Theoretical Perspective on Operando Spectroscopy of Fluxional Nanocatalysts

Poths, Patricia; Alexandrova, Anastassia N.

doi:10.1021/acs.jpclett.2c00628

Title: Theoretical Perspective on Operando Spectroscopy of Fluxional Nanocatalysts

Journal Article · Tue May 10 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00628· OSTI ID:1968775

^[1];

^[2]

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

Improvements in operando spectroscopy have enabled the catalysis community to investigate the dynamic nature of catalysts under operating conditions with increasing detail. Still, the highly dynamic nature of some catalysts, such as fluxional supported subnano clusters, presents a formidable challenge even for the most state-of-the-art techniques. Here, the reason is that such fluxional catalytic interfaces contain a variety of thermally accessible states. Operando spectroscopies used in catalysis generally fall into two categories: ensemble-based techniques, which provide spectra containing the signals of the entire ensemble of states of the catalyst and are not necessarily dominated by the most active species, and localized techniques, which provide atomistic-level information about the dynamics of active sites in a very small area, which might not include the most active species. Combining many different kinds of techniques can provide detailed insight; however, we propose that effective utilization of specific computational techniques and approaches within the fluxionality paradigm can fill the gap and enable atomistic characterization of the most relevant catalytic sites.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: SC0019152; AFOSR FA9550-19-1-0261

OSTI ID:: 1968775

Journal Information:: Journal of Physical Chemistry Letters, Vol. 13, Issue 19; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

