Surface-supported cluster catalysis: Ensembles of metastable states run the show

Zandkarimi, Borna; Alexandrova, Anastassia N.

doi:10.1002/wcms.1420

Title: Surface-supported cluster catalysis: Ensembles of metastable states run the show

Journal Article · 28 May 2019 · Wiley Interdisciplinary Reviews: Computational Molecular Science

DOI: https://doi.org/10.1002/wcms.1420 · OSTI ID:1594588

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Univ. of California, Los Angeles, CA (United States); University of California, Los Angeles
Univ. of California, Los Angeles, CA (United States)

It has recently been demonstrated that the dynamic behaviour of surface-supported nanocluster catalysts in realistic reaction conditions defies conventional models used in catalysis. This opens new doors in catalysis by giving more leverage in catalyst design, but also requires a major revision of the understanding of how dynamic heterogeneous catalytic interfaces operate, as well as of the computational approaches of catalyst modelling, and experimental methods of catalyst characterization. Key aspects of the new paradigm include the collective action of many catalyst states that form a statistical ensemble in reacting conditions, the catalytic activity and selectivity being driven by rare and metastable catalyst states, reaction thermodynamics and kinetics being controlled by different states of the catalyst, broken scaling relationships, non-Arrhenius behaviours, and catalyst dynamic restructuring being an essential part of the reaction mechanism. For computation, this complexity means the departure from the standard DFT calculations of reaction mechanisms on a single catalyst structure. For experiment, it calls for the development of operando characterization tools with the per-site resolution and the ability to find the minority sites that govern the catalytic activity. For catalyst design, the goal becomes the creation of the catalyst state (geometric and electronic) that might not be present in the as-prepared catalyst, but would develop in the reaction conditions and would have the desired activity then. While cluster catalysts are the most dramatic in their dynamic fluxionality, other amorphous interfaces also exhibit some of it, and thus are also subject to similar paradigm revision.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: SC0019152

OSTI ID:: 1594588

Journal Information:: Wiley Interdisciplinary Reviews: Computational Molecular Science, Journal Name: Wiley Interdisciplinary Reviews: Computational Molecular Science Journal Issue: 6 Vol. 9; ISSN 1759-0876

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (139)

Modern Methods of Crystal Structure Prediction Oganov, Artem R. Wiley‐VCH Verlag GmbH & Co https://doi.org/10.1002/9783527632831	book	November 2010
Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces Fernández, Eva M.; Moses, Poul G.; Toftelund, Anja Angewandte Chemie, Vol. 120, Issue 25 https://doi.org/10.1002/ange.200705739	journal	June 2008
Selective Propene Epoxidation on Immobilized Au _6–10 Clusters: The Effect of Hydrogen and Water on Activity and Selectivity Lee, Sungsik; Molina, Luis M.; López, María J. Angewandte Chemie, Vol. 121, Issue 8 https://doi.org/10.1002/ange.200804154	journal	January 2009
Structural, Electronic, and Impurity-Doping Effects in Nanoscale Chemistry: Supported Gold Nanoclusters Häkkinen, Hannu; Abbet, Stéphane; Sanchez, Antonio Angewandte Chemie International Edition, Vol. 42, Issue 11 https://doi.org/10.1002/anie.200390334	journal	March 2003
Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces Fernández, Eva M.; Moses, Poul G.; Toftelund, Anja Angewandte Chemie International Edition, Vol. 47, Issue 25 https://doi.org/10.1002/anie.200705739	journal	June 2008
Selective Propene Epoxidation on Immobilized Au _6-10 Clusters: The Effect of Hydrogen and Water on Activity and Selectivity Lee, Sungsik; Molina, Luis M.; López, María J. Angewandte Chemie International Edition, Vol. 48, Issue 8 https://doi.org/10.1002/anie.200804154	journal	February 2009
Structural, Electronic, and Impurity-Doping Effects in Nanoscale Chemistry: Supported Gold Nanoclusters. Haekkinen, Hannu; Abbet, Stephane; Sanchez, Antonio ChemInform, Vol. 34, Issue 21 https://doi.org/10.1002/chin.200321014	journal	May 2003
