Publications

Local Reaction Environment Deviations within Gas Diffusion Electrode Pores for CO2 Electrolysis

The local conditions inside a gas diffusion electrode (GDE) pore, especially in the electrical double layer (EDL) region, influence the charge transfer reactions and the selectivity of desired CO2ER products. Most GDE computational models ignore the EDL or are limited in their applicability at high potentials. In this work, we present a continuum model to describe the local environment inside a catalytic pore at varying potentials, electrolyte concentrations and pore diameters. The systems studied in this work are based on an Ag catalyst in contact with KHCO3 solution. Our study shows that steric effects dominate the local environment at high cathodic potentials (≪−25 mV vs pzc at the OHP), leading to a radial drop of CO2 concentration. We also observe a drop in pH value within 1 nm of the reaction plane due to electrostatic repulsion and attraction of OH and H+ ions, respectively. We studied the influence of pore radii (1–10 nm) on electric field and concentrations. Pores with a radius smaller than 5 nm show a higher mean potential, which lowers the mean CO2 concentration. Pores with a favourable local environment can be designed by regulating the ratio between the pore radius and Debye length.

Esaar N. Butt, Johan T. Padding and Remco Hartkamp


Electrochemical cell design and performance evaluation of polyvinyl ferrocene/carbon nanotube electrodes for selective formate separation

Selective ion separation is a fundamental challenge with applications ranging from the manufacturing of pharmaceuticals & industrial salts to water desalination. In particular, the separation of formate, a primary product of electrochemical carbon dioxide reduction, has attracted attention not only to reduce carbon emissions and energy costs but to provide new routes to value-added chemicals. In the present study, selective formate separation from an aqueous solution is demonstrated using an electrochemical flow cell with symmetric redox-active polyvinyl ferrocene electrodes. An electrosorption system equipped with an electrosorption cell, inline conductivity, and pH sensors was constructed to provide real-time measurements of the formate adsorption performance in continuous flow mode while varying operating conditions such as the flow rate, cell voltage, and electrolyte concentration. These parameters were optimized using a Box–Behnken experimental design to improve the formate adsorption selectivity. The flow cell results showed a selectivity higher than 6.0 toward the removal of formate in an electrolyte containing a 30-fold excess of perchlorate under optimal operation conditions (i.e., 0.5 mL/min flow rate, 1.0 V, and 15 mM electrolyte concentration). The performance of the flow cell was also tested using a solution that contained different liquid CO2 reduction products, and formate separation was achieved. The results suggest that the proper design of the electrochemical cell and efficient operation of the flow platform pave the way for scaling up the technology for selective formate separation.

Sevgi Polat, Ruud Kortlever, Hüseyin Burak Eral


Optimization and continuous-flow operation of electrochemically mediated selective formate separation by polyvinyl ferrocene/graphene oxide electrodes

Electrochemical carbon dioxide (CO2) reduction is a promising route to convert intermittent renewable energy into fuels and valuable chemical products. Separation of CO2 reduction products by ion-selective electrochemical technology may play a decisive role in the pursuit of commercially viable CO2 reduction processes. Selective separation of formate, one of the main CO2 reduction products, is assessed in the present study in an electrochemical flow cell with symmetric redox-active polyvinyl ferrocene (PVF) functionalized graphene oxide (GO) electrodes. First, experimental parameters such as the PVF/GO ratio, sonication time, and ultrasonic amplitude, were optimized in the electrode preparation process to improve the formate adsorption efficiency on a lab scale (1 × 2 cm electrodes) under static conditions. The electrochemical and morphological characteristics of the electrodes were investigated by cyclic voltammetry and scanning electron microscopy. To demonstrate continuous-flow operation, an electrosorption flow cell (8 × 8 cm) providing inline measurements was constructed. The flow cell results showed selectivity at > 5.5 toward the removal of formate from an electrolyte containing perchlorate at an excess of 30 times the normal value. The performance of the electrosorption cell was also tested using a mixture of methanol, ethanol, formate, and acetaldehyde produced in a CO2 reduction electrolyzer. In this demonstration, formate separation was achieved with a selectivity of > 4.0. The results suggest that the optimized design of the electrochemical cell and operation conditions of the flow platform pave the way for scaling up selective formate separation with PVF/GO electrodes.

Sevgi Polat, Ruud Kortlever, Hüseyin Burak Eral


The optimal electrode pore size and channel width in electrochemical flow cells

Microfluidic fuel cells, electrolyzers, and redox flow batteries utilize laminar flow channels to provide reactants, remove products and avoid their crossover. These devices often also employ porous flow-through electrodes as they offer a high surface area for the reaction and excellent mass transfer. The geometrical features of these electrodes and flow channels strongly influence energy efficiency. We derive explicit analytical relations for the optimal flow channel width and porous electrode volumetric surface area from the perspective of energy efficiency. These expressions are verified using a two-dimensional tertiary current distribution and porous electrode flow model in COMSOL and are shown to be able to predict optimal parameters in commonly used flow-through and interdigitated flow fields. The obtained analytical models can dramatically shorten modelling time and expedite the industrial design process. The optimal channel width and pore sizes we obtain, in the order of 100 microns and 1 micron respectively, are much smaller than those often used. This shows that there is a significant room for improvement of energy efficiency in flow cells that can sustain the resulting pressure drop.

A. Bhadra, J.W. Haverkort


Earlier publications