The Problem with Determining Atomic Structure at the Nanoscale Billinge, S. J. L.; Levin, I. Science, Vol. 316, Issue 5824 https://doi.org/10.1126/science.1135080	journal	April 2007
Operando Insights into Nanoparticle Transformations during Catalysis Bergmann, Arno; Roldan Cuenya, Beatriz ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b01831	journal	August 2019
Hydrogen Evolution on Restructured B-Rich WB: Metastable Surface States and Isolated Active Sites Zhang, Zisheng; Cui, Zhi-Hao; Jimenez-Izal, Elisa ACS Catalysis, Vol. 10, Issue 23 https://doi.org/10.1021/acscatal.0c03410	journal	November 2020
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
Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane Venegas, Juan M.; Zhang, Zisheng; Agbi, Theodore O. Angewandte Chemie International Edition, Vol. 59, Issue 38 https://doi.org/10.1002/anie.202003695	journal	July 2020
Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces Zhang, Zisheng; Zandkarimi, Borna; Alexandrova, Anastassia N. Accounts of Chemical Research, Vol. 53, Issue 2 https://doi.org/10.1021/acs.accounts.9b00531	journal	January 2020
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
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
Pt ₈ cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization Sun, Geng; Alexandrova, Anastassia N.; Sautet, Philippe The Journal of Chemical Physics, Vol. 151, Issue 19 https://doi.org/10.1063/1.5129296	journal	November 2019
Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics Halder, Avik; Ha, Mai‐Anh; Zhai, Huanchen ChemCatChem, Vol. 12, Issue 5 https://doi.org/10.1002/cctc.201901795	journal	January 2020
Oxidation Dynamics of Supported Catalytic Cu Clusters: Coupling to Fluxionality Guo, Han; Poths, Patricia; Sautet, Philippe ACS Catalysis, Vol. 12, Issue 1 https://doi.org/10.1021/acscatal.1c04100	journal	December 2021
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
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
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
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
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
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
Quantitative structural determination of active sites from in situ and operando XANES spectra: From standard ab initio simulations to chemometric and machine learning approaches Guda, Alexander A.; Guda, Sergey A.; Lomachenko, Kirill A. Catalysis Today, Vol. 336 https://doi.org/10.1016/j.cattod.2018.10.071	journal	October 2019
In Situ / Operando Electrocatalyst Characterization by X-ray Absorption Spectroscopy Timoshenko, Janis; Roldan Cuenya, Beatriz Chemical Reviews, Vol. 121, Issue 2 https://doi.org/10.1021/acs.chemrev.0c00396	journal	September 2020
Dynamic Behavior of Single-Atom Catalysts in Electrocatalysis: Identification of Cu-N ₃ as an Active Site for the Oxygen Reduction Reaction Yang, Ji; Liu, Wengang; Xu, Mingquan Journal of the American Chemical Society, Vol. 143, Issue 36 https://doi.org/10.1021/jacs.1c03788	journal	August 2021
Operando XAS/SAXS: Guiding Design of Single‐Atom and Subnanocluster Catalysts Fang, Lingzhe; Seifert, Soenke; Winans, Randall E. Small Methods, Vol. 5, Issue 5 https://doi.org/10.1002/smtd.202001194	journal	February 2021
A Perspective on Counting Catalytic Active Sites and Rates of Reaction Using X-Ray Spectroscopy Kondrat, S. A.; van Bokhoven, J. A. Topics in Catalysis, Vol. 62, Issue 17-20 https://doi.org/10.1007/s11244-018-1057-4	journal	October 2018
Applications of Modulation Excitation Spectroscopy in Heterogeneous Catalysis Müller, Philipp; Hermans, Ive Industrial & Engineering Chemistry Research, Vol. 56, Issue 5 https://doi.org/10.1021/acs.iecr.6b04855	journal	January 2017
Investigation of periodically driven systems by x-ray absorption spectroscopy using asynchronous data collection mode Singh, H.; Donetsky, D.; Liu, J. Review of Scientific Instruments, Vol. 89, Issue 4 https://doi.org/10.1063/1.5000679	journal	April 2018
Stroboscopic operando spectroscopy of the dynamics in heterogeneous catalysis by event-averaging Knudsen, Jan; Gallo, Tamires; Boix, Virgínia Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26372-y	journal	October 2021
Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions Foucher, Alexandre C.; Marcella, Nicholas; Lee, Jennifer D. ACS Nano, Vol. 15, Issue 12 https://doi.org/10.1021/acsnano.1c09450	journal	November 2021
Dynamical Change of Valence States and Structure in NiCu ₃ Nanoparticles during Redox Cycling Foucher, Alexandre C.; Marcella, Nicholas; Lee, Jennifer D. The Journal of Physical Chemistry C, Vol. 126, Issue 4 https://doi.org/10.1021/acs.jpcc.1c10824	journal	January 2022
