*Result*: Machine learning-based predictive control using on-line model linearization: Application to an experimental electrochemical reactor.

*The electrochemical reaction-based process, a new type of chemical process that can generate valuable products using renewable electricity, is a sustainable alternative to the traditional chemical manufacturing processes. One promising research area of electrochemical reaction processing is to reduce carbon dioxide (CO 2) into carbon-based products, which can contribute to closing the carbon cycle if CO 2 is directly captured from the atmosphere. In this work, we demonstrate a model predictive control (MPC) scheme that uses a neural network (NN) model as the process model to implement real-time multi-input-multi-output (MIMO) control in an electrochemical reactor for CO 2 reduction. Specifically, a long short-term memory network (LSTM) model is developed using historical experimental data of the electrochemical reactor to capture the nonlinear input-output relationship as an alternative to the complex, first principles-based model. Furthermore, the Koopman operator method is used to linearize the LSTM model to reduce the nonlinear optimization step in the MPC to a well-understood and easy-to-solve quadratic programming (QP) problem. The performance of the LSTM model, Koopman-based optimization, and MPC using the linearization of the LSTM model are evaluated with various simulations as well as open-loop and closed-loop experiments. As the results, the proposed MPC scheme can drive the two output states, that are concentrations of the products (C 2 H 4 and CO), to their desired setpoints by computing optimal input variables (surface potential and electrode rotation speed) in real-time in closed-loop experiments. Furthermore, a transfer learning-based method is utilized to update the NN model to handle process variability. • Recurrent neural network model on-line linearization. • Model predictive control using linearized model. • Implementation on an experimental electrochemical reactor. • Transfer learning implementation for model update. [ABSTRACT FROM AUTHOR]*