Molecular catalysis science: Perspective on unifying the fields of catalysis
Abstract
Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sumfrequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and h eterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Finally, unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1249733
- Alternate Identifier(s):
- OSTI ID: 1379334
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 19; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences, Washington, DC (United States)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; surface chemistry; nanocatalyst synthesis; in situ characterization; real-time dynamics
Citation Formats
Ye, Rong, Hurlburt, Tyler J., Sabyrov, Kairat, Alayoglu, Selim, and Somorjai, Gabor A. Molecular catalysis science: Perspective on unifying the fields of catalysis. United States: N. p., 2016.
Web. doi:10.1073/pnas.1601766113.
Ye, Rong, Hurlburt, Tyler J., Sabyrov, Kairat, Alayoglu, Selim, & Somorjai, Gabor A. Molecular catalysis science: Perspective on unifying the fields of catalysis. United States. https://doi.org/10.1073/pnas.1601766113
Ye, Rong, Hurlburt, Tyler J., Sabyrov, Kairat, Alayoglu, Selim, and Somorjai, Gabor A. Mon .
"Molecular catalysis science: Perspective on unifying the fields of catalysis". United States. https://doi.org/10.1073/pnas.1601766113.
@article{osti_1249733,
title = {Molecular catalysis science: Perspective on unifying the fields of catalysis},
author = {Ye, Rong and Hurlburt, Tyler J. and Sabyrov, Kairat and Alayoglu, Selim and Somorjai, Gabor A.},
abstractNote = {Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sumfrequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and h eterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Finally, unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.},
doi = {10.1073/pnas.1601766113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 19,
volume = 113,
place = {United States},
year = {Mon Apr 25 00:00:00 EDT 2016},
month = {Mon Apr 25 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1601766113
https://doi.org/10.1073/pnas.1601766113
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 76 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Advancing the Frontiers in Nanocatalysis, Biointerfaces, and Renewable Energy Conversion by Innovations of Surface Techniques
journal, November 2009
- Somorjai, Gabor A.; Frei, Heinz; Park, Jeong Y.
- Journal of the American Chemical Society, Vol. 131, Issue 46, p. 16589-16605
Synthesis of heterogeneous catalysts with well shaped platinum particles to control reaction selectivity
journal, October 2008
- Lee, Ilkeun; Morales, Ricardo; Albiter, Manuel A.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 40
Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts
journal, February 2009
- Jiao, Feng; Frei, Heinz
- Angewandte Chemie International Edition, Vol. 48, Issue 10
Fundamentals and applications of immobilized microfluidic enzymatic reactors
journal, January 2011
- Matosevic, Sandro; Szita, Nicolas; Baganz, Frank
- Journal of Chemical Technology & Biotechnology, Vol. 86, Issue 3
Single Nanocrystals of Platinum Prepared by Partial Dissolution of Au-Pt Nanoalloys
journal, January 2009
- Schrinner, M.; Ballauff, M.; Talmon, Y.
- Science, Vol. 323, Issue 5914
Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012
- Buurmans, Inge L. C.; Weckhuysen, Bert M.
- Nature Chemistry, Vol. 4, Issue 11
Enhanced CO Oxidation Rates at the Interface of Mesoporous Oxides and Pt Nanoparticles
journal, October 2013
- An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
- Journal of the American Chemical Society, Vol. 135, Issue 44
Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation
journal, July 2008
- Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang
- Nano Letters, Vol. 8, Issue 7
Tuning selectivity in catalysis by controlling particle shape
journal, January 2009
- Lee, Ilkeun; Delbecq, Françoise; Morales, Ricardo
- Nature Materials, Vol. 8, Issue 2
Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy
journal, August 2012
- van Schrojenstein Lantman, Evelien M.; Deckert-Gaudig, Tanja; Mank, Arjan J. G.
- Nature Nanotechnology, Vol. 7, Issue 9
Size and Shape Dependence on Pt Nanoparticles for the Methylcyclopentane/Hydrogen Ring Opening/Ring Enlargement Reaction
journal, June 2011
- Alayoglu, S.; Aliaga, C.; Sprung, C.
