journal of Chemical Physics, Vol. 117, Issue 7
DOI: 10.1063/1.1493178

Catalysis by Gold Nanoparticles: Epoxidation of Propene
journal, June 2004

Sinha, A. K.; Seelan, S.; Tsubota, S.
Topics in Catalysis, Vol. 29, Issue 3/4
DOI: 10.1023/B:TOCA.0000029791.69935.53

Support effect for nanosized Au catalysts in hydrogen production from formic acid decomposition
journal, January 2016

Zacharska, Monika; Chuvilin, Andrey L.; Kriventsov, Vladimir V.
Catalysis Science & Technology, Vol. 6, Issue 18
DOI: 10.1039/C6CY00552G

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Counting Au catalytic sites for the water–gas shift reaction
journal, September 2012

Shekhar, Mayank; Wang, Jun; Lee, Wen-Sheng
Journal of Catalysis, Vol. 293
DOI: 10.1016/j.jcat.2012.06.008

Density-functional study of ${Au}_{n} (n = 2 - 20)$ clusters: Lowest-energy structures and electronic properties
journal, July 2002

Wang, Jinlan; Wang, Guanghou; Zhao, Jijun
Physical Review B, Vol. 66, Issue 3
DOI: 10.1103/PhysRevB.66.035418

On the Electronic and Atomic Structures of Small Au _N ^- ( N = 4−14) Clusters: A Photoelectron Spectroscopy and Density-Functional Study
journal, August 2003

Häkkinen, Hannu; Yoon, Bokwon; Landman, Uzi
The Journal of Physical Chemistry A, Vol. 107, Issue 32
DOI: 10.1021/jp035437i

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013

Flytzani-Stephanopoulos, Maria
Accounts of Chemical Research, Vol. 47, Issue 3
DOI: 10.1021/ar4001845

Size-dependent catalytic activity of supported metal clusters
journal, November 1994

Xu, Z.; Xiao, F. -S.; Purnell, S. K.
Nature, Vol. 372, Issue 6504
DOI: 10.1038/372346a0

Adsorption of O2 and oxidation of CO at Au nanoparticles supported by TiO2(110)
journal, April 2004

Molina, L. M.; Rasmussen, M. D.; Hammer, B.
The Journal of Chemical Physics, Vol. 120, Issue 16
DOI: 10.1063/1.1687337

Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase
journal, August 2008

Gruene, P.; Rayner, D. M.; Redlich, B.
Science, Vol. 321, Issue 5889
DOI: 10.1126/science.1161166

Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures
journal, June 2009

Ojeda, Manuel; Iglesia, Enrique
Angewandte Chemie International Edition, Vol. 48, Issue 26
DOI: 10.1002/anie.200805723

Geometrical and Electronic Structures of Gold, Silver, and Gold−Silver Binary Clusters: Origins of Ductility of Gold and Gold−Silver Alloy Formation
journal, August 2003

Lee, Han Myoung; Ge, Maofa; Sahu, B. R.
The Journal of Physical Chemistry B, Vol. 107, Issue 37
DOI: 10.1021/jp034826+

Gold—an introductory perspective
journal, January 2008

Hutchings, Graham J.; Brust, Mathias; Schmidbaur, Hubert
Chemical Society Reviews, Vol. 37, Issue 9
DOI: 10.1039/b810747p

Conversion of cellulose to hydrocarbon fuels by progressive removal of oxygen
journal, October 2010

Serrano-Ruiz, Juan Carlos; Braden, Drew J.; West, Ryan M.
Applied Catalysis B: Environmental, Vol. 100, Issue 1-2, p. 184-189
DOI: 10.1016/j.apcatb.2010.07.029

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
DOI: 10.1063/1.1329672

Two-dimensional magic numbers in mass abundances of photofragmented bimetallic clusters
journal, January 2003

Janssens, Ewald; Tanaka, Hiromasa; Neukermans, Sven
New Journal of Physics, Vol. 5
DOI: 10.1088/1367-2630/5/1/346

Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition
journal, March 2014

Yoo, Jong Suk; Abild-Pedersen, Frank; Nørskov, Jens K.
ACS Catalysis, Vol. 4, Issue 4
DOI: 10.1021/cs400664z

Hydrogen-Promoted Oxygen Activation by Free Gold Cluster Cations
journal, July 2009

Lang, Sandra M.; Bernhardt, Thorsten M.; Barnett, Robert N.
Journal of the American Chemical Society, Vol. 131, Issue 25
DOI: 10.1021/ja9022368

Theoretical advances of the structures and catalytic activities of small-sized gold nanoclusters
journal, December 2013

Li, Yadong; Gao, Yi
Chinese Science Bulletin, Vol. 59, Issue 3
DOI: 10.1007/s11434-013-0047-y

Mechanistic Insight into the Styrene-Selective Oxidation on Subnanometer Gold Clusters (Au ₁₆ –Au ₂₀ , Au ₂₇ , Au ₂₈ , Au ₃₀ , and Au ₃₂ –Au ₃₅ ): A Density Functional Theory Study
journal, August 2014

Lin, Sisi; Pei, Yong
The Journal of Physical Chemistry C, Vol. 118, Issue 35
DOI: 10.1021/jp505018g

Trends in the structure and bonding of noble metal clusters
journal, October 2004

Fernández, Eva M.; Soler, José M.; Garzón, Ignacio L.
Physical Review B, Vol. 70, Issue 16
DOI: 10.1103/PhysRevB.70.165403

General properties of the electronic structure of alkali metal clusters and Ia-IIa mixed clusters
journal, March 1989

Fantucci, P.; Bonačić-Koutecký, V.; Koutecký, J.
Zeitschrift für Physik D Atoms, Molecules and Clusters, Vol. 12, Issue 1-4
DOI: 10.1007/BF01426963