Global minimum structure searches via particle swarm optimization Call, Seth T.; Zubarev, Dmitry Yu.; Boldyrev, Alexander I. Journal of Computational Chemistry, Vol. 28, Issue 7 https://doi.org/10.1002/jcc.20621	journal	January 2007
Structures at high pressure from random searching Pickard, C. J.; Needs, R. J. physica status solidi (b), Vol. 246, Issue 3 https://doi.org/10.1002/pssb.200880546	journal	March 2009
Global optimization of clusters using electronic structure methods Heiles, Sven; Johnston, Roy L. International Journal of Quantum Chemistry, Vol. 113, Issue 18 https://doi.org/10.1002/qua.24462	journal	May 2013
Challenges in the use of density functional theory to examine catalysis by M-doped ceria surfaces Krcha, Matthew D.; Janik, Michael J. International Journal of Quantum Chemistry, Vol. 114, Issue 1 https://doi.org/10.1002/qua.24548	journal	October 2013
Electronic factors determining the reactivity of metal surfaces Hammer, B.; Nørskov, J. K. Surface Science, Vol. 343, Issue 3 https://doi.org/10.1016/0039-6028(96)80007-0	journal	December 1995
Thermal decomposition and reformation of PdO catalysts; support effects Farrauto, Robert J.; Lampert, Jordan K.; Hobson, Melvin C. Applied Catalysis B: Environmental, Vol. 6, Issue 3 https://doi.org/10.1016/0926-3373(95)00015-1	journal	August 1995
Strong Metal-Support Interactions Badyal, J. P. S. The Chemical Physics of Solid Surfaces, Vol. 6, p. 311-340 https://doi.org/10.1016/b978-0-444-81468-5.50015-7	book	January 1993
Morphological effects of Au 13 clusters on the adsorption of CO 2 over anatase TiO 2 (101) Liu, Li; Liu, Zhongbo; Sun, Honggang Applied Surface Science, Vol. 399 https://doi.org/10.1016/j.apsusc.2016.12.089	journal	March 2017
Enzyme Millisecond Conformational Dynamics Do Not Catalyze the Chemical Step Pisliakov, Andrei V.; Cao, Jie; Kamerlin, Shina C. L. Biophysical Journal, Vol. 98, Issue 3 https://doi.org/10.1016/j.bpj.2009.12.1284	journal	January 2010
From conventional in situ to operando studies in Raman spectroscopy Guerrero-Pérez, M. Olga; Bañares, Miguel A. Catalysis Today, Vol. 113, Issue 1-2 https://doi.org/10.1016/j.cattod.2005.11.009	journal	March 2006
A decade+ of operando spectroscopy studies Chakrabarti, Anisha; Ford, Michael E.; Gregory, Daniel Catalysis Today, Vol. 283 https://doi.org/10.1016/j.cattod.2016.12.012	journal	April 2017
Reaction channels for the catalytic oxidation of CO on Pt(111) Eichler, A.; Hafner, J. Surface Science, Vol. 433-435 https://doi.org/10.1016/s0039-6028(99)00061-8	journal	August 1999
Theoretical Study of Ripening Mechanisms of Pd Clusters on Ceria Su, Ya-Qiong; Liu, Jin-Xun; Filot, Ivo A. W. Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b03555	journal	October 2017
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles Liu, Lichen; Corma, Avelino Chemical Reviews, Vol. 118, Issue 10 https://doi.org/10.1021/acs.chemrev.7b00776	journal	April 2018
AFFCK: Adaptive Force-Field-Assisted ab Initio Coalescence Kick Method for Global Minimum Search Zhai, Huanchen; Ha, Mai-Anh; Alexandrova, Anastassia N. Journal of Chemical Theory and Computation, Vol. 11, Issue 5 https://doi.org/10.1021/acs.jctc.5b00065	journal	April 2015
Firefly Algorithm for Structural Search Avendaño-Franco, Guillermo; Romero, Aldo H. Journal of Chemical Theory and Computation, Vol. 12, Issue 7 https://doi.org/10.1021/acs.jctc.5b01157	journal	June 2016
Ensemble-Average Representation of Pt Clusters in Conditions of Catalysis Accessed through GPU Accelerated Deep Neural Network Fitting Global Optimization Zhai, Huanchen; Alexandrova, Anastassia N. Journal of Chemical Theory and Computation, Vol. 12, Issue 12 https://doi.org/10.1021/acs.jctc.6b00994	journal	November 2016
Gaussian-Based Coupled-Cluster Theory for the Ground-State and Band Structure of Solids McClain, James; Sun, Qiming; Chan, Garnet Kin-Lic Journal of Chemical Theory and Computation, Vol. 13, Issue 3 https://doi.org/10.1021/acs.jctc.7b00049	journal	February 2017
Stochastic Self-Consistent Second-Order Green’s Function Method for Correlation Energies of Large Electronic Systems Neuhauser, Daniel; Baer, Roi; Zgid, Dominika Journal of Chemical Theory and Computation, Vol. 13, Issue 11 https://doi.org/10.1021/acs.jctc.7b00792	journal	October 2017
