Elementary Steps and Mechanisms: Sections 5.1 – 5.2

Freund, H.-J.; Santen, Rutger A. van; Neurock, M.; Boudart, M.; Mullins, C. B.; Norskov, J. K.; Stoltze, P.; Tamura, K.; Naito, S.; Jonkers, G.; Ertl, G.

doi:10.1002/9783527619474.ch5a

“…The most advanced method is microkinetic modelling, considering all elementary reaction steps according to a proposed mechanism [11] . This approach can be simplified by assuming one specific rate‐determining step (rds), or multiple steps in control, [12] and using the steady‐state approximation to derive a kinetic equation containing all concentrations, the rate constant of the rds (

{{k}_{0}{e}^{-{{{E}_{act}}\over{RT}}}}

), as well as all equilibrium constants of all other elementary steps.…”

Section: Kinetic Analysis In Heterogeneous Catalysismentioning

confidence: 99%

Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

Lefferts

2024

Angew Chem Int Ed

4

0

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Best practices in testing heterogeneous catalysts are translated to plasma‐catalytic experiments. Independent determination of plasma‐catalytic and plasma‐chemical contributions is essential. Non‐porous catalyst particles are preferred because active sites inside sub‐micron pores cannot contribute. Temperature variation is needed to determine kinetics, despite the complexity of thermal effects in plasma. Rigorous checks on catalyst deactivation and mass balance are needed. Plasma enhanced reversed reactions should be minimized by keeping conversion low and far from thermodynamic equilibrium, preventing underestimation of the rate of forward reaction. In contrast, plasma‐catalytic studies often aim at conversions surpassing thermodynamic equilibrium, not obtaining any information on kinetics. Calculation of catalyst activity per active sites (turn‐over‐frequency) requires also appropriate characterization to determine the number of active sites.The relationship between kinetics and thermodynamics for plasma‐catalysis is discussed using endothermic decomposition of CO2 and exothermic synthesis of ammonia from N2 and H2 as examples. Assuming Langmuir–Hinshelwood and Eley‐Rideal mechanisms, the effect of excitation of reactant molecules on activation barriers and surface coverages are discussed, influencing reaction rates. The consequences of reversed reactions are considered. Plasma‐catalysis with catalysts applied for thermal catalysis at much higher temperature should be avoided, as adsorbed species are bonded too strongly resulting in low rates.

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Surface Microcalorimetry

Gottfried

¹

,

Schuster

²

2015

Surface and Interface Science

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Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

Lefferts

2024

Angewandte Chemie

3

0

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Best practices in testing heterogeneous catalysts are translated to plasma‐catalytic experiments. Independent determination of plasma‐catalytic and plasma‐chemical contributions is essential. Non‐porous catalyst particles are preferred because active sites inside sub‐micron pores cannot contribute. Temperature variation is needed to determine kinetics, despite the complexity of thermal effects in plasma. Rigorous checks on catalyst deactivation and mass balance are needed. Plasma enhanced reversed reactions should be minimized by keeping conversion low and far from thermodynamic equilibrium, preventing underestimation of the rate of forward reaction. In contrast, plasma‐catalytic studies often aim at conversions surpassing thermodynamic equilibrium, not obtaining any information on kinetics. Calculation of catalyst activity per active sites (turn‐over‐frequency) requires also appropriate characterization to determine the number of active sites.The relationship between kinetics and thermodynamics for plasma‐catalysis is discussed using endothermic decomposition of CO2 and exothermic synthesis of ammonia from N2 and H2 as examples. Assuming Langmuir–Hinshelwood and Eley‐Rideal mechanisms, the effect of excitation of reactant molecules on activation barriers and surface coverages are discussed, influencing reaction rates. The consequences of reversed reactions are considered. Plasma‐catalysis with catalysts applied for thermal catalysis at much higher temperature should be avoided, as adsorbed species are bonded too strongly resulting in low rates.

show abstract

Elementary Steps and Mechanisms: Sections 5.1 – 5.2

Cited by 8 publications

References 714 publications

Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

Surface Microcalorimetry

Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

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