Odd-even alternation of global hardnesses in the Nan (n=2-9) clusters
journal, January 2000

Mineva, Tzonka; Russo, Nino; Toscano, Marirosa
International Journal of Quantum Chemistry, Vol. 80, Issue 2
DOI: 10.1002/1097-461X(2000)80:2<105::AID-QUA5>3.0.CO;2-K

Metallic Corner Atoms in Gold Clusters Supported on Rutile Are the Dominant Active Site during Water−Gas Shift Catalysis
journal, October 2010

Williams, W. Damion; Shekhar, Mayank; Lee, Wen-Sheng
Journal of the American Chemical Society, Vol. 132, Issue 40
DOI: 10.1021/ja1064262

A DFT Study of the CO Oxidation Mechanism on AlnAu (n = 1–12) Clusters
journal, January 2015

An, Xiaoyu; Guo, Ling; Li, Aixia
Journal of Cluster Science, Vol. 26, Issue 2
DOI: 10.1007/s10876-014-0838-6

Au20: A Tetrahedral Cluster
journal, February 2003

Li, J.
Science, Vol. 299, Issue 5608
DOI: 10.1126/science.1079879

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Kresse, G.; Furthmüller, J.
Computational Materials Science, Vol. 6, Issue 1, p. 15-50
DOI: 10.1016/0927-0256(96)00008-0

Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid
journal, April 2009

Huang, Wei; Bulusu, Satya; Pal, Rhitankar
ACS Nano, Vol. 3, Issue 5
DOI: 10.1021/nn900232d

Atomically precise cluster catalysis towards quantum controlled catalysts
journal, December 2014

Watanabe, Yoshihide
Science and Technology of Advanced Materials, Vol. 15, Issue 6
DOI: 10.1088/1468-6996/15/6/063501

Some recent theoretical advances in the understanding of the catalytic activity of Au
journal, September 2005

Molina, L. M.; Hammer, B.
Applied Catalysis A: General, Vol. 291, Issue 1-2
DOI: 10.1016/j.apcata.2005.01.050

CO oxidation on gold nanoparticles: Theoretical studies
journal, September 2005

Remediakis, Ioannis N.; Lopez, Nuria; Nørskov, Jens K.
Applied Catalysis A: General, Vol. 291, Issue 1-2
DOI: 10.1016/j.apcata.2005.01.052

Reaction-Relevant Gold Structures in the Low Temperature Water-Gas Shift Reaction on Au-CeO ₂
journal, August 2008

Deng, Weiling; Frenkel, Anatoly I.; Si, Rui
The Journal of Physical Chemistry C, Vol. 112, Issue 33
DOI: 10.1021/jp800075y

Probing the electronic properties and structural evolution of anionic gold clusters in the gas phase
journal, January 2012

Wang, Lei-Ming; Wang, Lai-Sheng
Nanoscale, Vol. 4, Issue 14
DOI: 10.1039/c2nr30186e

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter
ACS Catalysis, Vol. 4, Issue 12
DOI: 10.1021/cs500737p

When Gold Is Not Noble: Catalysis by Nanoparticles
journal, April 2003

Haruta, Masatake
The Chemical Record, Vol. 3, Issue 2
DOI: 10.1002/tcr.10053

Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels
journal, February 2010

Bond, J. Q.; Alonso, D. M.; Wang, D.
Science, Vol. 327, Issue 5969, p. 1110-1114
DOI: 10.1126/science.1184362

Structural Transitions from Pyramidal to Fused Planar to Tubular to Core/Shell Compact in Gold Clusters: Au _n ^- ( n = 21−25)
journal, February 2007

Bulusu, Satya; Li, Xi; Wang, Lai-Sheng
The Journal of Physical Chemistry C, Vol. 111, Issue 11
DOI: 10.1021/jp068897v

The use of titania- and iron oxide-supported gold catalysts for the hydrogenation of propyne
journal, September 2005

Lopez-Sanchez, Jose Antonio; Lennon, David
Applied Catalysis A: General, Vol. 291, Issue 1-2
DOI: 10.1016/j.apcata.2005.01.048

Structure and Surface Chemistry of Gold-Based Model Catalysts
journal, April 2011

Gong, Jinlong
Chemical Reviews, Vol. 112, Issue 5
DOI: 10.1021/cr200041p

Precision Synthesis of Subnanoparticles Using Dendrimers as a Superatom Synthesizer
journal, February 2014

Yamamoto, Kimihisa; Imaoka, Takane
Accounts of Chemical Research, Vol. 47, Issue 4
DOI: 10.1021/ar400257s

Structural Evolution of Medium-Sized Gold Clusters Au _n ^– ( n = 36, 37, 38): Appearance of Bulk-Like Face Centered Cubic Fragment
journal, March 2014

Shao, Nan; Huang, Wei; Mei, Wai-Ning
The Journal of Physical Chemistry C, Vol. 118, Issue 13
DOI: 10.1021/jp500582t

Structural evolution of Au nanoclusters: From planar to cage to tubular motifs
journal, October 2006

Xing, Xiaopeng; Yoon, Bokwon; Landman, Uzi
Physical Review B, Vol. 74, Issue 16
DOI: 10.1103/PhysRevB.74.165423

Finding the Most Catalytically Active Platinum Clusters With Low Atomicity
journal, July 2015

Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae
Angewandte Chemie International Edition, Vol. 54, Issue 34
DOI: 10.1002/anie.201504473

First-principles study of intermediate size silver clusters: Shape evolution and its impact on cluster properties
journal, October 2006

Yang, M.; Jackson, K. A.; Jellinek, J.
The Journal of Chemical Physics, Vol. 125, Issue 14
DOI: 10.1063/1.2351818

Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994

Blöchl, Peter E.; Jepsen, O.; Andersen, O. K.
Physical Review B, Vol. 49, Issue 23
DOI: 10.1103/PhysRevB.49.16223

Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation
journal, February 2011

Grabow, L. C.; Mavrikakis, M.
ACS Catalysis, Vol. 1, Issue 4
DOI: 10.1021/cs200055d

Catalytic Activities of Subnanometer Gold Clusters (Au ₁₆ –Au ₁₈ , Au ₂₀ , and Au ₂₇ –Au ₃₅ ) for CO Oxidation
journal, September 2011

Gao, Yi; Shao, Nan; Pei, Yong
ACS Nano, Vol. 5, Issue 10
DOI: 10.1021/nn201817b

Toward an Atomic-Level Understanding of Size-Specific Properties of Protected and Stabilized Gold Clusters
journal, February 2012

Tsukuda, Tatsuya
Bulletin of the Chemical Society of Japan, Vol. 85, Issue 2
DOI: 10.1246/bcsj.20110227

Size- and Structure-specificity in Catalysis by Gold Clusters
journal, April 2014

Taketoshi, Ayako; Haruta, Masatake
Chemistry Letters, Vol. 43, Issue 4
DOI: 10.1246/cl.131232

Advances in the catalysis of Au nanoparticles
journal, December 2001

Haruta, Masatake; Daté, Masakazu
Applied Catalysis A: General, Vol. 222, Issue 1-2
DOI: 10.1016/S0926-860X(01)00847-X

Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009

Kaden, W. E.; Wu, T.; Kunkel, W. A.
Science, Vol. 326, Issue 5954
DOI: 10.1126/science.1180297

Cu4 Cluster Doped Monolayer MoS2 for CO Oxidation
journal, June 2015

Chen, Z. W.; Yan, J. M.; Zheng, W. T.
Scientific Reports, Vol. 5, Issue 1
DOI: 10.1038/srep11230

Determining the size-dependent structure of ligand-free gold-cluster ions
journal, March 2010

Schooss, Detlef; Weis, Patrick; Hampe, Oliver
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1915
DOI: 10.1098/rsta.2009.0269

Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide
journal, February 1989

Haruta, M.
Journal of Catalysis, Vol. 115, Issue 2
DOI: 10.1016/0021-9517(89)90034-1

Low temperature water gas shift over gold catalysts
journal, September 2002

Andreeva, Donka
Gold Bulletin, Vol. 35, Issue 3
DOI: 10.1007/BF03214843

Active gold species on cerium oxide nanoshapes for methanol steam reforming and the water gas shift reactions
journal, January 2010

Yi, Nan; Si, Rui; Saltsburg, Howard
Energy & Environmental Science, Vol. 3, Issue 6
DOI: 10.1039/b924051a

Production of liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic acid
journal, January 2011

Braden, Drew J.; Henao, Carlos A.; Heltzel, Jacob
Green Chemistry, Vol. 13, Issue 7
DOI: 10.1039/c1gc15047b

Heterogeneous Gold-Based Catalysis for Green Chemistry: Low-Temperature CO Oxidation and Propene Oxidation
journal, June 2007

Min, Byoung Koun; Friend, Cynthia M.
Chemical Reviews, Vol. 107, Issue 6
DOI: 10.1021/cr050954d

Atomic Resolution Observation of a Size-Dependent Change in the Ripening Modes of Mass-Selected Au Nanoclusters Involved in CO Oxidation
journal, November 2015

Hu, Kuo-Juei; Plant, Simon R.; Ellis, Peter R.
Journal of the American Chemical Society, Vol. 137, Issue 48
DOI: 10.1021/jacs.5b08720

A golden age of catalysis: A perspective
journal, September 2005

Hutchings, Graham J.; Haruta, Masatake
Applied Catalysis A: General, Vol. 291, Issue 1-2
DOI: 10.1016/j.apcata.2005.05.044

Kinetic Control and Thermodynamic Selection in the Synthesis of Atomically Precise Gold Nanoclusters
journal, June 2011

Wu, Zhikun; MacDonald, Mark A.; Chen, Jenny
Journal of the American Chemical Society, Vol. 133, Issue 25
DOI: 10.1021/ja2028102

Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments
journal, February 2014

Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald
AIChE Journal, Vol. 60, Issue 4
DOI: 10.1002/aic.14401

DFT and In Situ EXAFS Investigation of Gold/Ceria−Zirconia Low-Temperature Water Gas Shift Catalysts: Identification of the Nature of the Active Form of Gold
journal, December 2005

Tibiletti, D.; Fonseca, A. Amieiro-; Burch, R.
The Journal of Physical Chemistry B, Vol. 109, Issue 47
DOI: 10.1021/jp054576s

2D-3D transition of gold cluster anions resolved
journal, May 2008

Johansson, Mikael P.; Lechtken, Anne; Schooss, Detlef
Physical Review A, Vol. 77, Issue 5
DOI: 10.1103/PhysRevA.77.053202

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

Nosé, Shuichi
The Journal of Chemical Physics, Vol. 81, Issue 1
DOI: 10.1063/1.447334

Size-dependent catalytic activity and geometries of size-selected Pt clusters on TiO₂(110) surfaces
journal, January 2011

Watanabe, Yoshihide; Wu, Xingyang; Hirata, Hirohito
Catalysis Science & Technology, Vol. 1, Issue 8, p. 1490-1495
DOI: 10.1039/c1cy00204j

Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts
journal, December 2013

Widmann, D.; Behm, R. J.
Accounts of Chemical Research, Vol. 47, Issue 3
DOI: 10.1021/ar400203e

Magic Number Pt ₁₃ and Misshapen Pt ₁₂ Clusters: Which One is the Better Catalyst?
journal, August 2013

Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae
Journal of the American Chemical Society, Vol. 135, Issue 35
DOI: 10.1021/ja405922m