Projection-Based Correlated Wave Function in Density Functional Theory Embedding for Periodic Systems Chulhai, Dhabih V.; Goodpaster, Jason D. Journal of Chemical Theory and Computation, Vol. 14, Issue 4 https://doi.org/10.1021/acs.jctc.7b01154	journal	March 2018
Stochastic Optimally Tuned Range-Separated Hybrid Density Functional Theory Neuhauser, Daniel; Rabani, Eran; Cytter, Yael The Journal of Physical Chemistry A, Vol. 120, Issue 19 https://doi.org/10.1021/acs.jpca.5b10573	journal	December 2015
Effect of Tin Coverage on Selectivity for Ethane Dehydrogenation over Platinum–Tin Alloys Hook, Alec; Massa, Jacob D.; Celik, Fuat E. The Journal of Physical Chemistry C, Vol. 120, Issue 48 https://doi.org/10.1021/acs.jpcc.6b08407	journal	November 2016
Predicting Selectivity for Ethane Dehydrogenation and Coke Formation Pathways over Model Pt–M Surface Alloys with ab Initio and Scaling Methods Hook, Alec; Celik, Fuat E. The Journal of Physical Chemistry C, Vol. 121, Issue 33 https://doi.org/10.1021/acs.jpcc.7b03789	journal	August 2017
Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases Ren, Zhibo; Liu, Ning; Chen, Biaohua The Journal of Physical Chemistry C, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpcc.7b10208	journal	January 2018
Reactivity of CO on Sulfur-Passivated Graphene-Supported Platinum Nanocluster Arrays Düll, Fabian; Späth, Florian; Bauer, Udo The Journal of Physical Chemistry C, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcc.8b01589	journal	May 2018
Subnanometer Substructures in Nanoassemblies Formed from Clusters under a Reactive Atmosphere Revealed Using Machine Learning Timoshenko, Janis; Halder, Avik; Yang, Bing The Journal of Physical Chemistry C, Vol. 122, Issue 37 https://doi.org/10.1021/acs.jpcc.8b07952	journal	August 2018
Local Fluxionality of Surface-Deposited Cluster Catalysts: The Case of Pt ₇ on Al ₂ O ₃ Zhai, Huanchen; Alexandrova, Anastassia N. The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00379	journal	March 2018
Dynamic Phase Diagram of Catalytic Surface of Hexagonal Boron Nitride under Conditions of Oxidative Dehydrogenation of Propane Zhang, Zisheng; Jimenez-Izal, Elisa; Hermans, Ive The Journal of Physical Chemistry Letters, Vol. 10, Issue 1 https://doi.org/10.1021/acs.jpclett.8b03373	journal	December 2018
Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis Zandkarimi, Borna; Alexandrova, Anastassia N. The Journal of Physical Chemistry Letters, Vol. 10, Issue 3 https://doi.org/10.1021/acs.jpclett.8b03680	journal	January 2019
Alloying Pt Sub-nano-clusters with Boron: Sintering Preventative and Coke Antagonist? Dadras, Jonny; Jimenez-Izal, Elisa; Alexandrova, Anastassia N. ACS Catalysis, Vol. 5, Issue 10 https://doi.org/10.1021/acscatal.5b01513	journal	August 2015
Toward Benchmarking in Catalysis Science: Best Practices, Challenges, and Opportunities Bligaard, Thomas; Bullock, R. Morris; Campbell, Charles T. ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.6b00183	journal	March 2016
Methane Activation at the Pd/CeO ₂ Interface Senftle, Thomas P.; van Duin, Adri C. T.; Janik, Michael J. ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02447	journal	December 2016
Quantitative Differences in Sulfur Poisoning Phenomena over Ruthenium and Palladium: An Attempt To Deconvolute Geometric and Electronic Poisoning Effects Using Model Catalysts Kolpin, Amy; Jones, Glenn; Jones, Simon ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02765	journal	December 2016
Fluxionality of Catalytic Clusters: When It Matters and How to Address It Zhai, Huanchen; Alexandrova, Anastassia N. ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b03243	journal	February 2017
Toward the Balance between the Reductionist and Systems Approaches in Computational Catalysis: Model versus Method Accuracy for the Description of Catalytic Systems Pidko, Evgeny A. ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b00290	journal	May 2017
Ethylene Dehydrogenation on Pt _4,7,8 Clusters on Al ₂ O ₃ : Strong Cluster Size Dependence Linked to Preferred Catalyst Morphologies Baxter, Eric T.; Ha, Mai-Anh; Cass, Ashley C. ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.7b00409	journal	April 2017
