Efficient Electrochemical Reduction through Flow Cells Using Spherical-Polymer Based Carbon Supported Catalysts as Fixed-Bed Electrode
Authors: Schmidpeter Jana , Unger Amalia , Peña Leidy , Shimelis Olga , Abrahamson Joe , Glaesel Jan , Schulz Michael , Etzold Bastian J.M. 
Published: August 2024

The transition to economically friendly feedstocks and the electrification of chemical synthesis reactions gained much attention in the recent years. To be able to compete with the conventional processes, it is crucial not only to concentrate on the electrochemical reactions itself but also to constantly improve the reactor concepts. A vast variety of designs are imaginable and already well-described – from a simple, undivided beaker cell setup to a divided flow cell with separate electrolytes at cathode and anode. [1] As electrode material not only flat metal electrodes are studied, but also the concept of using carbon supported metal nanoparticles is well-known to employ high dispersion to lower the total amount of required metal. [2,3] While there are already commercial flow reactors and electrodes available for electrosynthesis with flat standard electrodes, reactors using a fixed-bed of porous carbon with nanodispersed metals as electrode just recently started to attract attention. [4] Dealing with the pressure drop over the catalyst bed, while the electrical contact is still ensured, are key challenges for this reactor design. Spherical polymer-based carbons (SPBC) combine porous carbons properties with a high purity and especially spherical character. [5] While these advantages led already to commercial products for chromatographic applications (e.g. Carboxen®) the potential regarding flow-electrochemistry has not been leveraged. Key developments for this are reproducible synthesis procedures to deposit active metal on the SPBCs and the design of an electrochemical flow cell using these catalysts in a fixed-bed electrode configuration.

The first part of this work presents the deposition of Cu through different impregnation and reduction procedures on a SPBC (Carboxen® 1032, 50 µm, Merck). The carbon was characterized by physisorption, TPD-MS, TPO, Raman and SEM. The resulting metal-impregnated carbon catalysts were additionally investigated regarding the metal loading. Using the applied impregnation and reduction parameters targeted metal loadings (3 – 20 wt%) could be well achieved. The second part focuses on the design and commissioning of a flow-cell for the application of the SPBC-supported catalysts as a fixed-bed at the cathode side. Electrochemical synthesis reactions are targeted in the cell and the reduction of 5-HMF to BHMF was chosen as the test reaction in this work. In the framework of the cell development multiple aspects not only regarding the construction but also reaction engineering issues had to be considered: material stability of the pump, fixation and pressure drop of catalyst bed, choice of electrolyte, effect of dissolved oxygen in the catholyte, optimal flow rate, reliable electrochemical protocol and selection of contact material. The latter has to be a compromise between chemical inertness and an enhanced electron transfer between the catalyst bed and the contact material (e.g. soft foil vs. hard metal). Figure 1A shows the current voltage characteristics of two possible contact materials (graphite foil, boron-doped diamond (BDD)) in the targeted electrolyte (0.5M borate buffer with 0.25M potassium chloride). Here, the graphite foil clearly shows a higher activity towards the hydrogen evolution reaction which may result in a less effective electrolysis later on. The comparison of BDD as contact material without and with a catalyst bed (Carboxen® 1032 loaded with 20 wt% Cu) resulted in a significant shift in the current voltage characteristic to lower overpotentials. Therefore, the electronic contact with the carbon bed is clearly enabled and the carbon spheres loaded with copper catalyze the reaction. Figure 1B presents the results of the test reaction with the conversion of the educt 5-HMF as well as the selectivity to the targeted product BHMF over the reaction time with BDD as contact material without and with a fixed bed of Cu/SPBC catalyst. The experiments prove full 5-HMF conversion within 23 h on stream in combination with a high selectivity towards BHMF with the catalyst bed. The mass-based productivity reaches values of up to 1.78 mmol h-1 gCu
-1 and is therefore about 15 times higher compared to the use of conventional Cu foil (Pliterature = 0.11 mmol h-1 gCu
-1 [6]). It is possible that due to the metal-support approach in the fixed-bed configuration, the copper is leveraged more efficiently and small amounts allow to provide sufficient metal surface area for the catalytic reaction.

References: [1] Perry et al. J. Electrochem. Soc. (2020), [2] Lee et al. ChemSusChem (2021), [3] Schmitt et al. Energy Adv. (2023), [4] Crettenand WO2020/120776 A1 (2020), [5] Klefer et al. Chemcial Engineering & Technology (2016), [6] De Luna et al. ChemSusChem (2022).

Figure 1