Size and Support Effects for the Water–Gas Shift Catalysis over Gold Nanoparticles Supported on Model Al ₂ O ₃ and TiO ₂
journal, February 2012

Shekhar, Mayank; Wang, Jun; Lee, Wen-Sheng
Journal of the American Chemical Society, Vol. 134, Issue 10
DOI: 10.1021/ja210083d

Relationship between Ionization Potential, Polarizability, and Softness: A Case Study of Lithium and Sodium Metal Clusters
journal, August 2004

Chandrakumar, K. R. S.; Ghanty, Tapan K.; Ghosh, Swapan K.
The Journal of Physical Chemistry A, Vol. 108, Issue 32
DOI: 10.1021/jp048522e

Analysis of the odd-even alternation in simple metal clusters
journal, June 1996

Gr�nbeck, H.; Ros�n, A.
Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 36, Issue 2
DOI: 10.1007/BF01426630

CO Oxidation on Au _n /TiO ₂ Catalysts Produced by Size-Selected Cluster Deposition
journal, May 2004

Lee, Sungsik; Fan, Chaoyang; Wu, Tianpin
Journal of the American Chemical Society, Vol. 126, Issue 18
DOI: 10.1021/ja049436v

Trends in the Catalytic CO Oxidation Activity of Nanoparticles
journal, June 2008

Falsig, Hanne; Hvolbæk, Britt; Kristensen, Iben S.
Angewandte Chemie International Edition, Vol. 47, Issue 26
DOI: 10.1002/anie.200801479

Size-Dependent Structural Evolution and Chemical Reactivity of Gold Clusters
journal, January 2007

Yoon, Bokwon; Koskinen, Pekka; Huber, Bernd
ChemPhysChem, Vol. 8, Issue 1
DOI: 10.1002/cphc.200600524

A Schiff base modified gold catalyst for green and efficient H ₂ production from formic acid
journal, January 2015

Liu, Qinggang; Yang, Xiaofeng; Huang, Yanqiang
Energy & Environmental Science, Vol. 8, Issue 11
DOI: 10.1039/C5EE02506K

Pd Clusters Supported on Amorphous, Low-Porosity Carbon Spheres for Hydrogen Production from Formic Acid
journal, April 2015

Bulushev, Dmitri A.; Bulusheva, Lyubov G.; Beloshapkin, Sergey
ACS Applied Materials & Interfaces, Vol. 7, Issue 16
DOI: 10.1021/acsami.5b00983

Selective Hydrogenation of Acetylene over Au/Al ₂ O ₃ Catalyst
journal, November 2000

Jia, Jifei; Haraki, Kenta; Kondo, Junko N.
The Journal of Physical Chemistry B, Vol. 104, Issue 47
DOI: 10.1021/jp001213d

Hydrogen from formic acid decomposition over Pd and Au catalysts
journal, September 2010

Bulushev, Dmitri A.; Beloshapkin, Sergey; Ross, Julian R. H.
Catalysis Today, Vol. 154, Issue 1-2
DOI: 10.1016/j.cattod.2010.03.050

Novel Gold Catalysts for the Oxidation of Carbon Monoxide at a Temperature far Below 0 °C
journal, February 1987

Haruta, Masatake; Kobayashi, Tetsuhiko; Sano, Hiroshi
Chemistry Letters, Vol. 16, Issue 2
DOI: 10.1246/cl.1987.405

The Important Role of Hydroxyl on Oxidation Catalysis by Gold Nanoparticles
journal, November 2013

Ide, Matthew S.; Davis, Robert J.
Accounts of Chemical Research, Vol. 47, Issue 3
DOI: 10.1021/ar4001907

Evolution of Small Copper Clusters and Dissociative Chemisorption of Hydrogen
journal, January 2005

Guvelioglu, Galip H.; Ma, Pingping; He, Xiaoyi
Physical Review Letters, Vol. 94, Issue 2
DOI: 10.1103/PhysRevLett.94.026103

Decomposition of formic acid over silica encapsulated and amine functionalised gold nanoparticles
journal, January 2017

Mielby, Jerrik; Kunov-Kruse, Andreas Jonas; Kegnæs, Søren
Journal of Catalysis, Vol. 345
DOI: 10.1016/j.jcat.2016.11.020

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

Perdew, John P.; Wang, Yue
Physical Review B, Vol. 45, Issue 23, p. 13244-13249
DOI: 10.1103/PhysRevB.45.13244

Atomically Dispersed Au–(OH) _x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction
journal, March 2013

Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria
Journal of the American Chemical Society, Vol. 135, Issue 10
DOI: 10.1021/ja312646d

Far-IR Spectra of Small Neutral Gold Clusters in the Gas Phase
journal, January 2014

Gruene, Philipp; Butschke, Burkhard; Lyon, Jonathan T.
Zeitschrift für Physikalische Chemie, Vol. 228, Issue 4-5
DOI: 10.1515/zpch-2014-0480

The critical role of water at the gold-titania interface in catalytic CO oxidation
journal, September 2014

Saavedra, J.; Doan, H. A.; Pursell, C. J.
Science, Vol. 345, Issue 6204
DOI: 10.1126/science.1256018

Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions
journal, July 2009

Yamamoto, Kimihisa; Imaoka, Takane; Chun, Wang-Jae
Nature Chemistry, Vol. 1, Issue 5
DOI: 10.1038/nchem.288

CO Oxidation on TiO ₂ (110) Supported Subnanometer Gold Clusters: Size and Shape Effects
journal, December 2013

Li, Lei; Gao, Yi; Li, Hui
Journal of the American Chemical Society, Vol. 135, Issue 51
DOI: 10.1021/ja410292s

Gas-phase epoxidation of propylene over small gold ensembles on TS-1
journal, September 2005

Taylor, B.; Lauterbach, J.; Delgass, W. N.
Applied Catalysis A: General, Vol. 291, Issue 1-2
DOI: 10.1016/j.apcata.2005.02.039