Beyond Mean-Field Microkinetics: Toward Accurate and Efficient Theoretical Modeling in Heterogeneous Catalysis Chen, Zheng; Wang, He; Su, Neil Qiang ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b00943	journal	April 2018
Nanoalloying MgO-Deposited Pt Clusters with Si To Control the Selectivity of Alkane Dehydrogenation Jimenez-Izal, Elisa; Zhai, Huanchen; Liu, Ji-Yuan ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02443	journal	July 2018
Strong metal-support interactions Tauster, S. J. Accounts of Chemical Research, Vol. 20, Issue 11 https://doi.org/10.1021/ar00143a001	journal	November 1987
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300361m	journal	April 2013
Embedded Correlated Wavefunction Schemes: Theory and Applications Libisch, Florian; Huang, Chen; Carter, Emily A. Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar500086h	journal	May 2014
Strong Metal-Support Interactions Tauster, S. J. ACS Symposium Series https://doi.org/10.1021/bk-1986-0298.ch001	book	February 1986
Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides Sattler, Jesper J. H. B.; Ruiz-Martinez, Javier; Santillan-Jimenez, Eduardo Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5002436	journal	August 2014
Size-Dependent Sulfur Poisoning of Silica-Supported Monodisperse Pt Nanoparticle Hydrogenation Catalysts Baldyga, Lyndsey M.; Blavo, Selasi O.; Kuo, Chun-Hong ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300625m	journal	November 2012
Introduction to Special Issue on Operando and In Situ Studies of Catalysis Jones, Christopher W.; Tao, Franklin (Feng); Garland, Marc V. ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs3006692	journal	September 2012
Rutile-Deposited Pt–Pd clusters: A Hypothesis Regarding the Stability at 50/50 Ratio Ha, Mai-Anh; Dadras, Jonny; Alexandrova, Anastassia ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5011426	journal	September 2014
Comparative in Operando Studies in Heterogeneous Catalysis: Atomic and Electronic Structural Features in the Hydrogenation of Ethylene over Supported Pd and Pt Catalysts Jung, Ulrich; Elsen, Annika; Li, Yuanyuan ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/cs501846g	journal	February 2015
Chemistry of Supported Palladium Nanoparticles during Methane Oxidation Nilsson, Johan; Carlsson, Per-Anders; Fouladvand, Sheedeh ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs502036d	journal	March 2015
Search for the Li _n ^0/+1/-1 ( n = 5−7) Lowest-Energy Structures Using the ab Initio Gradient Embedded Genetic Algorithm (GEGA). Elucidation of the Chemical Bonding in the Lithium Clusters Alexandrova, Anastassia N.; Boldyrev, Alexander I. Journal of Chemical Theory and Computation, Vol. 1, Issue 4 https://doi.org/10.1021/ct050093g	journal	May 2005
cluster : Searching for Unique Low Energy Minima of Structures Using a Novel Implementation of a Genetic Algorithm Kanters, René P. F.; Donald, Kelling J. Journal of Chemical Theory and Computation, Vol. 10, Issue 12 https://doi.org/10.1021/ct500744k	journal	November 2014
Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide Tauster, S. J.; Fung, S. C.; Garten, R. L. Journal of the American Chemical Society, Vol. 100, Issue 1 https://doi.org/10.1021/ja00469a029	journal	January 1978
Catalytic Oxidation of Carbon Monoxide on Monodispersed Platinum Clusters: Each Atom Counts Heiz, U.; Sanchez, A.; Abbet, S. Journal of the American Chemical Society, Vol. 121, Issue 13 https://doi.org/10.1021/ja983616l	journal	April 1999
Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer–Tropsch Synthesis Li, Wei-Zhen; Liu, Jin-Xun; Gu, Jun Journal of the American Chemical Society, Vol. 139, Issue 6 https://doi.org/10.1021/jacs.6b10375	journal	February 2017
Boron Switch for Selectivity of Catalytic Dehydrogenation on Size-Selected Pt Clusters on Al ₂ O ₃ Ha, Mai-Anh; Baxter, Eric T.; Cass, Ashley C. Journal of the American Chemical Society, Vol. 139, Issue 33 https://doi.org/10.1021/jacs.7b05894	journal	August 2017
Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity Sun, Geng; Sautet, Philippe Journal of the American Chemical Society, Vol. 140, Issue 8 https://doi.org/10.1021/jacs.7b11239	journal	February 2018
