We created a digital twin of our autonomous workflow by coupling BO to COMSOL, enabling autonomous finite element simulations (Figure ). The finite element simulations incorporating parameters Ccat, Csub, and ν were coupled with BO, with nearly identical parameter constraints as our automated electrochemistry platform used further on. We used the digital twin to evaluate the performance of our CV descriptors, where we compared kc values calculated from equation 5 to the ground truth kc values that were input into the simulation. Additionally, we incorporated simulated measurement artifacts to ensure our descriptors were robust to practical experimental conditions. In this fully autonomous workflow, simulated experiments are automatically run, analyzed, and the next parameters to sample are suggested by the BO algorithm. We tested both the error-based and hysteresis-based descriptors by performing 15iteration autonomous experiments, with kreal spanning seven orders of magnitude (Supplementary Note SNB and Figure ). Parameters were constrained based on practical experimental values, with Csub ranging from 1 to 300 mM, Ccat ranging from 1 to 6 mM, and ν ranging from 1 mV/s to 5 V/s. A single point in the constrained parameter space was chosen randomly as the starting point of the autonomous experiment, and all subsequently sampled parameters were suggested by the BO algorithm. This initial seed point was the same for both descriptors characterized here, to ensure a fair comparison between methods. Figures 4b and Figure show the digital twin results of two BO campaigns with true kc = 10 M -1 s -1 using the error-based and hysteresis-based descriptors, respectively. We observed that the error-based descriptor led to poor convergence and displayed unpredictable behavior as the optimization proceeded. In contrast, optimization with the hysteresis-based descriptor estimated the correct kc value within 5% error after only 8 iterations on average (Figure ). We chose to use the hysteresis-based descriptor for all following autonomous experiments. Figure shows the BO trajectory across the kinetic zone diagram converging onto the KS zone. Figure also shows the improved accuracy and precision of the BO method vs. a random sampling approach for various values of kc. These results highlight the superior performance of the hysteresis-based descriptor, supporting its use in subsequent autonomous experiments.