- Catalysis Letters, Vol. 141, Issue 7
Dendrimer-Encapsulated Pt Nanoparticles: Synthesis, Characterization, and Applications to Catalysis
journal, March 1999
- Crooks, R. M.; Zhao, M.
- Advanced Materials, Vol. 11, Issue 3
Enzyme Structure with Two Catalytic Sites for Double-Sieve Selection of Substrate
journal, April 1998
- Nureki, O.
- Science, Vol. 280, Issue 5363
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles
journal, November 2008
- Tao, F.; Grass, M. E.; Zhang, Y.
- Science, Vol. 322, Issue 5903
An SFG Study of Interfacial Amino Acids at the Hydrophilic SiO 2 and Hydrophobic Deuterated Polystyrene Surfaces
journal, April 2011
- Holinga, George J.; York, Roger L.; Onorato, Robert M.
- Journal of the American Chemical Society, Vol. 133, Issue 16
Small Gold Clusters Formed in Solution Give Reaction Turnover Numbers of 107 at Room Temperature
journal, December 2012
- Oliver-Meseguer, J.; Cabrero-Antonino, J. R.; Dominguez, I.
- Science, Vol. 338, Issue 6113
Dendrimer-Encapsulated Metal Nanoparticles: Synthesis, Characterization, and Applications to Catalysis
journal, March 2001
- Crooks, Richard M.; Zhao, Mingqi; Sun, Li
- Accounts of Chemical Research, Vol. 34, Issue 3
Mapping Local Charge Recombination Heterogeneity by Multidimensional Nanospectroscopic Imaging
journal, December 2012
- Bao, W.; Melli, M.; Caselli, N.
- Science, Vol. 338, Issue 6112
Break-Up of Stepped Platinum Catalyst Surfaces by High CO Coverage
journal, February 2010
- Tao, F.; Dag, S.; Wang, L. -W.
- Science, Vol. 327, Issue 5967
Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology
journal, April 2008
- Salmeron, M.; Schlogl, R.
- Surface Science Reports, Vol. 63, Issue 4
Energy conversion from catalytic reaction to hot electron current with metal-semiconductor Schottky nanodiodes
journal, January 2006
- Park, Jeong Young; Somorjai, Gabor A.
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 24, Issue 4
A Dynamic Knockout Reveals That Conformational Fluctuations Influence the Chemical Step of Enzyme Catalysis
journal, April 2011
- Bhabha, G.; Lee, J.; Ekiert, D. C.
- Science, Vol. 332, Issue 6026
Taking Ockham's razor to enzyme dynamics and catalysis
journal, January 2012
- Glowacki, David R.; Harvey, Jeremy N.; Mulholland, Adrian J.
- Nature Chemistry, Vol. 4, Issue 3
Friction Anisotropy-Driven Domain Imaging on Exfoliated Monolayer Graphene
journal, June 2011
- Choi, J. S.; Kim, J. -S.; Byun, I. -S.
- Science, Vol. 333, Issue 6042
Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles
journal, November 2009
- Witham, Cole A.; Huang, Wenyu; Tsung, Chia-Kuang
- Nature Chemistry, Vol. 2, Issue 1
Asymmetric Catalysis at the Mesoscale: Gold Nanoclusters Embedded in Chiral Self-Assembled Monolayer as Heterogeneous Catalyst for Asymmetric Reactions
journal, March 2013
- Gross, Elad; Liu, Jack H.; Alayoglu, Selim
- Journal of the American Chemical Society, Vol. 135, Issue 10
The Dynamic Energy Landscape of Dihydrofolate Reductase Catalysis
journal, September 2006
- Boehr, D. D.; McElheny, D.; Dyson, H. J.