A Linear Scaling Relation for CO Oxidation on CeO ₂ -Supported Pd Liu, Jin-Xun; Su, Yaqiong; Filot, Ivo A. W. Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.7b13624	journal	March 2018
Probing the Transformation of Boron Nitride Catalysts under Oxidative Dehydrogenation Conditions Love, Alyssa M.; Thomas, Brijith; Specht, Sarah E. Journal of the American Chemical Society, Vol. 141, Issue 1 https://doi.org/10.1021/jacs.8b08165	journal	November 2018
Molecular Structure of a Supported VO ₄ Cluster and Its Interfacial Geometry as a Function of the SiO ₂ , Nb ₂ O ₅ , and ZrO ₂ Support Keller, Daphne E.; Koningsberger, Diek C.; Weckhuysen, Bert M. The Journal of Physical Chemistry B, Vol. 110, Issue 29 https://doi.org/10.1021/jp060749h	journal	July 2006
Probe Microscope Observation of Platinum Atoms Deposited on the TiO ₂ (110)-(1 × 1) Surface Sasahara, Akira; Pang, Chi Lun; Onishi, Hiroshi The Journal of Physical Chemistry B, Vol. 110, Issue 27 https://doi.org/10.1021/jp062000c	journal	July 2006
H·(H ₂ O) _n Clusters: Microsolvation of the Hydrogen Atom via Molecular ab Initio Gradient Embedded Genetic Algorithm (GEGA) Alexandrova, Anastassia N. The Journal of Physical Chemistry A, Vol. 114, Issue 48 https://doi.org/10.1021/jp1092543	journal	December 2010
Mechanisms of the Oxygen Reduction Reaction on Defective Graphene-Supported Pt Nanoparticles from First-Principles Lim, Dong-Hee; Wilcox, Jennifer The Journal of Physical Chemistry C, Vol. 116, Issue 5 https://doi.org/10.1021/jp210796e	journal	January 2012
Pt–Zn Clusters on Stoichiometric MgO(100) and TiO ₂ (110): Dramatically Different Sintering Behavior Dadras, Jonny; Shen, Lu; Alexandrova, Anastassia The Journal of Physical Chemistry C, Vol. 119, Issue 11 https://doi.org/10.1021/jp512277x	journal	March 2015
Theoretical Studies of Palladium−Gold Nanoclusters: Pd−Au Clusters with up to 50 Atoms Pittaway, Faye; Paz-Borbón, Lauro Oliver; Johnston, Roy L. The Journal of Physical Chemistry C, Vol. 113, Issue 21 https://doi.org/10.1021/jp9006075	journal	May 2009
Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing up to 110 Atoms Wales, David J.; Doye, Jonathan P. K. The Journal of Physical Chemistry A, Vol. 101, Issue 28 https://doi.org/10.1021/jp970984n	journal	July 1997
Fluxionality of Au Clusters at Ceria Surfaces during CO Oxidation: Relationships among Reactivity, Size, Cohesion, and Surface Defects from DFT Simulations Ghosh, Prasenjit; Farnesi Camellone, Matteo; Fabris, Stefano The Journal of Physical Chemistry Letters, Vol. 4, Issue 14 https://doi.org/10.1021/jz4009079	journal	June 2013
A Guided Stochastic Energy-Domain Formulation of the Second Order Møller–Plesset Perturbation Theory Ge, Qinghui; Gao, Yi; Baer, Roi The Journal of Physical Chemistry Letters, Vol. 5, Issue 1 https://doi.org/10.1021/jz402206m	journal	December 2013
High Sintering Resistance of Size-Selected Platinum Cluster Catalysts by Suppressed Ostwald Ripening Wettergren, Kristina; Schweinberger, Florian F.; Deiana, Davide Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl502686u	journal	September 2014
Why gold is the noblest of all the metals Hammer, B.; Norskov, J. K. Nature, Vol. 376, Issue 6537 https://doi.org/10.1038/376238a0	journal	July 1995
Towards the computational design of solid catalysts Nørskov, J.; Bligaard, T.; Rossmeisl, J. Nature Chemistry, Vol. 1, Issue 1, p. 37-46 https://doi.org/10.1038/nchem.121	journal	April 2009
Observation of an all-boron fullerene Zhai, Hua-Jin; Zhao, Ya-Fan; Li, Wei-Li Nature Chemistry, Vol. 6, Issue 8 https://doi.org/10.1038/nchem.1999	journal	July 2014
Gallium-rich Pd–Ga phases as supported liquid metal catalysts Taccardi, N.; Grabau, M.; Debuschewitz, J. Nature Chemistry, Vol. 9, Issue 9 https://doi.org/10.1038/nchem.2822	journal	July 2017
Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10389	journal	January 2016
Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7511	journal	March 2015
Complex structural dynamics of nanocatalysts revealed in Operando conditions by correlated imaging and spectroscopy probes Li, Y.; Zakharov, D.; Zhao, S. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8583	journal	June 2015
Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P. Nature Materials, Vol. 8, Issue 3 https://doi.org/10.1038/nmat2384	journal	February 2009
Entropic contributions enhance polarity compensation for CeO2(100) surfaces Capdevila-Cortada, Marçal; López, Núria Nature Materials, Vol. 16, Issue 3 https://doi.org/10.1038/nmat4804	journal	November 2016
Raman spectroscopy during catalytic operations with on-line activity measurement (operando spectroscopy): a method for understanding the active centres of cations supported on porous materials Bañares, Miguel A.; Guerrero-Pérez, M. Olga; Fierro, José Luis G. J. Mater. Chem., Vol. 12, Issue 11 https://doi.org/10.1039/B204494C	journal	January 2002
Scaling relations between adsorption energies for computational screening and design of catalysts Montemore, Matthew M.; Medlin, J. Will Catal. Sci. Technol., Vol. 4, Issue 11 https://doi.org/10.1039/C4CY00335G	journal	January 2014
Tailoring nano-catalysts: turning gold nanoparticles on bulk metal oxides to inverse nano-metal oxides on large gold particles Zhao, Guofeng; Wu, Xin-Ping; Chai, Ruijuan Chemical Communications, Vol. 51, Issue 27 https://doi.org/10.1039/C5CC00016E	journal	January 2015
The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO ₂ photoreduction Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R. Physical Chemistry Chemical Physics, Vol. 17, Issue 38 https://doi.org/10.1039/C5CP03674G	journal	January 2015
The Birmingham parallel genetic algorithm and its application to the direct DFT global optimisation of Ir _N (N = 10–20) clusters Davis, Jack B. A.; Shayeghi, Armin; Horswell, Sarah L. Nanoscale, Vol. 7, Issue 33 https://doi.org/10.1039/C5NR03774C	journal	January 2015
Global minimization of gold clusters by combining neural network potentials and the basin-hopping method Ouyang, Runhai; Xie, Yu; Jiang, De-en Nanoscale, Vol. 7, Issue 36 https://doi.org/10.1039/C5NR03903G	journal	January 2015
Operando chemistry of catalyst surfaces during catalysis Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A. Chemical Society Reviews, Vol. 46, Issue 7 https://doi.org/10.1039/C6CS00931J	journal	January 2017
Reactivity of diatomics and of ethylene on zeolite-supported 13-atom platinum nanoclusters Keppeler, M.; Bräuning, G.; Radhakrishnan, S. G. Catalysis Science & Technology, Vol. 6, Issue 18 https://doi.org/10.1039/C6CY00182C	journal	January 2016
Controllable decoration of palladium sub-nanoclusters on reduced graphene oxide with superior catalytic performance in selective oxidation of alcohols Lei, Lijun; Wu, Zhiwei; Wang, Ruiyi Catalysis Science & Technology, Vol. 7, Issue 23 https://doi.org/10.1039/C7CY01732D	journal	January 2017
Oxidative strong metal–support interactions (OMSI) of supported platinum-group metal catalysts Tang, Hailian; Su, Yang; Guo, Yalin Chemical Science, Vol. 9, Issue 32 https://doi.org/10.1039/C8SC01392F	journal	January 2018
Determining the active site in a catalytic process: Operando spectroscopy is more than a buzzword Weckhuysen, Bert M. Physical Chemistry Chemical Physics, Vol. 5, Issue 20 https://doi.org/10.1039/b309650p	journal	January 2003
Operando spectroscopy: fundamental and technical aspects of spectroscopy of catalysts under working conditions Weckhuysen, Bert M. Physical Chemistry Chemical Physics, Vol. 5, Issue 20 https://doi.org/10.1039/b309654h	journal	January 2003
Size-dependent catalytic activity and geometries of size-selected Pt clusters on TiO₂(110) surfaces Watanabe, Yoshihide; Wu, Xingyang; Hirata, Hirohito Catalysis Science & Technology, Vol. 1, Issue 8, p. 1490-1495 https://doi.org/10.1039/c1cy00204j	journal	January 2011
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional Heyd, Jochen; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 121, Issue 3, p. 1187-1192 https://doi.org/10.1063/1.1760074	journal	July 2004
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
Modeling doped and defective oxides in catalysis with density functional theory methods: Room for improvements Pacchioni, Gianfranco The Journal of Chemical Physics, Vol. 128, Issue 18 https://doi.org/10.1063/1.2819245	journal	May 2008
