RESUMO
Electrochemical oxygen reduction is a promising and sustainable alternative to the current industrial production method for hydrogen peroxide (H2O2), which is a green oxidant in many (emerging) applications in the chemical industry, water treatment, and fuel cells. Low solubility of O2 in water causes severe mass transfer limitations and loss of H2O2 selectivity at industrially relevant current densities, complicating the development of practical-scale electrochemical H2O2 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 H2O2 production. We monitored the H2O2 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 H2O2 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 H2O2 and proves unsuitable for H2O2 synthesis. Although the mass transfer limitations seem to be alleviated on the microscale in the flow-through system, the high O2 consumption and H2O2 production cause challenges in maintaining the initially reached current density and Faradaic efficiency (FE). The decreasing ratio between the concentrations of the O2 and H2O2 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.
RESUMO
CO2 conversion is an important part of the transition towards clean fuels and chemicals. However, low solubility of CO2 in water and its slow diffusion cause mass transfer limitations in aqueous electrochemical CO2 reduction. This significantly limits the partial current densities towards any desired CO2-reduction product. We propose using flowable suspension electrodes to spread the current over a larger volume and alleviate mass transfer limitations, which could allow high partial current densities for CO2 conversion even in aqueous environments. To identify the requirements for a well-performing suspension electrode, we use a transmission line model to simulate the local electric and ionic current distributions throughout a channel and show that the electrocatalysis is best distributed over the catholyte volume when the electric, ionic and charge transfer resistances are balanced. In addition, we used electrochemical impedance spectroscopy to measure the different resistance contributions and correlated the results with rheology measurements to show that particle size and shape impact the ever-present trade-off between conductivity and flowability. We combine the modelling and experimental results to evaluate which carbon type is most suitable for use in a suspension electrode for CO2 reduction, and predict a good reaction distribution throughout activated carbon and carbon black suspensions. Finally, we tested several suspension electrodes in a CO2 electrolyzer. Even though mass transport limitations should be reduced, the CO partial current densities are capped at 2.8 mA cm-2, which may be due to engineering limitations. We conclude that using suspension electrodes is challenging for sensitive reactions like CO2 reduction, and may be more suitable for use in other electrochemical conversion reactions suffering from mass transfer limitations that are less affected by competing reactions and contaminations.