20-Fold Increased Limiting Currents in Oxygen Reduction with Cu-tmpa by Replacing Flow-By with Flow-Through Electrodes

ACS Sustainable Chemistry & Engineering, vol. 12, pp. 12909–12918

Abstract

High Resolution Image Download MS PowerPoint Slide Electrochemical oxygen reduction is a promising and sustainable alternative to the current industrial production method for hydrogen peroxide (H 2 O 2 ), which is a green oxidant in many (emerging) applications in the chemical industry, water treatment, and fuel cells. Low solubility of O 2 in water causes severe mass transfer limitations and loss of H 2 O 2 selectivity at industrially relevant current densities, complicating the development of practical-scale electrochemical H 2 O 2 synthesis systems. We tested a flow-by and flow-through configuration and suspension electrodes in an electrochemical flow cell to investigate the influence of electrode configuration and flow conditions on mass transfer and H 2 O 2 production. We monitored the H 2 O 2 production using Cu-tmpa (tmpa = tris(2-pyridylmethyl)amine) as a homogeneous copper-based catalyst in a pH-neutral phosphate buffer during 1 h of catalysis and estimated the limiting current density from CV scans. We achieve the highest H 2 O 2 production and a 15–20 times higher geometrical limiting current density in the flow-through configuration compared to the flow-by configuration due to the increased surface area and foam structure that improved mass transfer. The activated carbon (AC) material in suspension electrodes, which have an even larger surface area, decomposes all produced H 2 O 2 and proves unsuitable for H 2 O 2 synthesis. Although the mass transfer limitations seem to be alleviated on the microscale in the flow-through system, the high O 2 consumption and H 2 O 2 production cause challenges in maintaining the initially reached current density and Faradaic efficiency (FE). The decreasing ratio between the concentrations of the O 2 and H 2 O 2 in the bulk electrolyte will likely pose a challenge when proceeding to larger systems with longer electrodes. Tuning the reactor design and operating conditions will be essential in maximizing the FE and current density.

Authors 5

1. Nathalie E. G. Ligthart

   Delft University of Technology

   Affiliation as printed

   Department of Chemical Engineering, Delft University of Technology, Van der Maasweg 9, 2629HZ Delft, The Netherlands

2. Phebe H. van Langevelde Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

3. Johan Tiemen Padding

   Delft University of Technology

   Affiliation as printed

   Department of Process and Energy, Delft University of Technology, Leeghwaterstraat 39, 2628 CB Delft, The Netherlands

4. Dennis G. H. Hetterscheid Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

5. David A. Vermaas corresponding

   Delft University of Technology

   Affiliation as printed

   Department of Chemical Engineering, Delft University of Technology, Van der Maasweg 9, 2629HZ Delft, The Netherlands