Structural growth behavior and polarizability of CdnTen (n=1–14) clusters Wang, Jianguang; Ma, Li; Zhao, Jijun The Journal of Chemical Physics, Vol. 130, Issue 21 https://doi.org/10.1063/1.3147519	journal	June 2009
Koopmans’ springs to life Salzner, Ulrike; Baer, Roi The Journal of Chemical Physics, Vol. 131, Issue 23 https://doi.org/10.1063/1.3269030	journal	December 2009
Fast reaction products from the oxidation of CO on Pt(111): Angular and velocity distributions of the CO ₂ product molecules Allers, K. ‐H.; Pfnür, H.; Feulner, P. The Journal of Chemical Physics, Vol. 100, Issue 5 https://doi.org/10.1063/1.466332	journal	March 1994
Development of a ReaxFF potential for Pd/O and application to palladium oxide formation Senftle, Thomas P.; Meyer, Randall J.; Janik, Michael J. The Journal of Chemical Physics, Vol. 139, Issue 4 https://doi.org/10.1063/1.4815820	journal	July 2013
Communication: Embedded fragment stochastic density functional theory Neuhauser, Daniel; Baer, Roi; Rabani, Eran The Journal of Chemical Physics, Vol. 141, Issue 4 https://doi.org/10.1063/1.4890651	journal	July 2014
Sublinear scaling for time-dependent stochastic density functional theory Gao, Yi; Neuhauser, Daniel; Baer, Roi The Journal of Chemical Physics, Vol. 142, Issue 3 https://doi.org/10.1063/1.4905568	journal	January 2015
Self-consistent second-order Green’s function perturbation theory for periodic systems Rusakov, Alexander A.; Zgid, Dominika The Journal of Chemical Physics, Vol. 144, Issue 5 https://doi.org/10.1063/1.4940900	journal	February 2016
Communication: Finite size correction in periodic coupled cluster theory calculations of solids Liao, Ke; Grüneis, Andreas The Journal of Chemical Physics, Vol. 145, Issue 14 https://doi.org/10.1063/1.4964307	journal	October 2016
Clusters, surfaces, and catalysis Somorjai, G. A.; Contreras, A. M.; Montano, M. Proceedings of the National Academy of Sciences, Vol. 103, Issue 28 https://doi.org/10.1073/pnas.0507691103	journal	June 2006
Enzyme millisecond conformational dynamics do not catalyze the chemical step Pisliakov, A. V.; Cao, J.; Kamerlin, S. C. L. Proceedings of the National Academy of Sciences, Vol. 106, Issue 41 https://doi.org/10.1073/pnas.0909150106	journal	September 2009
Ab initio random structure searching Pickard, Chris J.; Needs, R. J. Journal of Physics: Condensed Matter, Vol. 23, Issue 5 https://doi.org/10.1088/0953-8984/23/5/053201	journal	January 2011
Quantum chemical treatments of metal clusters Weigend, Florian; Ahlrichs, Reinhart Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1915 https://doi.org/10.1098/rsta.2009.0268	journal	March 2010
Density-functional calculation of effective Coulomb interactions in metals Anisimov, V. I.; Gunnarsson, O. Physical Review B, Vol. 43, Issue 10, p. 7570-7574 https://doi.org/10.1103/PhysRevB.43.7570	journal	April 1991
Reaction channels for the catalytic oxidation of CO on Pt(111) Eichler, A.; Hafner, J. Physical Review B, Vol. 59, Issue 8 https://doi.org/10.1103/PhysRevB.59.5960	journal	February 1999
Quantum effects on the structure of pure and binary metallic nanoclusters Ferrando, R.; Fortunelli, A.; Rossi, G. Physical Review B, Vol. 72, Issue 8 https://doi.org/10.1103/PhysRevB.72.085449	journal	August 2005
Comment on “Taming multiple valency with density functionals: A case study of defective ceria” Kresse, Georg; Blaha, Peter; Da Silva, Juarez L. F. Physical Review B, Vol. 72, Issue 23 https://doi.org/10.1103/PhysRevB.72.237101	journal	December 2005
First-principles study for low-spin LaCoO 3 with a structurally consistent Hubbard U Hsu, Han; Umemoto, Koichiro; Cococcioni, Matteo Physical Review B, Vol. 79, Issue 12 https://doi.org/10.1103/PhysRevB.79.125124	journal	March 2009
Self-consistent hybrid functional for condensed systems Skone, Jonathan H.; Govoni, Marco; Galli, Giulia Physical Review B, Vol. 89, Issue 19 https://doi.org/10.1103/PhysRevB.89.195112	journal	May 2014
Simple screened exact-exchange approach for excitonic properties in solids Yang, Zeng-hui; Sottile, Francesco; Ullrich, Carsten A. Physical Review B, Vol. 92, Issue 3 https://doi.org/10.1103/PhysRevB.92.035202	journal	July 2015
Swift G W beyond 10,000 electrons using sparse stochastic compression Vlček, Vojtěch; Li, Wenfei; Baer, Roi Physical Review B, Vol. 98, Issue 7 https://doi.org/10.1103/PhysRevB.98.075107	journal	August 2018