Alloying with Sn Suppresses Sintering of Size-Selected Subnano Pt Clusters on SiO ₂ with and without Adsorbates Zandkarimi, Borna; Gorey, Timothy J.; Li, Guangjing Chemistry of Materials, Vol. 32, Issue 19 https://doi.org/10.1021/acs.chemmater.0c02926	journal	September 2020
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
Dynamic Surface Reconstruction of Single-Atom Bimetallic Alloy under Operando Electrochemical Conditions Liu, Xiaokang; Ao, Chengcheng; Shen, Xinyi Nano Letters, Vol. 20, Issue 11 https://doi.org/10.1021/acs.nanolett.0c03475	journal	October 2020
The Comparison between Single Atom Catalysis and Surface Organometallic Catalysis Samantaray, Manoja K.; D’Elia, Valerio; Pump, Eva Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00238	journal	October 2019
Coordination structure at work: Atomically dispersed heterogeneous catalysts Zhang, Zhun; Li, Hengyu; Wu, Danfeng Coordination Chemistry Reviews, Vol. 460 https://doi.org/10.1016/j.ccr.2022.214469	journal	June 2022
Inherent Size Effects on XANES of Nanometer Metal Clusters: Size-Selected Platinum Clusters on Silica Dai, Yang; Gorey, Timothy J.; Anderson, Scott L. The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b10167	journal	December 2016
Interpreting the Operando XANES of Surface-Supported Subnanometer Clusters: When Fluxionality, Oxidation State, and Size Effect Fight Zandkarimi, Borna; Sun, Geng; Halder, Avik The Journal of Physical Chemistry C, Vol. 124, Issue 18 https://doi.org/10.1021/acs.jpcc.0c02823	journal	April 2020
Structural Rearrangements of Subnanometer Cu Oxide Clusters Govern Catalytic Oxidation Sun, Geng; Alexandrova, Anastassia N.; Sautet, Philippe ACS Catalysis, Vol. 10, Issue 9 https://doi.org/10.1021/acscatal.0c00824	journal	April 2020
Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size Poths, Patricia; Sun, Geng; Sautet, Philippe The Journal of Physical Chemistry C, Vol. 126, Issue 4 https://doi.org/10.1021/acs.jpcc.1c10356	journal	January 2022
Self-consistency, spin-orbit and other advances in the FDMNES code to simulate XANES and RXD experiments Joly, Y.; Bunău, O.; Lorenzo, J. E. Journal of Physics: Conference Series, Vol. 190 https://doi.org/10.1088/1742-6596/190/1/012007	journal	November 2009
Dynamic structure in supported Pt nanoclusters: Real-time density functional theory and x-ray spectroscopy simulations Vila, F.; Rehr, J. J.; Kas, J. Physical Review B, Vol. 78, Issue 12 https://doi.org/10.1103/PhysRevB.78.121404	journal	September 2008
Mapping XANES spectra on structural descriptors of copper oxide clusters using supervised machine learning Liu, Yang; Marcella, Nicholas; Timoshenko, Janis The Journal of Chemical Physics, Vol. 151, Issue 16 https://doi.org/10.1063/1.5126597	journal	October 2019
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
Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy Timoshenko, Janis; Anspoks, Andris; Cintins, Arturs Physical Review Letters, Vol. 120, Issue 22 https://doi.org/10.1103/PhysRevLett.120.225502	journal	May 2018
Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles Timoshenko, Janis; Lu, Deyu; Lin, Yuewei The Journal of Physical Chemistry Letters, Vol. 8, Issue 20 https://doi.org/10.1021/acs.jpclett.7b02364	journal	October 2017
Ab initio theory and calculations of X-ray spectra Rehr, John J.; Kas, Joshua J.; Prange, Micah P. Comptes Rendus Physique, Vol. 10, Issue 6 https://doi.org/10.1016/j.crhy.2008.08.004	journal	July 2009
Efficient implementation of core-excitation Bethe–Salpeter equation calculations Gilmore, K.; Vinson, John; Shirley, E. L. Computer Physics Communications, Vol. 197 https://doi.org/10.1016/j.cpc.2015.08.014	journal	December 2015
Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations Collinge, Greg; Yuk, Simuck F.; Nguyen, Manh-Thuong ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c01501	journal	July 2020
Operando Effects on the Structure and Dynamics of Pt _n Sn _m /γ-Al ₂ O ₃ from Ab Initio Molecular Dynamics and X-ray Absorption Spectra Vila, Fernando D.; Rehr, John J.; Kelly, Shelly D. The Journal of Physical Chemistry C, Vol. 117, Issue 24 https://doi.org/10.1021/jp403931z	journal	June 2013
Bridging the Pressure Gap in CO Oxidation Blomberg, Sara; Hejral, Uta; Shipilin, Mikhail ACS Catalysis, Vol. 11, Issue 15 https://doi.org/10.1021/acscatal.1c00806	journal	July 2021
On the relation between X-ray Photoelectron Spectroscopy and XAFS Mårtensson, N.; Söderstrom, J.; Svensson, S. Journal of Physics: Conference Series, Vol. 430 https://doi.org/10.1088/1742-6596/430/1/012131	journal	April 2013
Single Atom Catalysts: A Review of Characterization Methods Kottwitz, Matthew; Li, Yuanyuan; Wang, Haodong Chemistry–Methods, Vol. 1, Issue 6 https://doi.org/10.1002/cmtd.202100020	journal	June 2021
