TY - JOUR
T1 - A Geometric Interpretation of Kinetic Zone Diagrams in Electrochemistry
AU - Plumeré, Nicolas
AU - Johnson, Ben A.
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/12/18
Y1 - 2024/12/18
N2 - Electrochemical systems with increasing complexity are gaining importance in catalytic energy conversion applications. Due to the interplay between transport phenomena and chemical kinetics, predicting optimization is a challenge, with numerous parameters controlling the overall performance. Zone diagrams provide a way to identify specific kinetic regimes and track how variations in the governing parameters translate the system between either adverse or optimal kinetic states. However, the current procedures for constructing zone diagrams are restricted to simplified systems with a minimal number of governing parameters. We present a computationally based method that maps the entire parameter space of multidimensional electrochemical systems and automatically identifies kinetic regimes. Once the current output over a discrete set of parameters is interpreted as a geometric surface, its geometry encodes all of the information needed to construct a zone diagram. Zone boundaries and limiting zones are defined by curved and flat regions, respectively. This geometric framework enables a systematic exploration of the parameter space, which is not readily accessible by analytical or direct numerical methods. This will become increasingly valuable for the rational design of electrochemical systems with intrinsically high complexity.
AB - Electrochemical systems with increasing complexity are gaining importance in catalytic energy conversion applications. Due to the interplay between transport phenomena and chemical kinetics, predicting optimization is a challenge, with numerous parameters controlling the overall performance. Zone diagrams provide a way to identify specific kinetic regimes and track how variations in the governing parameters translate the system between either adverse or optimal kinetic states. However, the current procedures for constructing zone diagrams are restricted to simplified systems with a minimal number of governing parameters. We present a computationally based method that maps the entire parameter space of multidimensional electrochemical systems and automatically identifies kinetic regimes. Once the current output over a discrete set of parameters is interpreted as a geometric surface, its geometry encodes all of the information needed to construct a zone diagram. Zone boundaries and limiting zones are defined by curved and flat regions, respectively. This geometric framework enables a systematic exploration of the parameter space, which is not readily accessible by analytical or direct numerical methods. This will become increasingly valuable for the rational design of electrochemical systems with intrinsically high complexity.
UR - http://www.scopus.com/inward/record.url?scp=85211083700&partnerID=8YFLogxK
U2 - 10.1021/jacs.4c13271
DO - 10.1021/jacs.4c13271
M3 - Article
AN - SCOPUS:85211083700
SN - 0002-7863
VL - 146
SP - 34771
EP - 34785
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 50
ER -