Hydrogen Production by Dehydrogenation of Formic Acid on Atomically Dispersed Gold on Ceria
journal, March 2013

Yi, Nan; Saltsburg, Howard; Flytzani-Stephanopoulos, Maria
ChemSusChem, Vol. 6, Issue 5
DOI: 10.1002/cssc.201200957

The structures of small gold cluster anions as determined by a combination of ion mobility measurements and density functional calculations
journal, October 2002

Furche, Filipp; Ahlrichs, Reinhart; Weis, Patrick
The Journal of Chemical Physics, Vol. 117, Issue 15
DOI: 10.1063/1.1507582

Odd-even staggering in simple models of metal clusters
journal, December 1994

Manninen, M.; Mansikka-aho, J.; Nishioka, H.
Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 31, Issue 4
DOI: 10.1007/BF01445004

CO Oxidation on Rutile-Supported Au Nanoparticles
journal, February 2005

Remediakis, Ioannis N.; Lopez, Nuria; Nørskov, Jens K.
Angewandte Chemie International Edition, Vol. 44, Issue 12
DOI: 10.1002/anie.200461699

Efficient Subnanometric Gold-Catalyzed Hydrogen Generation via Formic Acid Decomposition under Ambient Conditions
journal, May 2012

Bi, Qing-Yuan; Du, Xian-Long; Liu, Yong-Mei
Journal of the American Chemical Society, Vol. 134, Issue 21
DOI: 10.1021/ja301696e

Thiolate-Mediated Selectivity Control in Aerobic Alcohol Oxidation by Porous Carbon-Supported Au ₂₅ Clusters
journal, September 2014

Yoskamtorn, Tatchamapan; Yamazoe, Seiji; Takahata, Ryo
ACS Catalysis, Vol. 4, Issue 10
DOI: 10.1021/cs501010x

A DFT-Based Study of the Low-Energy Electronic Structures and Properties of Small Gold Clusters
journal, August 2005

Jain, Prashant K.
Structural Chemistry, Vol. 16, Issue 4
DOI: 10.1007/s11224-005-6350-8

Ultraviolet photoelectron spectra of coinage metal clusters
journal, February 1992

Taylor, K. J.; Pettiette‐Hall, C. L.; Cheshnovsky, O.
The Journal of Chemical Physics, Vol. 96, Issue 4
DOI: 10.1063/1.461927

CO oxidation mechanism on a MgO(1 0 0) supported Pt x Au 3−x clusters
journal, November 2015

Zhang, Wei; Cui, Rong; Wu, Hao
Applied Surface Science, Vol. 356
DOI: 10.1016/j.apsusc.2015.08.081

A Critical Size for Emergence of Nonbulk Electronic and Geometric Structures in Dodecanethiolate-Protected Au Clusters
journal, January 2015

Negishi, Yuichi; Nakazaki, Tafu; Malola, Sami
Journal of the American Chemical Society, Vol. 137, Issue 3
DOI: 10.1021/ja5109968

Trends in the Catalytic CO Oxidation Activity of Nanoparticles
journal, June 2008

Falsig, Hanne; Hvolbæk, Britt; Kristensen, Iben S.
Angewandte Chemie, Vol. 120, Issue 26
DOI: 10.1002/ange.200801479

Finding the Most Catalytically Active Platinum Clusters With Low Atomicity
journal, July 2015

Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae
Angewandte Chemie, Vol. 127, Issue 34
DOI: 10.1002/ange.201504473

Au20: A Tetrahedral Cluster.
journal, May 2003

Li, Jun; Li, Xi; Zhai, Hua-Jin
ChemInform, Vol. 34, Issue 20
DOI: 10.1002/chin.200320001

When Gold Is Not Noble: Catalysis by Nanoparticles
journal, August 2003

Haruta, Masatake
ChemInform, Vol. 34, Issue 32
DOI: 10.1002/chin.200332203

Some Recent Theoretical Advances in the Understanding of the Catalytic Activity of Au
journal, December 2005

Molina, L. M.; Hammer, B.
ChemInform, Vol. 36, Issue 49
DOI: 10.1002/chin.200549239

Heterogeneous Gold-Based Catalysis for Green Chemistry: Low-Temperature CO Oxidation and Propene Oxidation
journal, September 2007

Min, Byoung Koun; Friend, Cynthia M.
ChemInform, Vol. 38, Issue 37
DOI: 10.1002/chin.200737236

Amorphization-induced surface electronic states modulation of cobaltous oxide nanosheets for lithium-sulfur batteries
journal, May 2021

Li, Ruilong; Rao, Dewei; Zhou, Jianbin
Nature Communications, Vol. 12, Issue 1
DOI: 10.1038/s41467-021-23349-9

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021

Chen, Ruyi; Cui, Qirui; Liao, Liyang
Nature Communications, Vol. 12, Issue 1
DOI: 10.1038/s41467-021-23414-3

High-resolution X-ray luminescence extension imaging
journal, February 2021

Ou, Xiangyu; Qin, Xian; Huang, Bolong
Nature, Vol. 590, Issue 7846
DOI: 10.1038/s41586-021-03251-6

CO Oxidation on Rutile-Supported Au Nanoparticles
journal, February 2005

Remediakis, Ioannis N.; Lopez, Nuria; Nørskov, Jens K.
Angewandte Chemie, Vol. 117, Issue 12
DOI: 10.1002/ange.200461699

On the Electronic and Atomic Structures of Small AuN- (N = 4—14) Clusters: A Photoelectron Spectroscopy and Density-Functional Study.
journal, November 2003

Haekkinen, Hannu; Yoon, Bokwon; Landman, Uzi
ChemInform, Vol. 34, Issue 45
DOI: 10.1002/chin.200345006