Surface science under reaction conditions: CO oxidation on Pt and Pd model catalysts van Spronsen, Matthijs A.; Frenken, Joost W. M.; Groot, Irene M. N. Chemical Society Reviews, Vol. 46, Issue 14 https://doi.org/10.1039/C7CS00045F	journal	January 2017
Calculation of core level shifts within DFT using pseudopotentials and localized basis sets García-Gil, S.; García, A.; Ordejón, P. The European Physical Journal B, Vol. 85, Issue 7 https://doi.org/10.1140/epjb/e2012-30334-5	journal	July 2012
Synergistic Application of XPS and DFT to Investigate Metal Oxide Surface Catalysis Trinh, Quang Thang; Bhola, Kartavya; Amaniampong, Prince Nana The Journal of Physical Chemistry C, Vol. 122, Issue 39 https://doi.org/10.1021/acs.jpcc.8b05499	journal	September 2018
Atomistic-Level Description of GaN/Water Interface by a Combined Spectroscopic and First-Principles Computational Approach Sato, Masahiro; Imazeki, Yuki; Takeda, Takahito The Journal of Physical Chemistry C, Vol. 124, Issue 23 https://doi.org/10.1021/acs.jpcc.0c02192	journal	May 2020
CO ₂ Hydrogenation to Formate and Formic Acid by Bimetallic Palladium–Copper Hydride Clusters Liu, Gaoxiang; Poths, Patricia; Zhang, Xinxing Journal of the American Chemical Society, Vol. 142, Issue 17 https://doi.org/10.1021/jacs.0c01855	journal	April 2020
Structure and Dynamics of Reactant Coadsorption on Single Crystal Model Catalysts by HP-STM and AP-XPS: A Mini Review Wu, Cheng Hao; Eren, Baran; Salmeron, Miquel B. Topics in Catalysis, Vol. 59, Issue 5-7 https://doi.org/10.1007/s11244-015-0527-1	journal	January 2016
Real-time imaging of adatom-promoted graphene growth on nickel Patera, Laerte L.; Bianchini, Federico; Africh, Cristina Science, Vol. 359, Issue 6381 https://doi.org/10.1126/science.aan8782	journal	March 2018
Atomic level fluxional behavior and activity of CeO2-supported Pt catalysts for CO oxidation Vincent, Joshua L.; Crozier, Peter A. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26047-8	journal	October 2021
Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction Li, Yuanyuan; Kottwitz, Matthew; Vincent, Joshua L. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21132-4	journal	February 2021
Structural changes in noble metal nanoparticles during CO oxidation and their impact on catalyst activity Chee, See Wee; Arce-Ramos, Juan Manuel; Li, Wenqing Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16027-9	journal	May 2020
Reagent-Triggered Isomerization of Fluxional Cluster Catalyst via Dynamic Coupling Guo, Han; Sautet, Philippe; Alexandrova, Anastassia N. The Journal of Physical Chemistry Letters, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jpclett.0c00548	journal	March 2020
Global Activity Search Uncovers Reaction Induced Concomitant Catalyst Restructuring for Alkane Dissociation on Model Pt Catalysts Sun, Geng; Fuller, Jack T.; Alexandrova, Anastassia N. ACS Catalysis, Vol. 11, Issue 3 https://doi.org/10.1021/acscatal.0c05421	journal	January 2021
Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights Yang, An-Chih; Choksi, Tej; Streibel, Verena Proceedings of the National Academy of Sciences, Vol. 117, Issue 26 https://doi.org/10.1073/pnas.2002342117	journal	June 2020
Toward Rational Design of Oxide-Supported Single-Atom Catalysts: Atomic Dispersion of Gold on Ceria Liu, Jin-Cheng; Wang, Yang-Gang; Li, Jun Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b01602	journal	April 2017
Time Scale and Elementary Steps of CO-Induced Disintegration of Surface Rhodium Clusters Suzuki, Akane; Inada, Yasuhiro; Yamaguchi, Aritomo Angewandte Chemie, Vol. 115, Issue 39 https://doi.org/10.1002/ange.200352318	journal	October 2003
The dynamics of overlayer formation on catalyst nanoparticles and strong metal-support interaction Beck, Arik; Huang, Xing; Artiglia, Luca Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17070-2	journal	June 2020

Similar Records

Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces

Journal Article · Fri Jan 24 00:00:00 EST 2020 · Accounts of Chemical Research · OSTI ID:1968775

Zhang, Zisheng; Zandkarimi, Borna; Alexandrova, Anastassia N.

Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Journal Article · Thu Jan 20 00:00:00 EST 2022 · Journal of Physical Chemistry. C · OSTI ID:1968775

Poths, Patricia; Sun, Geng; Sautet, Philippe; +1 more

Ensemble representation of catalytic interfaces: soloists, orchestras, and everything in-between

Journal Article · Wed Jul 13 00:00:00 EDT 2022 · Chemical Science · OSTI ID:1968775

Lavroff, Robert H.; Morgan, Harry W. T.; Zhang, Zisheng; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysts
Cluster chemistry
Metal clusters
Molecular structure
X-ray absorption near edge spectroscopy

Title: Theoretical Perspective on Operando Spectroscopy of Fluxional Nanocatalysts

Citation Formats

References (65)

Similar Records

Related Subjects