Transient Pseudo-Random Binary Sequence Measurements for the Rapid Determination of Elementary Rate Constants for Heterogeneous Catalytic Reactions

Transient Pseudo-Random Binary Sequence Measurements for the Rapid Determination of Elementary Rate Constants for Heterogeneous Catalytic Reactions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Transient Pseudo-Random Binary Sequence Measurements for the Rapid Determination of Elementary Rate Constants for Heterogeneous Catalytic Reactions Robert Rioux, Zayne Weber, Alireze Javanmard, Ran Wang, Michael Janik, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9171848/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Accurate determination of elementary kinetic parameters is essential for rational heterogeneous catalyst design. Conventional steady-state approaches are time-consuming and provide limited mechanistic insight. Transient techniques offer richer kinetic data but are constrained by instrumentation-limited perturbations, model-simplifying assumptions, or specialized reactors. We demonstrate transient pseudo-random binary sequence (PRBS) perturbations as a rapid and broadband excitation approach for unbiased microkinetic analysis. A packed-bed reactor with a fast-acting valve delivered PRBS-driven CO pulses during CO oxidation over Pd/SiO2. The resulting transient outlet responses were measured at millisecond timescales and analyzed using an integrated microkinetic–reactor model. The approach enables simultaneous extraction of 10 elementary rate constants from a transient PRBS experiment. Steady-state simulations based on PRBS-fitted rate constants accurately predicted apparent activation energies, reaction orders, and the rate determining step. Compared with traditional steady-state workflows, PRBS experiments reduce experimental and analysis time by ~16-fold and ~4-fold, providing a practical platform for high-throughput, quantitative kinetic characterization. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Catalysis/Catalytic mechanisms Full Text Additional Declarations There is NO Competing Interest. Supplementary Files PRBSExperimentalSINatureCatalysis.docx NATCATAL-26030738 SI Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9171848","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":628400699,"identity":"cdc523bc-6ea8-4294-8b74-44159f3846a7","order_by":0,"name":"Robert 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Conventional steady-state approaches are time-consuming and provide limited mechanistic insight. Transient techniques offer richer kinetic data but are constrained by instrumentation-limited perturbations, model-simplifying assumptions, or specialized reactors. We demonstrate transient pseudo-random binary sequence (PRBS) perturbations as a rapid and broadband excitation approach for unbiased microkinetic analysis. A packed-bed reactor with a fast-acting valve delivered PRBS-driven CO pulses during CO oxidation over Pd/SiO2. The resulting transient outlet responses were measured at millisecond timescales and analyzed using an integrated microkinetic–reactor model. The approach enables simultaneous extraction of 10 elementary rate constants from a transient PRBS experiment. Steady-state simulations based on PRBS-fitted rate constants accurately predicted apparent activation energies, reaction orders, and the rate determining step. 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