Low Temperature Water Gas Shift over Gold Catalysts
journal, February 2003

Andreeva, Donka
ChemInform, Vol. 34, Issue 7
DOI: 10.1002/chin.200307193

Erratum: Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions
journal, September 2010

Yamamoto, Kimihisa; Imaoka, Takane; Chun, Wang-Jae
Nature Chemistry, Vol. 2, Issue 9
DOI: 10.1038/nchem.829

Similar Records in DOE PAGES and OSTI.GOV collections:

Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments

Journal Article Singh, Suyash ; Li, Sha ; Carrasquillo-Flores, Ronald ; ... - AIChE Journal

A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path,more »« less
https://doi.org/10.1002/aic.14401
Kinetic Isolation between Turnovers on Au ₁₈ Nanoclusters: Formic Acid Decomposition One Molecule at a Time

Journal Article Chen, Benjamin W. J. ; Stamatakis, Michail ; Mavrikakis, Manos - ACS Catalysis

Formic acid (HCOOH or FA) is a clean, safe, and renewable hydrogen storage material. Although Au catalysts decompose vapor-phase FA with high activity and selectivity toward hydrogen, the active site and reaction mechanism remain unclear. Here, we show that the subnanometric Au₁₈ cluster (0.8 nm in diameter) is likely the active species for FA decomposition. We performed coverage self-consistent, density functional theory-based kinetic Monte Carlo simulations of FA decomposition on gas-phase Au18 clusters, predicting 100% selectivity toward hydrogen and turnover frequencies close to experimentally determined values. The active site is made up of a triangular ensemble of three atoms eachmore »« less
Cited by 12
https://doi.org/10.1021/acscatal.9b02167

Full Text Available
On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

Journal Article Li, Sha ; Scaranto, Jessica ; Mavrikakis, Manos - Topics in Catalysis

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore »« less
Cited by 33
https://doi.org/10.1007/s11244-016-0672-1

Full Text Available
Boron Nitride-supported Sub-nanometer Pd ₆ Clusters for Formic Acid Decomposition: A DFT Study

Journal Article Schimmenti, Roberto ; Cortese, Remedios ; Duca, Dario ; ... - ChemCatChem

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd₆ clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO₂ and H₂. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate to monodentate HCOO conversion.more »« less
Cited by 22
https://doi.org/10.1002/cctc.201700248

Full Text Available
Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study

Journal Article Chen, Benjamin J. ; Bhandari, Saurabh ; Mavrikakis, Manos - ACS Catalysis

Hydrogen bonding interactions alter the nanoscale reaction mechanisms of many chemistries. Yet, it remains unclear how they affect heterogeneously catalyzed decomposition of formic acid (FA), a reaction of intense interest since FA is a promising hydrogen carrier. In this work, we elucidate how hydrogen bonding affects the reaction mechanisms for FA decomposition on Cu(111) by combining first-principles density functional theory calculations to calculate reaction energetics, Latin-hypercube sampling to elucidate stable high-coverage adsorbate configurations, and coverage self-consistent mean-field microkinetic models to predict reaction kinetics. We demonstrate that hydrogen-bonded complexes of FA with formate (bimolecular FA–HCOO complexes) can play a dominant rolemore »« less
https://doi.org/10.1021/acscatal.0c05695

Full Text Available

Similar Records

Title: On the nature of active sites for formic acid decomposition on gold catalysts

Abstract

Citation Formats

Production of CO-free H2 from formic acid. A comparative study of the catalytic behavior of Pt metals on a carbon support journal, April 2011

On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation journal, April 2004

Shells of electrons in metal doped simple metal clusters journal, June 2004

Structure determination of gold clusters by trapped ion electron diffraction: Au14−–Au19− journal, January 2009

Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H2 journal, July 2011

Al 12 X (X = Ni, Pd, Pt, Ti, and Zr) Clusters: Promising Low-Cost and High-Activity Catalysts for CO Oxidation journal, December 2013

Characterization of copper clusters through the use of density functional theory reactivity descriptors journal, August 2002

Catalysis by Gold Nanoparticles: Epoxidation of Propene journal, June 2004

Support effect for nanosized Au catalysts in hydrogen production from formic acid decomposition journal, January 2016

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Counting Au catalytic sites for the water–gas shift reaction journal, September 2012

Density-functional study of Au n ( n = 2 – 2 0 ) clusters: Lowest-energy structures and electronic properties journal, July 2002

On the Electronic and Atomic Structures of Small Au N - ( N = 4−14) Clusters: A Photoelectron Spectroscopy and Density-Functional Study journal, August 2003

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction journal, November 2013

Size-dependent catalytic activity of supported metal clusters journal, November 1994

Adsorption of O2 and oxidation of CO at Au nanoparticles supported by TiO2(110) journal, April 2004

Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase journal, August 2008

Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures journal, June 2009

Geometrical and Electronic Structures of Gold, Silver, and Gold−Silver Binary Clusters: Origins of Ductility of Gold and Gold−Silver Alloy Formation journal, August 2003

Gold—an introductory perspective journal, January 2008

Conversion of cellulose to hydrocarbon fuels by progressive removal of oxygen journal, October 2010

A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal, December 2000

Two-dimensional magic numbers in mass abundances of photofragmented bimetallic clusters journal, January 2003

Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition journal, March 2014

Hydrogen-Promoted Oxygen Activation by Free Gold Cluster Cations journal, July 2009

Theoretical advances of the structures and catalytic activities of small-sized gold nanoclusters journal, December 2013

Mechanistic Insight into the Styrene-Selective Oxidation on Subnanometer Gold Clusters (Au 16 –Au 20 , Au 27 , Au 28 , Au 30 , and Au 32 –Au 35 ): A Density Functional Theory Study journal, August 2014

Trends in the structure and bonding of noble metal clusters journal, October 2004

