Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis

Zandkarimi, Borna; Alexandrova, Anastassia N.

doi:10.1021/acs.jpclett.8b03680

Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis

Journal Article · Fri Jan 11 04:00:00 EST 2019 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b03680· OSTI ID:1492942

^[1]; ^[2]

Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry; University of California, Los Angeles
Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry; California NanoSystems Institute, Los Angeles, CA (United States)

Scaling relationships in catalysis impose fundamental limitations on the catalyst maximal performance; therefore, there is a continuous hunt for ways of circumventing them. In this study, we show that, at the subnano-scale, scaling relationships can be broken through catalyst dynamics. Oxygen reduction reaction (ORR), which can be catalyzed by Pt nanoparticles, is used as our study case. Subnanometer gas-phase and graphene-deposited Ptn cluster catalysts are shown to exhibit poor correlation between binding energies of the intermediates, O, OH, and OOH, involved in the scaling relationships for ORR. The effect is due to the highly fluxional behavior of subnanometer clusters, which easily adapt their structures to the bound adsorbates and varying coverage and in some cases even reshape the structure upon changing environment. Lastly, this fluxional behavior is also commonplace for clusters and contrasts them to extended surfaces, suggesting that breaking scaling relationships is likely a rule more than an exception in nanocluster catalysis.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); USDOD; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: SC0019152; AC02-05CH11231

OSTI ID:: 1492942

Alternate ID(s):: OSTI ID: 1755383
OSTI ID: 1594250

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Vol. 10; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Modern Methods of Crystal Structure Prediction Oganov, Artem R. Wiley‐VCH Verlag GmbH & Co https://doi.org/10.1002/9783527632831	book	November 2010
Engineering Multimetallic Nanocrystals for Highly Efficient Oxygen Reduction Catalysts Wang, Wei; Lei, Bo; Guo, Shaojun Advanced Energy Materials, Vol. 6, Issue 17 https://doi.org/10.1002/aenm.201600236	journal	April 2016
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
Theoretical Studies of Potential-Dependent and Competing Mechanisms of the Electrocatalytic Oxygen Reduction Reaction on Pt(111) Keith, John A.; Jacob, Timo Angewandte Chemie International Edition, Vol. 49, Issue 49 https://doi.org/10.1002/anie.201004794	journal	October 2010
Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction Guo, Shaojun; Zhang, Sen; Sun, Shouheng Angewandte Chemie International Edition, Vol. 52, Issue 33 https://doi.org/10.1002/anie.201207186	journal	June 2013
Finding the Most Catalytically Active Platinum Clusters With Low Atomicity Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae Angewandte Chemie International Edition, Vol. 54, Issue 34 https://doi.org/10.1002/anie.201504473	journal	July 2015
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
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Effect of temperature on the oxygen reduction reaction kinetic at nitrogen-doped carbon nanotubes for fuel cell cathode Wong, W. Y.; Daud, W. R. W.; Mohamad, A. B. International Journal of Hydrogen Energy, Vol. 40, Issue 35 https://doi.org/10.1016/j.ijhydene.2015.06.006	journal	September 2015
Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces Nilekar, Anand Udaykumar; Mavrikakis, Manos Surface Science, Vol. 602, Issue 14 https://doi.org/10.1016/j.susc.2008.05.036	journal	July 2008
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 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
Effect of Temperature and Pressure on the Kinetics of the Oxygen Reduction Reaction Tse, Edmund C. M.; Gewirth, Andrew A. The Journal of Physical Chemistry A, Vol. 119, Issue 8 https://doi.org/10.1021/acs.jpca.5b00572	journal	February 2015
DFT Global Optimization of Gas-Phase Subnanometer Ru–Pt Clusters Demiroglu, Ilker; Yao, Kezi; Hussein, Heider A. The Journal of Physical Chemistry C, Vol. 121, Issue 20 https://doi.org/10.1021/acs.jpcc.6b11329	journal	January 2017
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
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
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
Understanding and Breaking Scaling Relations in Single-Site Catalysis: Methane to Methanol Conversion by Fe ^IV ═O Gani, Terry Z. H.; Kulik, Heather J. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03597	journal	January 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
Temperature Dependence of Oxygen Reduction Reaction Activity at Stabilized Pt Skin-PtCo Alloy/Graphitized Carbon Black Catalysts Prepared by a Modified Nanocapsule Method Okaya, Kazuki; Yano, Hiroshi; Kakinuma, Katsuyoshi ACS Applied Materials & Interfaces, Vol. 4, Issue 12 https://doi.org/10.1021/am302224n	journal	December 2012
Platinum-Based Oxygen Reduction Electrocatalysts Wu, Jianbo; Yang, Hong Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300359w	journal	April 2013
Graphene-Supported Nanoelectrocatalysts for Fuel Cells: Synthesis, Properties, and Applications Liu, Minmin; Zhang, Ruizhong; Chen, Wei Chemical Reviews, Vol. 114, Issue 10 https://doi.org/10.1021/cr400523y	journal	March 2014
Magic Number Pt ₁₃ and Misshapen Pt ₁₂ Clusters: Which One is the Better Catalyst? Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae Journal of the American Chemical Society, Vol. 135, Issue 35 https://doi.org/10.1021/ja405922m	journal	August 2013
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
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
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
Identification of the Scaling Relations for Binary Noble-Metal Nanoparticles Fu, Qiang; Cao, Xinrui; Luo, Yi The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp311104w	journal	February 2013
Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces Jiang, T.; Mowbray, D. J.; Dobrin, S. The Journal of Physical Chemistry C, Vol. 113, Issue 24 https://doi.org/10.1021/jp811185g	journal	May 2009
Electrocatalysis on Platinum Nanoparticles: Particle Size Effect on Oxygen Reduction Reaction Activity Shao, Minhua; Peles, Amra; Shoemaker, Krista Nano Letters, Vol. 11, Issue 9 https://doi.org/10.1021/nl2017459	journal	September 2011
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
Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers Calle-Vallejo, Federico; Loffreda, David; Koper, Marc T. M. Nature Chemistry, Vol. 7, Issue 5 https://doi.org/10.1038/nchem.2226	journal	April 2015
Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions Yamamoto, Kimihisa; Imaoka, Takane; Chun, Wang-Jae Nature Chemistry, Vol. 1, Issue 5 https://doi.org/10.1038/nchem.288	journal	July 2009
How strain can break the scaling relations of catalysis Khorshidi, Alireza; Violet, James; Hashemi, Javad Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0054-0	journal	April 2018
Origin of high oxygen reduction reaction activity of Pt12 and strategy to obtain better catalyst using sub-nanosized Pt-alloy clusters Miyazaki, Kasumi; Mori, Hirotoshi Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep45381	journal	March 2017
Pure and Zn-doped Pt clusters go flat and upright on MgO(100) Shen, Lu; Dadras, Jonny; Alexandrova, Anastassia N. Phys. Chem. Chem. Phys., Vol. 16, Issue 48 https://doi.org/10.1039/C4CP01877J	journal	January 2014
Scaling relations between adsorption energies for computational screening and design of catalysts Montemore, Matthew M.; Medlin, J. Will Catal. Sci. Technol., Vol. 4, Issue 11 https://doi.org/10.1039/C4CY00335G	journal	January 2014
Linear scaling relationships and volcano plots in homogeneous catalysis – revisiting the Suzuki reaction Busch, Michael; Wodrich, Matthew D.; Corminboeuf, Clémence Chemical Science, Vol. 6, Issue 12 https://doi.org/10.1039/C5SC02910D	journal	January 2015
How covalence breaks adsorption-energy scaling relations and solvation restores them Calle-Vallejo, Federico; Krabbe, Alexander; García-Lastra, Juan M. Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC02123A	journal	January 2017
ORR viability of alumina-supported platinum nanocluster: exploring oxidation behaviour by DFT Nigam, Sandeep; Majumder, Chiranjib Physical Chemistry Chemical Physics, Vol. 19, Issue 29 https://doi.org/10.1039/C7CP04029F	journal	January 2017
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
Graphene field-effect transistors Reddy, Dharmendar; Register, Leonard F.; Carpenter, Gary D. Journal of Physics D: Applied Physics, Vol. 44, Issue 31 https://doi.org/10.1088/0022-3727/44/31/313001	journal	July 2011
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
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction Huang, X.; Zhao, Z.; Cao, L. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa8765	journal	June 2015
Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors Calle-Vallejo, F.; Tymoczko, J.; Colic, V. Science, Vol. 350, Issue 6257 https://doi.org/10.1126/science.aab3501	journal	October 2015
Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis Bu, Lingzheng; Zhang, Nan; Guo, Shaojun Science, Vol. 354, Issue 6318 https://doi.org/10.1126/science.aah6133	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
Progress in the Development of Oxygen Reduction Reaction Catalysts for Low-Temperature Fuel Cells Li, Dongguo; Lv, Haifeng; Kang, Yijin Annual Review of Chemical and Biomolecular Engineering, Vol. 7, Issue 1 https://doi.org/10.1146/annurev-chembioeng-080615-034526	journal	June 2016
The Effect of Oxidation Temperature for the Oxygen Reduction Reaction Activity of Defective Multi-Walled Carbon Nanotubes (MWCNT) Chen, Jiuting; Eguchi, Kouya; Waki, Keiko ECS Transactions, Vol. 80, Issue 8 https://doi.org/10.1149/08008.0677ecst	journal	August 2017
Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters Tang, Zhenghua; Wu, Wen; Wang, Kai Catalysts, Vol. 8, Issue 2 https://doi.org/10.3390/catal8020065	journal	February 2018
Volcano plots in hydrogen electrocatalysis – uses and abuses Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth Beilstein Journal of Nanotechnology, Vol. 5 https://doi.org/10.3762/bjnano.5.96	journal	January 2014

