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Model-based Experimental Design in Electrochemistry 10.17863/CAM.18768 Nguyen, H. Viet Fisher, Adrian The following thesis applies an experimental design framework to investigate properties of electron transfer kinetics and homogeneous catalytic reactions. The approach is model-based and the classical Butler-Volmer description is chosen to describe the fundamental electrochemical reaction at a conductive interface. The methodology focuses on two significant design variables: the applied potential at the electrode and mass transport mode induced by physical arrangement. An important problem in electrochemistry is the recovery of model parameters from output current measurements. In this work, the identifiability function is proposed as a measure of correspondence between the parameters and output variable. Under diffusion-limit conditions, plain Monte Carlo optimization shows that the function is globally non-identifiable, or equivalently the correspondence is generally non-unique. However by selecting linear voltammetry as the applied potential, the primary parameters in the Butler-Volmer description are theoretically recovered from a single set of data. The result is accomplished via applications of Sobol ranking to reduce the parameter set and a sensitivity equation to inverse these parameters. The use of hydrodynamic tools for investigating electron transfer reactions is next considered. The work initially focuses on the rotating disk and its generalization - the rocking disk mechanism. A numerical framework is developed to analyze the latter, most notably the derivation of a Levich-like expression for the limiting current. The results are then used to compute corresponding identifiability functions for each of the above configurations. Potential effectiveness of each device in recovering kinetic parameters are straightforwardly evaluated by comparing the functional values. Furthermore, another hydrodynamic device - the rotating drum, which is highly suitable for viscous and resistive solvents, is theoretically analyzed. Combined with previous results, this rotating drum configuration shows promising potential as an alternative tool to traditional electrode arrangement. The final chapter illustrates the combination of modulated input signal and appro- priate mass transport regimes to express electro-catalytic effects. An AC voltammetry technique plays an important role in this approach and is discussed step-by-step from simple redox reaction to the complete EC′ catalytic mechanism. A general algorithm based on forward and inverse Fourier transform functions for extracting harmonic currents from the total current is presented. The catalytic effect is evaluated and compared for three cases: macro, micro electrodes under diffusion control condition and in micro fluidic environments. Experimental data are also included to support the simulated design results. University of Cambridge 2018-07-31 Thesis Doctoral Doctor of Philosophy (PhD) en https://www.repository.cam.ac.uk/handle/1810/271773 https://www.repository.cam.ac.uk/bitstreams/a6c05d54-63b9-42c3-bedd-2c34af03a018/download 87eda9de84448d1f82354d60eee3eb5f https://www.repository.cam.ac.uk/bitstreams/339d50d0-7b4b-43ec-be25-bd45d02ed1f6/download ad3b78496458ee6c102c86fc00de83fb https://www.rioxx.net/licenses/all-rights-reserved/ Electrochemistry Electro-catalysis Monte Carlo Sampling Fast Fourier Transform