Modelling and Simulating CO2 Electro-Reduction to Formic Acid Using Microfluidic Electrolytic Cells: The Influence of Bi-Sn Catalyst and 1-Ethyl-3-Methyl Imidazolium Tetra-Fluoroborate Electrolyte on Cell Performance

A modified steady-state numerical model is developed for the electrochemical reduction of CO2 to formic acid. The numerical model achieves a CD (current density) (~60 mA/cm2), FE-faradaic efficiency (~98%) and conversion (~80%) for CO2 electro-reduction to formic acid in a microfluidic cell. The model integrates charge and species transport, mass conservation, and momentum with electrochemistry. Specifically, the influences of Bi-Sn based nanoparticle catalyst (on the cathode surface) at different mole fractions and 1-ethyl-3-methyl imidazolium tetra-fluoroborate ([EMIM][BF4]) electrolyte, on CD, FE and CO2 conversion to formic acid is studied. The reaction is carried out at a constant concentration of electrolyte (85% v/v., [EMIM][BF4]). Based on the mass transfer characteristics analysis (concentration contours), mole ratio 0.5:0.5 Bi-Sn catalyst displays the highest CO2 mole consumption in the cathode gas channel. After validating with experimental data (polarisation curves) from literature, extensive simulations reveal performance measure: CD, FE and CO2 conversion. Increasing the negative cathode potential increases the current densities for both formic acid and H2 formations. However, H2 formations are minimal as a result of insufficient hydrogen ions in the ionic liquid electrolyte. Moreover, the limited hydrogen ions have a negative effect on formic acid CD. As CO2 flow rate increases, CD, FE and CO2 conversion increases.

Effects of Formic Acid on the Chemical State and Morphology of As-synthesized and Annealed ZnO Films

Zinc oxide thin films with various microstructures were grown on substrates by using HCOOH-sols. The reaction mechanism of the sol system was investigated by performing an XPS analysis of as-synthesized films, due to the products of hydrolysis and condensation in the sol system contributing to the chemical state of the as-synthesized films. The chemical structures of the assynthesized films related to the microstructures of the final annealed films were also studied. The results of the Zn 2p3/2, C 1s and O1s XPS patterns indicate that the hydrolysis reaction in the sol system is strongly influenced by the HCOOH agent. The results of XRD and FE-SEM demonstrated the microstructures of the annealed films are related to the content of hydrolyzed zinc hydrate (Zn-OH) species present, and that content of the Zn-OH species in the sol system increases the HCOOH adding, and these Zn-OH species existing in the sol phase are responsible for large ZnO crystallites in the final annealed films.