The carbon dioxide electrocatalytic reduction is central for the development of regenerative cycles of electrochemical energy conversion and storage. Herein, the gaseous products of the CO 2 electroreduction were monitored by using an electrochemical cell on line coupled to a differential electrochemical mass spectrometer (DEMS), aiming at searching for electrocatalysts with high selectivity for CO formation. The results showed that, among the studied materials, the Cu 4 Sn/C alloy nanoparticles were stable during potentiostatic polarizations as revealed by in situ X-ray absorption spectroscopy (XAS), and the on line DEMS measurements showed the production of CO, suppression of methane and ethylene formations, and diminishing of the hydrogen evolution reaction, in relation to that on pure Cu 2 O-Cu/C. The faradaic efficiencies for CO formation were 13 and 23% for Cu 4 Sn/C and Au/C (a known electrocatalyst for CO), respectively, determined by experiments of in line gas chromatography (GC). The selectivity of Cu 4 Sn/C for CO formation was ascribed to the role of Sn atoms on stabilizing adsorbed HCOO intermediates, and hindering further hydrogenation, letting CO free for desorption. These results are expected to be used as a guide for further development of electrocatalysts with a fine-tuning of composition for increasing the faradaic efficiency of CO 2 electroreduction to CO.Keywords: CO 2 electrochemical reduction, on line DEMS, in line GC, CO formation, Cu 4 Sn/C alloy
IntroductionConcomitantly with the growth of the world population, the energy demand is increasing. To satisfy this scenario, fossil fuels, such as oil, coal and natural gas, are being exhaustively used. Unfortunately, together to the dependence on these fuels, large amounts of carbon dioxide (CO 2 ) are emitted into the environment and, so, this is not a sustainable cycle. This has initiated research projects to investigate efficient processes for using the available CO 2 in the atmosphere. The electrochemical reduction of carbon dioxide is, in principle, an efficient manner that can be explored. In this context, the electroreduction of CO 2 to fuels with high-energy density or to industrial chemicals, that can be further processed to produce useful fuels, such as CO, using photovoltaic panels, with the consecutive utilization as fuel in fuel cells, would define a sustainable or regenerative cycle. [1][2][3][4][5][6][7] In the case of performing the CO 2 electroreduction to CO in parallel with the water electroreduction (or the hydrogen evolution reaction (HER)), the mixture CO + H 2 (syngas) is produced. 8,9 In the chemical industry, CO/H 2 mixtures are reacted to form methanol or other liquid fuels, such as diesel, by using the Fischer-Tropsch process. 10 The CO 2 electrochemical reduction can be productselective by using different electrocatalysts. However, even for two-electron products, it is decisive to know the kinetically important steps of the studied reaction. Also, synthesizing an optimized electrocatalyst that do not catalyze undesi...