Methods—A Potential–Dependent Thiele Modulus to Quantify the Effectiveness of Porous Electrocatalysts

Wan, Charles Tai-Chieh; Greco, Katharine V.; Alazmi, Amira; Darling, Robert M.; Chiang, Yet-Ming; Brushett, Fikile R.

doi:10.1149/1945-7111/ac34ce

Methods—A Potential–Dependent Thiele Modulus to Quantify the Effectiveness of Porous Electrocatalysts

Journal Article · Wed Dec 01 04:00:00 EST 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac34ce· OSTI ID:1983007

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Electrochemical reactors often employ high surface area electrocatalysts to accelerate volumetric reaction rates and increase productivity. While electrocatalysts can alleviate kinetic overpotentials, diffusional resistances at the pore-scale often prevent full catalyst utilization. The effect of intraparticle diffusion on the overall reaction rate can be quantified through an effectiveness factor expression governed by the Thiele modulus parameter. This analytical approach is integral to the development of catalytic structures for thermochemical processes and has previously been extended to electrochemical processes by accounting for the relationship between reaction kinetics and electrode overpotential. In this paper, we illustrate the method by deriving the expression for the potential-dependent Thiele modulus and using it to quantify the effectiveness factor for porous electrocatalytic structures. Specifically, we demonstrate the application of this mathematical framework to spherical microparticles as a function of applied overpotential across catalyst properties and reactant characteristics. The relative effects of kinetics and mass transport are related to overall reaction rates, revealing markedly lower catalyst utilization at increasing overpotential. Subsequently, we generalize the analysis to different catalyst shapes and provide guidance on the design of porous catalytic materials for use in electrochemical reactors.

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1983007

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 168; ISSN 0013-4651

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

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