- Science, Vol. 313, Issue 5793, p. 1638-1642
Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability
journal, January 2007
- Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
- Science, Vol. 315, Issue 5811, p. 493-497
Cobalt Particle Size Effects in the Fischer–Tropsch Synthesis and in the Hydrogenation of CO2 Studied with Nanoparticle Model Catalysts on Silica
journal, December 2013
- Melaet, Gérôme; Lindeman, Avery E.; Somorjai, Gabor A.
- Topics in Catalysis, Vol. 57, Issue 6-9
Hydrogen Oxidation-Driven Hot Electron Flow Detected by Catalytic Nanodiodes
journal, November 2009
- Hervier, Antoine; Renzas, J. Russell; Park, Jeong Y.
- Nano Letters, Vol. 9, Issue 11
Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation
journal, April 2009
- Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu
- Journal of the American Chemical Society, Vol. 131, Issue 16
Highly Active Heterogeneous Palladium Nanoparticle Catalysts for Homogeneous Electrophilic Reactions in Solution and the Utilization of a Continuous Flow Reactor
journal, December 2010
- Huang, Wenyu; Liu, Jack Hung-Chang; Alayoglu, Pinar
- Journal of the American Chemical Society, Vol. 132, Issue 47
Direct Imaging of Covalent Bond Structure in Single-Molecule Chemical Reactions
journal, May 2013
- de Oteyza, D. G.; Gorman, P.; Chen, Y. -C.
- Science, Vol. 340, Issue 6139
Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks
journal, November 1998
- Yang, Peidong; Zhao, Dongyuan; Margolese, David I.
- Nature, Vol. 396, Issue 6707
Nanomaterials in transistors: From high-performance to thin-film applications
journal, August 2015
- Franklin, A. D.
- Science, Vol. 349, Issue 6249
A Reactive Oxide Overlayer on Rhodium Nanoparticles during CO Oxidation and Its Size Dependence Studied by In Situ Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, November 2008
- Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.
- Angewandte Chemie International Edition, Vol. 47, Issue 46
SFG-surface vibrational spectroscopy studies of structure sensitivity and insensitivity in catalytic reactions: cyclohexene dehydrogenation and ethylene hydrogenation on Pt (1 1 1) and Pt (1 0 0) crystal surfaces
journal, December 2000
- McCrea, Keith R.; Somorjai, Gabor A.
- Journal of Molecular Catalysis A: Chemical, Vol. 163, Issue 1-2
In Situ X-Ray Photoelectron Spectroscopy Studies of Gas-Solid Interfaces at Near-Ambient Conditions
journal, December 2007
- Bluhm, Hendrik; Hävecker, Michael; Knop-Gericke, Axel
- MRS Bulletin, Vol. 32, Issue 12
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014
- Velasco-Velez, J. -J.; Wu, C. H.; Pascal, T. A.
- Science, Vol. 346, Issue 6211
Structure and Chemical State of the Pt(557) Surface during Hydrogen Oxidation Reaction Studied by in Situ Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy
journal, August 2013
- Zhu, Zhongwei; Melaet, Gérôme; Axnanda, Stephanus
- Journal of the American Chemical Society, Vol. 135, Issue 34
Nonlinear Optics in Relativistic Plasmas and Laser Wake Field Acceleration of Electrons
journal, July 1996
- Umstadter, D.; Chen, S. -Y.; Maksimchuk, A.
- Science, Vol. 273, Issue 5274
Nonadditivity of nanoparticle interactions
journal, October 2015
- Silvera Batista, C. A.; Larson, R. G.; Kotov, N. A.
- Science, Vol. 350, Issue 6257
Colloidal nanocrystal synthesis and the organic–inorganic interface
journal, September 2005
- Yin, Yadong; Alivisatos, A. Paul
- Nature, Vol. 437, Issue 7059, p. 664-670
In Situ Surface and Reaction Probe Studies with Model Nanoparticle Catalysts
journal, September 2012
- Alayoglu, Selim; Krier, James M.; Michalak, William D.
