Catalytic Resonance Theory: Turnover Efficiency and the Resonance Frequency

Canavan, Jesse R.; Hopkins, Justin A.; Foley, Brandon L.; Abdelrahman, Omar A.; Dauenhauer, Paul J.

doi:10.1021/acscatal.4c06623

Catalytic Resonance Theory: Turnover Efficiency and the Resonance Frequency

Journal Article · Mon Dec 23 00:00:00 EST 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.4c06623· OSTI ID:2483271

Canavan, Jesse R. ^[1]; ^[1]; ^[2]; Abdelrahman, Omar A. ^[3]; ^[1]

University of Minnesota, Minneapolis, MN (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
University of Minnesota, Minneapolis, MN (United States); University of Houston, TX (United States)

Programmable catalysts exhibiting forced oscillation in the free energy of reacting surface species were simulated to understand the general mechanisms leading to efficient use of the input energy. Catalytic ratchets with either positive or negative adsorbate scaling exhibited oscillation conditions of both high and low turnover efficiency, yielding catalytic turnover frequencies either close to or significantly lower than the applied catalyst oscillation frequency, respectively. The “effective rate”, defined as the product of the catalytic turnover frequency and the turnover efficiency (ηTOE), was limited via two catalytic mechanisms: a leaky catalytic ratchet existed when molecules repeatedly traversed backward through the catalytic transition state upon catalyst oscillation, while a catalytic ratchet with low surface participation exhibited reduced formation of a gas-phase final product due to low surface product coverage. Furthermore, a single applied frequency yielding a maximum effective catalytic rate defined as the “resonance frequency” provided maximum combined benefit for catalytic rate and efficiency.

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This content will become publicly available on Tue Dec 23 00:00:00 EST 2025

Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023464; AC52-07NA27344

OSTI ID:: 2483271

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (37)

Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems Razdan, Neil K.; Lin, Ting C.; Bhan, Aditya Chemical Reviews, Vol. 123, Issue 6 https://doi.org/10.1021/acs.chemrev.2c00510	journal	February 2023
A Career in Catalysis: Enrique Iglesia Barton, David G.; Bhan, Aditya; Deshlahra, Prashant ACS Catalysis, Vol. 14, Issue 14 https://doi.org/10.1021/acscatal.4c02557	journal	June 2024
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S. Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.033	journal	August 2015
The activity of cadmium oxide as a catalyst for hydrogen dehydrogenation Balandin, A. A.; Ferapontov, V. A.; Tolstopyatova, A. A. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 9, Issue 10 https://doi.org/10.1007/BF00906559	journal	October 1960
The Multiplet Theory of Catalysis — Energy Factors in Catalysis Balandin, A. A. Russian Chemical Reviews, Vol. 33, Issue 5 https://doi.org/10.1070/RC1964v033n05ABEH001407	journal	May 1964
Catalytic resonance of ammonia synthesis by simulated dynamic ruthenium crystal strain Wittreich, Gerhard R.; Liu, Shizhong; Dauenhauer, Paul J. Science Advances, Vol. 8, Issue 4 https://doi.org/10.1126/sciadv.abl6576	journal	January 2022
The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts Logadottir, A.; Rod, T. H.; Nørskov, J. K. Journal of Catalysis, Vol. 197, Issue 2 https://doi.org/10.1006/jcat.2000.3087	journal	January 2001
Dynamic Promotion of the Oxygen Evolution Reaction via Programmable Metal Oxides Gathmann, Sallye R.; Bartel, Christopher J.; Grabow, Lars C. ACS Energy Letters, Vol. 9, Issue 5 https://doi.org/10.1021/acsenergylett.4c00365	journal	April 2024
Atmospheric Plasma-Assisted Ammonia Synthesis Enhanced via Synergistic Catalytic Absorption Peng, Peng; Chen, Paul; Addy, Min ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 1 https://doi.org/10.1021/acssuschemeng.8b03887	journal	November 2018
Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis Mehta, Prateek; Barboun, Patrick; Herrera, Francisco A. Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0045-1	journal	April 2018
Lattice strain effects on CO oxidation on Pt(111) Grabow, Lars; Xu, Ye; Mavrikakis, Manos Physical Chemistry Chemical Physics, Vol. 8, Issue 29 https://doi.org/10.1039/b606131a	journal	January 2006
Tunable intrinsic strain in two-dimensional transition metal electrocatalysts Wang, Lei; Zeng, Zhenhua; Gao, Wenpei Science, Vol. 363, Issue 6429 https://doi.org/10.1126/science.aat8051	journal	February 2019
Dynamic Control of Elementary Step Energetics via Pulsed Illumination Enhances Photocatalysis on Metal Nanoparticles Qi, Ji; Resasco, Joaquin; Robatjazi, Hossein ACS Energy Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsenergylett.0c01978	journal	October 2020
Alumina Graphene Catalytic Condenser for Programmable Solid Acids Onn, Tzia Ming; Gathmann, Sallye R.; Wang, Yuxin JACS Au, Vol. 2, Issue 5 https://doi.org/10.1021/jacsau.2c00114	journal	May 2022
Platinum Graphene Catalytic Condenser for Millisecond Programmable Metal Surfaces Onn, Tzia Ming; Gathmann, Sallye R.; Guo, Silu Journal of the American Chemical Society, Vol. 144, Issue 48 https://doi.org/10.1021/jacs.2c09481	journal	November 2022
Flexible and Extensive Platinum Ion Gel Condensers for Programmable Catalysis Onn, Tzia Ming; Oh, Kyung-Ryul; Adrahtas, Demetra Z. ACS Nano, Vol. 18, Issue 1 https://doi.org/10.1021/acsnano.3c09815	journal	December 2023
Alumina–Titania Nanolaminate Condensers for Hot Programmable Catalysis Oh, Kyung-Ryul; Walton, Amber; Chalmers, Jason A. ACS Materials Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acsmaterialslett.4c00652	journal	July 2024
Principles of Dynamic Heterogeneous Catalysis: Surface Resonance and Turnover Frequency Response Ardagh, M. Alexander; Abdelrahman, Omar A.; Dauenhauer, Paul J. ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01606	journal	May 2019
The Catalytic Mechanics of Dynamic Surfaces: Stimulating Methods for Promoting Catalytic Resonance Shetty, Manish; Walton, Amber; Gathmann, Sallye R. ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c03336	journal	September 2020
Catalytic resonance theory: superVolcanoes, catalytic molecular pumps, and oscillatory steady state Ardagh, M. Alexander; Birol, Turan; Zhang, Qi Catalysis Science & Technology, Vol. 9, Issue 18 https://doi.org/10.1039/C9CY01543D	journal	January 2019
Catalytic resonance theory: Negative dynamic surfaces for programmable catalysts Gathmann, Sallye R.; Ardagh, M. Alexander; Dauenhauer, Paul J. Chem Catalysis, Vol. 2, Issue 1 https://doi.org/10.1016/j.checat.2021.12.006	journal	January 2022
Clarifying mechanisms and kinetics of programmable catalysis Foley, Brandon L.; Razdan, Neil K. iScience, Vol. 27, Issue 4 https://doi.org/10.1016/j.isci.2024.109543	journal	April 2024
Nonequilibrium steady states, ratchets, and kinetic asymmetry Astumian, R. Dean Matter, Vol. 6, Issue 8 https://doi.org/10.1016/j.matt.2023.07.007	journal	August 2023
Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction Borsley, Stefan; Leigh, David A.; Roberts, Benjamin M. W. Angewandte Chemie International Edition, Vol. 63, Issue 23 https://doi.org/10.1002/anie.202400495	journal	May 2024
Catalytic resonance theory: the catalytic mechanics of programmable ratchets Murphy, Madeline A.; Gathmann, Sallye R.; Getman, Rachel Chemical Science, Vol. 15, Issue 34 https://doi.org/10.1039/D4SC04069D	journal	January 2024
Catalytic resonance theory: parallel reaction pathway control Ardagh, M. Alexander; Shetty, Manish; Kuznetsov, Anatoliy Chemical Science, Vol. 11, Issue 13 https://doi.org/10.1039/C9SC06140A	journal	January 2020
Writing the Programs of Programmable Catalysis Psarellis, Yorgos M.; Kavousanakis, Michail E.; Dauenhauer, Paul J. ACS Catalysis, Vol. 13, Issue 11 https://doi.org/10.1021/acscatal.3c00864	journal	May 2023
Up up down down left right left right B A Start for the catalytic hackers of programmable materials Dauenhauer, Paul J. Matter, Vol. 6, Issue 12 https://doi.org/10.1016/j.matt.2023.11.008	journal	December 2023
Energy Flows in Static and Programmable Catalysts Abdelrahman, Omar A.; Dauenhauer, Paul J. ACS Energy Letters, Vol. 8, Issue 5 https://doi.org/10.1021/acsenergylett.3c00522	journal	April 2023
Reciprocal Relations in Irreversible Processes. I. Onsager, Lars Physical Review, Vol. 37, Issue 4 https://doi.org/10.1103/PhysRev.37.405	journal	February 1931
Non-equilibrium Steady States in Catalysis, Molecular Motors, and Supramolecular Materials: Why Networks and Language Matter Aprahamian, Ivan; Goldup, Stephen M. Journal of the American Chemical Society, Vol. 145, Issue 26 https://doi.org/10.1021/jacs.2c12665	journal	June 2023
“If Pigs Could Fly” Chemistry: A Tutorial on the Principle of Microscopic Reversibility Blackmond, Donna G. Angewandte Chemie International Edition, Vol. 48, Issue 15 https://doi.org/10.1002/anie.200804566	journal	December 2008
Rates and Reversibilities in Interconnected Reaction Networks Lin, Ting C.; Razdan, Neil K.; Bhan, Aditya ACS Catalysis, Vol. 12, Issue 5 https://doi.org/10.1021/acscatal.1c05344	journal	February 2022
Catalytic resonance theory: Circumfluence of programmable catalytic loops Murphy, Madeline A.; Gathmann, Sallye R.; Bartel, Christopher J. Journal of Catalysis, Vol. 430 https://doi.org/10.1016/j.jcat.2024.115343	journal	February 2024
Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces Fields, Meredith; Tsai, Charlie; Chen, Leanne D. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.6b03403	journal	March 2017
Establishing and Understanding Adsorption–Energy Scaling Relations with Negative Slopes Su, Hai-Yan; Sun, Keju; Wang, Wei-Qi The Journal of Physical Chemistry Letters, Vol. 7, Issue 24 https://doi.org/10.1021/acs.jpclett.6b02430	journal	November 2016
Data for Catalytic Resonance Theory: Turnover Efficiency and the Resonance Frequency Dauenhauer, Paul; Hopkins, Justin A.; Foley, Brandon R. Data Repository for the University of Minnesota (DRUM) https://doi.org/10.13020/egsm-k060	dataset	January 2024

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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42 ENGINEERING
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Catalytic Resonance Theory: Turnover Efficiency and the Resonance Frequency

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