Cited By (5)

Solid-to-liquid phase transitions of sub-nanometer clusters enhance chemical transformation Sun, Juan-Juan; Cheng, Jun Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13509-3	journal	November 2019
Surface‐supported cluster catalysis: Ensembles of metastable states run the show Zandkarimi, Borna; Alexandrova, Anastassia N. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6 https://doi.org/10.1002/wcms.1420	journal	May 2019
Strategies to break linear scaling relationships Pérez-Ramírez, Javier; López, Núria Nature Catalysis, Vol. 2, Issue 11 https://doi.org/10.1038/s41929-019-0376-6	journal	October 2019
Escaping scaling relationships for water dissociation at interfacial sites of zirconia-supported Rh and Pt clusters Kauppinen, Minttu M.; Korpelin, Ville; Verma, Anand Mohan The Journal of Chemical Physics, Vol. 151, Issue 16 https://doi.org/10.1063/1.5126261	journal	October 2019
Interface-confined triangular FeO _x nanoclusters on Pt(111) Zhou, Zhiwen; Liu, Ping; Yang, Fan The Journal of Chemical Physics, Vol. 151, Issue 21 https://doi.org/10.1063/1.5129266	journal	December 2019

Similar Records

Fluxionality of Subnano Clusters Reshapes the Activity Volcano of Electrocatalysis

Journal Article · Fri May 20 00:00:00 EDT 2022 · ChemCatChem · OSTI ID:1976293

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY
ORR
catalysis
fluxionality
nanoclusters
scaling relations

Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis

Citation Formats

References (56)

Cited By (5)

Similar Records

Related Subjects