Fundamental Gaps in Finite Systems from Eigenvalues of a Generalized Kohn-Sham Method Stein, Tamar; Eisenberg, Helen; Kronik, Leeor Physical Review Letters, Vol. 105, Issue 26 https://doi.org/10.1103/PhysRevLett.105.266802	journal	December 2010
Self-Averaging Stochastic Kohn-Sham Density-Functional Theory Baer, Roi; Neuhauser, Daniel; Rabani, Eran Physical Review Letters, Vol. 111, Issue 10 https://doi.org/10.1103/PhysRevLett.111.106402	journal	September 2013
Breaking the Theoretical Scaling Limit for Predicting Quasiparticle Energies: The Stochastic G W Approach Neuhauser, Daniel; Gao, Yi; Arntsen, Christopher Physical Review Letters, Vol. 113, Issue 7 https://doi.org/10.1103/PhysRevLett.113.076402	journal	August 2014
Molecular Geometry Optimization with a Genetic Algorithm Deaven, D. M.; Ho, K. M. Physical Review Letters, Vol. 75, Issue 2 https://doi.org/10.1103/PhysRevLett.75.288	journal	July 1995
Density Functional Theory with Correct Long-Range Asymptotic Behavior Baer, Roi; Neuhauser, Daniel Physical Review Letters, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevLett.94.043002	journal	February 2005
Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard U Approach Kulik, Heather J.; Cococcioni, Matteo; Scherlis, Damian A. Physical Review Letters, Vol. 97, Issue 10 https://doi.org/10.1103/PhysRevLett.97.103001	journal	September 2006
Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation Herzing, A. A.; Kiely, C. J.; Carley, A. F. Science, Vol. 321, Issue 5894 https://doi.org/10.1126/science.1159639	journal	September 2008
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles Tao, F.; Grass, M. E.; Zhang, Y. Science, Vol. 322, Issue 5903 https://doi.org/10.1126/science.1164170	journal	November 2008
Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts Grant, J. T.; Carrero, C. A.; Goeltl, F. Science, Vol. 354, Issue 6319 https://doi.org/10.1126/science.aaf7885	journal	December 2016
Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design Greeley, Jeffrey Annual Review of Chemical and Biomolecular Engineering, Vol. 7, Issue 1 https://doi.org/10.1146/annurev-chembioeng-080615-034413	journal	June 2016
Atomistic Simulations of Activated Processes in Materials Henkelman, G. Annual Review of Materials Research, Vol. 47, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121616	journal	July 2017
Computational Design of Clusters for Catalysis Jimenez-Izal, Elisa; Alexandrova, Anastassia N. Annual Review of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1146/annurev-physchem-050317-014216	journal	April 2018
Novel Gold Catalysts for the Oxidation of Carbon Monoxide at a Temperature far Below 0 °C Haruta, Masatake; Kobayashi, Tetsuhiko; Sano, Hiroshi Chemistry Letters, Vol. 16, Issue 2 https://doi.org/10.1246/cl.1987.405	journal	February 1987
Fast reaction products from the oxidation of CO on Pt(111): Angular and velocity distributions of the CO2 product molecules Allers, K. -H.; Pfnür, Herbert; Feulner, P. College Park, MD : American Institute of Physics https://doi.org/10.15488/2769	other	January 1994
Understanding Heteroatom-Mediated Metal–Support Interactions in Functionalized Carbons: A Perspective Review Campisi, Sebastiano; Chan-Thaw, Carine; Villa, Alberto Applied Sciences, Vol. 8, Issue 7 https://doi.org/10.3390/app8071159	journal	July 2018
Sublinear scaling for time-dependent stochastic density functional theory Gao, Yi; Neuhauser, Daniel; Baer, Roi arXiv https://doi.org/10.48550/arxiv.1410.6133	text	January 2014
Self-consistent hybrid functional for condensed systems Skone, Jonathan H.; Govoni, Marco; Galli, Giulia arXiv https://doi.org/10.48550/arxiv.1501.03184	text	January 2015
Gaussian-based coupled-cluster theory for the ground state and band structure of solids McClain, James; Sun, Qiming; Chan, Garnet Kin-Lic arXiv https://doi.org/10.48550/arxiv.1701.04832	preprint	January 2017
Stochastic self-consistent second-order Green's function method for correlation energies of large electronic systems Neuhauser, Daniel; Baer, Roi; Zgid, Dominika arXiv https://doi.org/10.48550/arxiv.1707.08296	preprint	January 2017

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