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Modulation engineering : stimulation design for enhanced kinetic information from modulation-excitation experiments on catalytic systems

Valentijn De Coster, Nadadur Veeraraghavan Srinath, Parviz Yazdani (UGent) , Hilde Poelman (UGent) and Vladimir Galvita (UGent)
(2023) ACS CATALYSIS. 13(7). p.5084-5095
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Abstract
Modulation excitation (ME) with phase-sensitive detection (PSD) is an emerging strategy to selectively characterize catalytic species that actively participate in a chemical reaction. The commonly applied square-wave (SW) modulations, however, contain a limited frequency content, impeding rigorous kinetic analysis of short-lived reaction intermediates through PSD analysis by considering higher-order harmonics. To overcome this bottleneck, a "modulation engineering" approach is designed, whereby stimulation shapes with a complementary frequency content are superposed onto a base modulation, thus subjecting the system to a more complex frequency pattern in a single experiment. Building on practical and mathematical considerations, this design scheme's feasibility is demonstrated using a superposition of SW and rectangular wave stimulations, applied to H2/CO2 concentration modulation-excitation X-ray absorption spectroscopy of a Ni/MgFeAlO4 methane dry reforming (DRM) catalyst at the Fe and Ni K edge. Under redox conditions, PSD evidences Ni <-> Ni2+ and Fe0 <-> Fe2+ <-> Fe3+ redox events, wherein Fe2+ <-> Fe3+ transitions exhibit faster kinetics, adding insight into this material's redox functionalities under DRM conditions. This approach is extendable to other ME-based characterization techniques and provides a general, time-efficient framework to expand the transient kinetic insights that can be obtained for catalytic systems through ME with PSD.
Keywords
Catalysis, General Chemistry, X-ray absorption spectroscopy, phase-sensitive detection, Ni-Fe alloy, transient XAS, surface sensitivity, RAY-ABSORPTION SPECTROSCOPY, MULTIVARIATE CURVE RESOLUTION, IN-SITU, INFRARED-SPECTROSCOPY, REACTION CELL, ACTIVE-SITES, MCR-ALS, REDUCTION, METHANE, SUPPORT

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Citation

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MLA
De Coster, Valentijn, et al. “Modulation Engineering : Stimulation Design for Enhanced Kinetic Information from Modulation-Excitation Experiments on Catalytic Systems.” ACS CATALYSIS, vol. 13, no. 7, 2023, pp. 5084–95, doi:10.1021/acscatal.3c00646.
APA
De Coster, V., Srinath, N. V., Yazdani, P., Poelman, H., & Galvita, V. (2023). Modulation engineering : stimulation design for enhanced kinetic information from modulation-excitation experiments on catalytic systems. ACS CATALYSIS, 13(7), 5084–5095. https://doi.org/10.1021/acscatal.3c00646
Chicago author-date
De Coster, Valentijn, Nadadur Veeraraghavan Srinath, Parviz Yazdani, Hilde Poelman, and Vladimir Galvita. 2023. “Modulation Engineering : Stimulation Design for Enhanced Kinetic Information from Modulation-Excitation Experiments on Catalytic Systems.” ACS CATALYSIS 13 (7): 5084–95. https://doi.org/10.1021/acscatal.3c00646.
Chicago author-date (all authors)
De Coster, Valentijn, Nadadur Veeraraghavan Srinath, Parviz Yazdani, Hilde Poelman, and Vladimir Galvita. 2023. “Modulation Engineering : Stimulation Design for Enhanced Kinetic Information from Modulation-Excitation Experiments on Catalytic Systems.” ACS CATALYSIS 13 (7): 5084–5095. doi:10.1021/acscatal.3c00646.
Vancouver
1.
De Coster V, Srinath NV, Yazdani P, Poelman H, Galvita V. Modulation engineering : stimulation design for enhanced kinetic information from modulation-excitation experiments on catalytic systems. ACS CATALYSIS. 2023;13(7):5084–95.
IEEE
[1]
V. De Coster, N. V. Srinath, P. Yazdani, H. Poelman, and V. Galvita, “Modulation engineering : stimulation design for enhanced kinetic information from modulation-excitation experiments on catalytic systems,” ACS CATALYSIS, vol. 13, no. 7, pp. 5084–5095, 2023.
@article{01H6EB0F4JGRE8YE9XHD4BA870,
  abstract     = {{Modulation excitation (ME) with phase-sensitive detection (PSD) is an emerging strategy to selectively characterize catalytic species that actively participate in a chemical reaction. The commonly applied square-wave (SW) modulations, however, contain a limited frequency content, impeding rigorous kinetic analysis of short-lived reaction intermediates through PSD analysis by considering higher-order harmonics. To overcome this bottleneck, a "modulation engineering" approach is designed, whereby stimulation shapes with a complementary frequency content are superposed onto a base modulation, thus subjecting the system to a more complex frequency pattern in a single experiment. Building on practical and mathematical considerations, this design scheme's feasibility is demonstrated using a superposition of SW and rectangular wave stimulations, applied to H2/CO2 concentration modulation-excitation X-ray absorption spectroscopy of a Ni/MgFeAlO4 methane dry reforming (DRM) catalyst at the Fe and Ni K edge. Under redox conditions, PSD evidences Ni <-> Ni2+ and Fe0 <-> Fe2+ <-> Fe3+ redox events, wherein Fe2+ <-> Fe3+ transitions exhibit faster kinetics, adding insight into this material's redox functionalities under DRM conditions. This approach is extendable to other ME-based characterization techniques and provides a general, time-efficient framework to expand the transient kinetic insights that can be obtained for catalytic systems through ME with PSD.}},
  author       = {{De Coster, Valentijn and Srinath, Nadadur Veeraraghavan and Yazdani, Parviz and Poelman, Hilde and Galvita, Vladimir}},
  issn         = {{2155-5435}},
  journal      = {{ACS CATALYSIS}},
  keywords     = {{Catalysis,General Chemistry,X-ray absorption spectroscopy,phase-sensitive detection,Ni-Fe alloy,transient XAS,surface sensitivity,RAY-ABSORPTION SPECTROSCOPY,MULTIVARIATE CURVE RESOLUTION,IN-SITU,INFRARED-SPECTROSCOPY,REACTION CELL,ACTIVE-SITES,MCR-ALS,REDUCTION,METHANE,SUPPORT}},
  language     = {{eng}},
  number       = {{7}},
  pages        = {{5084--5095}},
  title        = {{Modulation engineering : stimulation design for enhanced kinetic information from modulation-excitation experiments on catalytic systems}},
  url          = {{http://doi.org/10.1021/acscatal.3c00646}},
  volume       = {{13}},
  year         = {{2023}},
}
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