General properties of the electronic structure of alkali metal clusters and Ia-IIa mixed clusters journal, March 1989

Odd-even alternation of global hardnesses in the Nan (n=2-9) clusters journal, January 2000

Metallic Corner Atoms in Gold Clusters Supported on Rutile Are the Dominant Active Site during Water−Gas Shift Catalysis journal, October 2010

A DFT Study of the CO Oxidation Mechanism on AlnAu (n = 1–12) Clusters journal, January 2015

Au20: A Tetrahedral Cluster journal, February 2003

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid journal, April 2009

Atomically precise cluster catalysis towards quantum controlled catalysts journal, December 2014

Some recent theoretical advances in the understanding of the catalytic activity of Au journal, September 2005

CO oxidation on gold nanoparticles: Theoretical studies journal, September 2005

Reaction-Relevant Gold Structures in the Low Temperature Water-Gas Shift Reaction on Au-CeO 2 journal, August 2008

Probing the electronic properties and structural evolution of anionic gold clusters in the gas phase journal, January 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study journal, November 2014

When Gold Is Not Noble: Catalysis by Nanoparticles journal, April 2003

Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels journal, February 2010

Structural Transitions from Pyramidal to Fused Planar to Tubular to Core/Shell Compact in Gold Clusters: Au n - ( n = 21−25) journal, February 2007

The use of titania- and iron oxide-supported gold catalysts for the hydrogenation of propyne journal, September 2005

Structure and Surface Chemistry of Gold-Based Model Catalysts journal, April 2011

Precision Synthesis of Subnanoparticles Using Dendrimers as a Superatom Synthesizer journal, February 2014

Structural Evolution of Medium-Sized Gold Clusters Au n – ( n = 36, 37, 38): Appearance of Bulk-Like Face Centered Cubic Fragment journal, March 2014

Structural evolution of Au nanoclusters: From planar to cage to tubular motifs journal, October 2006

Finding the Most Catalytically Active Platinum Clusters With Low Atomicity journal, July 2015

First-principles study of intermediate size silver clusters: Shape evolution and its impact on cluster properties journal, October 2006

Improved tetrahedron method for Brillouin-zone integrations journal, June 1994

Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation journal, February 2011

Catalytic Activities of Subnanometer Gold Clusters (Au 16 –Au 18 , Au 20 , and Au 27 –Au 35 ) for CO Oxidation journal, September 2011

Toward an Atomic-Level Understanding of Size-Specific Properties of Protected and Stabilized Gold Clusters journal, February 2012

Size- and Structure-specificity in Catalysis by Gold Clusters journal, April 2014

Advances in the catalysis of Au nanoparticles journal, December 2001

Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces journal, November 2009

Cu4 Cluster Doped Monolayer MoS2 for CO Oxidation journal, June 2015

Determining the size-dependent structure of ligand-free gold-cluster ions journal, March 2010

Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide journal, February 1989

Low temperature water gas shift over gold catalysts journal, September 2002

Active gold species on cerium oxide nanoshapes for methanol steam reforming and the water gas shift reactions journal, January 2010

Production of liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic acid journal, January 2011

Heterogeneous Gold-Based Catalysis for Green Chemistry: Low-Temperature CO Oxidation and Propene Oxidation journal, June 2007

Atomic Resolution Observation of a Size-Dependent Change in the Ripening Modes of Mass-Selected Au Nanoclusters Involved in CO Oxidation journal, November 2015

A golden age of catalysis: A perspective journal, September 2005

Kinetic Control and Thermodynamic Selection in the Synthesis of Atomically Precise Gold Nanoclusters journal, June 2011

Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments journal, February 2014

DFT and In Situ EXAFS Investigation of Gold/Ceria−Zirconia Low-Temperature Water Gas Shift Catalysts: Identification of the Nature of the Active Form of Gold journal, December 2005

2D-3D transition of gold cluster anions resolved journal, May 2008

A unified formulation of the constant temperature molecular dynamics methods journal, July 1984

Size-dependent catalytic activity and geometries of size-selected Pt clusters on TiO2(110) surfaces journal, January 2011

Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts journal, December 2013

Magic Number Pt 13 and Misshapen Pt 12 Clusters: Which One is the Better Catalyst? journal, August 2013

Size and Support Effects for the Water–Gas Shift Catalysis over Gold Nanoparticles Supported on Model Al 2 O 3 and TiO 2 journal, February 2012

Production of CO-free H2 from formic acid. A comparative study of the catalytic behavior of Pt metals on a carbon support
journal, April 2011

On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation
journal, April 2004

Shells of electrons in metal doped simple metal clusters
journal, June 2004

Structure determination of gold clusters by trapped ion electron diffraction: Au14−–Au19−
journal, January 2009

Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H₂
journal, July 2011

Al ₁₂ X (X = Ni, Pd, Pt, Ti, and Zr) Clusters: Promising Low-Cost and High-Activity Catalysts for CO Oxidation
journal, December 2013

Characterization of copper clusters through the use of density functional theory reactivity descriptors
journal, August 2002

Catalysis by Gold Nanoparticles: Epoxidation of Propene
journal, June 2004

Support effect for nanosized Au catalysts in hydrogen production from formic acid decomposition
journal, January 2016

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Counting Au catalytic sites for the water–gas shift reaction
journal, September 2012

Density-functional study of ${Au}_{n} (n = 2 - 20)$ clusters: Lowest-energy structures and electronic properties
journal, July 2002

On the Electronic and Atomic Structures of Small Au _N ^- ( N = 4−14) Clusters: A Photoelectron Spectroscopy and Density-Functional Study
journal, August 2003

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013

Size-dependent catalytic activity of supported metal clusters
journal, November 1994

Adsorption of O2 and oxidation of CO at Au nanoparticles supported by TiO2(110)
journal, April 2004

Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase
journal, August 2008

Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures
journal, June 2009

Geometrical and Electronic Structures of Gold, Silver, and Gold−Silver Binary Clusters: Origins of Ductility of Gold and Gold−Silver Alloy Formation
journal, August 2003

Gold—an introductory perspective
journal, January 2008

Conversion of cellulose to hydrocarbon fuels by progressive removal of oxygen
journal, October 2010

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Two-dimensional magic numbers in mass abundances of photofragmented bimetallic clusters
journal, January 2003

Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition
journal, March 2014

Hydrogen-Promoted Oxygen Activation by Free Gold Cluster Cations
journal, July 2009

Theoretical advances of the structures and catalytic activities of small-sized gold nanoclusters
journal, December 2013

Mechanistic Insight into the Styrene-Selective Oxidation on Subnanometer Gold Clusters (Au ₁₆ –Au ₂₀ , Au ₂₇ , Au ₂₈ , Au ₃₀ , and Au ₃₂ –Au ₃₅ ): A Density Functional Theory Study
journal, August 2014

Trends in the structure and bonding of noble metal clusters
journal, October 2004

General properties of the electronic structure of alkali metal clusters and Ia-IIa mixed clusters
journal, March 1989

Odd-even alternation of global hardnesses in the Nan (n=2-9) clusters
journal, January 2000

Metallic Corner Atoms in Gold Clusters Supported on Rutile Are the Dominant Active Site during Water−Gas Shift Catalysis
journal, October 2010

A DFT Study of the CO Oxidation Mechanism on AlnAu (n = 1–12) Clusters
journal, January 2015

Au20: A Tetrahedral Cluster
journal, February 2003

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid
journal, April 2009

Atomically precise cluster catalysis towards quantum controlled catalysts
journal, December 2014

Some recent theoretical advances in the understanding of the catalytic activity of Au
journal, September 2005

CO oxidation on gold nanoparticles: Theoretical studies
journal, September 2005

Reaction-Relevant Gold Structures in the Low Temperature Water-Gas Shift Reaction on Au-CeO ₂
journal, August 2008

Probing the electronic properties and structural evolution of anionic gold clusters in the gas phase
journal, January 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

When Gold Is Not Noble: Catalysis by Nanoparticles
journal, April 2003

Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels
journal, February 2010

Structural Transitions from Pyramidal to Fused Planar to Tubular to Core/Shell Compact in Gold Clusters: Au _n ^- ( n = 21−25)
journal, February 2007

The use of titania- and iron oxide-supported gold catalysts for the hydrogenation of propyne
journal, September 2005

Structure and Surface Chemistry of Gold-Based Model Catalysts
journal, April 2011

Precision Synthesis of Subnanoparticles Using Dendrimers as a Superatom Synthesizer
journal, February 2014

Structural Evolution of Medium-Sized Gold Clusters Au _n ^– ( n = 36, 37, 38): Appearance of Bulk-Like Face Centered Cubic Fragment
journal, March 2014

Structural evolution of Au nanoclusters: From planar to cage to tubular motifs
journal, October 2006

Finding the Most Catalytically Active Platinum Clusters With Low Atomicity
journal, July 2015

First-principles study of intermediate size silver clusters: Shape evolution and its impact on cluster properties
journal, October 2006

Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994

Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation
journal, February 2011

Catalytic Activities of Subnanometer Gold Clusters (Au ₁₆ –Au ₁₈ , Au ₂₀ , and Au ₂₇ –Au ₃₅ ) for CO Oxidation
journal, September 2011

Toward an Atomic-Level Understanding of Size-Specific Properties of Protected and Stabilized Gold Clusters
journal, February 2012

Size- and Structure-specificity in Catalysis by Gold Clusters
journal, April 2014

Advances in the catalysis of Au nanoparticles
journal, December 2001

Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009

Cu4 Cluster Doped Monolayer MoS2 for CO Oxidation
journal, June 2015

Determining the size-dependent structure of ligand-free gold-cluster ions
journal, March 2010

Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide
journal, February 1989

Low temperature water gas shift over gold catalysts
journal, September 2002

Active gold species on cerium oxide nanoshapes for methanol steam reforming and the water gas shift reactions
journal, January 2010

Production of liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic acid
journal, January 2011

Heterogeneous Gold-Based Catalysis for Green Chemistry: Low-Temperature CO Oxidation and Propene Oxidation
journal, June 2007

Atomic Resolution Observation of a Size-Dependent Change in the Ripening Modes of Mass-Selected Au Nanoclusters Involved in CO Oxidation
journal, November 2015

A golden age of catalysis: A perspective
journal, September 2005

Kinetic Control and Thermodynamic Selection in the Synthesis of Atomically Precise Gold Nanoclusters
journal, June 2011

Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments
journal, February 2014

DFT and In Situ EXAFS Investigation of Gold/Ceria−Zirconia Low-Temperature Water Gas Shift Catalysts: Identification of the Nature of the Active Form of Gold
journal, December 2005

2D-3D transition of gold cluster anions resolved
journal, May 2008

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

Size-dependent catalytic activity and geometries of size-selected Pt clusters on TiO₂(110) surfaces
journal, January 2011

Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts
journal, December 2013

Magic Number Pt ₁₃ and Misshapen Pt ₁₂ Clusters: Which One is the Better Catalyst?
journal, August 2013

Size and Support Effects for the Water–Gas Shift Catalysis over Gold Nanoparticles Supported on Model Al ₂ O ₃ and TiO ₂
journal, February 2012

Relationship between Ionization Potential, Polarizability, and Softness: A Case Study of Lithium and Sodium Metal Clusters
journal, August 2004

Analysis of the odd-even alternation in simple metal clusters
journal, June 1996

CO Oxidation on Au _n /TiO ₂ Catalysts Produced by Size-Selected Cluster Deposition
journal, May 2004