- ACS Catalysis, Vol. 2, Issue 11
Nanoscale chemical imaging of a working catalyst by scanning transmission X-ray microscopy
journal, November 2008
- de Smit, Emiel; Swart, Ingmar; Creemer, J. Fredrik
- Nature, Vol. 456, Issue 7219
Finite Size Effects in Chemical Bonding: From Small Clusters to Solids
journal, June 2011
- Kleis, J.; Greeley, J.; Romero, N. A.
- Catalysis Letters, Vol. 141, Issue 8
Shape-Controlled Synthesis of Gold and Silver Nanoparticles
journal, December 2002
- Sun, Yugang; Xia, Younan
- Science, Vol. 298, Issue 5601, p. 2176-2179
Vibrational Promotion of Electron Transfer
journal, October 2000
- Huang, Y.
- Science, Vol. 290, Issue 5489
A Pt-Cluster-Based Heterogeneous Catalyst for Homogeneous Catalytic Reactions: X-ray Absorption Spectroscopy and Reaction Kinetic Studies of Their Activity and Stability against Leaching
journal, August 2011
- Li, Yimin; Liu, Jack Hung-Chang; Witham, Cole A.
- Journal of the American Chemical Society, Vol. 133, Issue 34
Designed Catalysts from Pt Nanoparticles Supported on Macroporous Oxides for Selective Isomerization of n -Hexane
journal, May 2014
- An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
- Journal of the American Chemical Society, Vol. 136, Issue 19
In Situ IR and X-ray High Spatial-Resolution Microspectroscopy Measurements of Multistep Organic Transformation in Flow Microreactor Catalyzed by Au Nanoclusters
journal, February 2014
- Gross, Elad; Shu, Xing-Zhong; Alayoglu, Selim
- Journal of the American Chemical Society, Vol. 136, Issue 9
Hydrogenation of benzene and toluene over size controlled Pt/SBA-15 catalysts: Elucidation of the Pt particle size effect on reaction kinetics
journal, August 2012
- Pushkarev, Vladimir V.; An, Kwangjin; Alayoglu, Selim
- Journal of Catalysis, Vol. 292
Facet development during platinum nanocube growth
journal, August 2014
- Liao, H. -G.; Zherebetskyy, D.; Xin, H.
- Science, Vol. 345, Issue 6199
Carrier-free immobilized enzymes for biocatalysis
journal, November 2009
- Roessl, Ulrich; Nahálka, Jozef; Nidetzky, Bernd
- Biotechnology Letters, Vol. 32, Issue 3
Pt Nanocrystals: Shape Control and Langmuir−Blodgett Monolayer Formation
journal, January 2005
- Song, Hyunjoon; Kim, Franklin; Connor, Stephen
- The Journal of Physical Chemistry B, Vol. 109, Issue 1
Good vibrations in enzyme-catalysed reactions
journal, January 2012
- Hay, Sam; Scrutton, Nigel S.
- Nature Chemistry, Vol. 4, Issue 3
Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time
journal, September 2012
- Gross, Elad; Liu, Jack Hung-Chang; Toste, F. Dean
- Nature Chemistry, Vol. 4, Issue 11
Strong Interactions in Supported-Metal Catalysts
journal, March 1981
- Tauster, S. J.; Fung, S. C.; Baker, R. T. K.
- Science, Vol. 211, Issue 4487, p. 1121-1125
Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999
- Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
- Nature, Vol. 402, Issue 6759, p. 276-279
Surface properties probed by second-harmonic and sum-frequency generation
journal, February 1989
- Shen, Y. R.
- Nature, Vol. 337, Issue 6207
Immobilized Biocatalysts: Novel Approaches and Tools for Binding Enzymes to Supports
journal, August 2011
- Torres-Salas, Pamela; del Monte-Martinez, Alberto; Cutiño-Avila, Bessy
- Advanced Materials, Vol. 23, Issue 44
Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998
- Zhao, Dongyuan; Feng, Jianglin; Huo, Qisheng
- Science, Vol. 279, Issue 5350, p. 548-552