Cu2O-based catalysts for the electrochemical reduction of CO2 at gas-diffusion electrodes

Gas-diffusion electrodes are prepared with commercial Cu2O and Cu2O–ZnO mixtures deposited onto carbon papers and evaluated for the continuous CO2 gas phase electroreduction in a filter-press electrochemical cell. The process mainly produced methanol, as well as small quantities of ethanol and n-propanol. The analysis includes the evaluation of key variables with effect in the electroreduction process: current density (j = 10–40 mA cm−2), electrolyte flow/area ratio (Qe/A = 1–3 ml min−1 cm−2) and CO2 gas flow/area ratio (Qg/A = 10–40 ml min−1 cm−2), using a 0.5 M KHCO3 aqueous solution. The maximum CO2 conversion efficiency to liquid-phase products was 54.8% and 31.4% for Cu2O and Cu2O/ZnO-based electrodes at an applied potential of −1.39 and −1.16 V vs. Ag/AgCl, respectively. Besides, the Cu2O/ZnO electrodes are expected to catalyze the CO2 electroreduction for over 20 h. These results may provide new insights into the application of gas diffusion electrodes to alleviate mass transfer limitations in electrochemical systems for the transformation of CO2 to alcohols.The authors gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO), under the projects CTQ2013-48280-C3-1-R, CTQ2014-55716- REDT and Juan de la Cierva program (JCI-2012-12073)

Sn nanoparticles on gas diffusion electrodes: Synthesis, characterization and use for continuous CO2 electroreduction to formate

Electrochemical reduction of CO2 has been pointed out as an interesting strategy to convert CO2 into useful chemicals. In addition, coupling CO2 electroreduction with renewable energies would allow storing electricity from intermittent renewable sources such as wind or solar power. In this work, an easy and fast method is adapted for the synthesis of pure and carbon supported Sn nanoparticles. The resulting nanoparticles have been characterized by transmission electron microscopy and their electrocatalytic properties towards CO2 reduction evaluated by cyclic voltammetry. Carbon supported Sn nanoparticles have been subsequently used to prepare Gas Diffusion Electrodes (Sn/C-GDEs). The electrodes have been characterized by scanning electron microscopy and also by cyclic voltammetry. Finally, the electrodes were tested on a continuous and single pass CO2 electroreduction filter-press type cell system in aqueous solution, to obtain formate at ambient pressure and temperature. These Sn/C-GDEs allow working at high current densities with low catholyte flow. Thus, for instance, at 150 mA cm−2, a 70% Faradaic Efficiency (FE) was obtained with a formate concentration of 2.5 g L−1. Interestingly, by increasing the current density to 200 mA cm−2 and decreasing the flow rate, a concentration over 16 g L−1 was reached. Despite the high concentrations obtained, further research is still required to keep high FE operating at high current densities.This work was conducted under the framework of the Spanish Ministry of Economy and Competitiveness projects CTQ2013-48280-C3-1-R and CTQ2013-48280-C3-3-R. Andrés Del Castillo also acknowledges the research grant from University of Cantabria, co-financed by the Regional Government of Cantabria

Methanol electrosynthesis from CO2 at Cu2O/ZnO prompted by pyridine-based aqueous solutions

In this study, we examine the electrochemical-driven reduction of CO2 to methanol at Cu2O/ZnO gas diffusion electrodes in soluble pyridine-based electrolytes at different concentrations. The process is evaluated first by cyclic voltammetric analyses and then, for the continuous reduction of CO2 in a filter-press electrochemical cell. The results showed that the use of pyridine-based soluble co-catalysts lowered the overpotential for the electrochemical reduction of CO2, enhancing also reaction performance (i.e. reaction rate and Faradaic efficiency). Reaction outcome is discussed on the basis of the role that N-ligands play on the mechanism and the inductive effect caused by the electron-releasing or electron-withdrawing substituents of the aromatic ring. In particular, the maximum methanol formation rate and Faradaic efficiency reached at the 2-methylpyridine (with electron-releasing substituents)-based system with a pH of 7.6 and an applied current density of j = 1 mA cm−2 were r = 2.91 μmol m−2 s−1 and FE = 16.86%, respectively. These values significantly enhance those obtained in the absence of any molecular catalyst (r = 0.21 μmol m−2 s−1 and FE = 1.2%). The performance was further enhanced when lowering the electrolyte pH by adding HCl (r = 4.42 μmol m−2 s−1 and FE = 25.6% at pH = 5), although the system showed deactivation in the long run (5 h) which appears largely to be due to a change in product selectivity of the reaction (i.e. formation of ethylene).The authors gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO), under the projects CTQ2013-48280-C3-1-R, CTQ2014-55716-REDT and Juan de la Cierva program (JCI-2012-12073)