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Catalysts 2021, 11, 482 tions. Its interaction with the catalyst nanoparticles probably contributes to decre energy barrier of the RDS: *CO + *H → *CHO and the barrier to the coupling o termediate, promoting more reduced products. For an efficient CO2 reduction, an optimal balance needs to be searched a electroactive surface area, the ionic conductivity and the hydrophilic/hydropho erties of the catalyst layer [41]. The study of the effect of the ionomer content w taken in this experimental work. A Nafion content of 15%wt maximises the FE an densities towards carbon products (mainly formate and CO). In literature, a de on the Nafion content of the electrode performance is demonstrated. Zhou and co and current densities towards carbon products (mainly formate and CO). In literature, a reported an optimal loading of 20%wt in terms of FE and current density for an dependence on the Nafion content of the electrode performance is demonstrated. Zhou electrode [42]. The obtained results can be used as a starting point for future opt 11 of 19 undertaken in this experimental work. A Nafion content of 15%wt maximises the FE and co-workers reported an optimal loading of 20%wt in terms of FE and current density of the catalyst layer preparation on GDEs. for an Sn-based electrode [42]. The obtained results can be used as a starting point for future optimisation of the catalyst layer preparation on GDEs. Figure 8. Faradaic efficiencies (FEs) (a) and productivities of gas and liquid products (b) for Cu-06 catalyst with different mass percentage of Nafion. The tests were carried out in 0.1 M KHCO3 Figure 8. Faradaic efficiencies (FEs) (a) and productivities of gas and liquid products (b) for Cu-06 catalyst with diff aqueous electrolyte at −1.5 V vs. Ag/AgCl. mass percentage of Nafion. The tests were carried out in 0.1 M KHCO3 aqueous electrolyte at −1.5 V vs. Ag/AgCl. The XRD patterns of the Cu-06 electrode with 45% of Nafion (after test) is shown in The XRD patterns of the Cu-06 electrode with 45% of Nafion (after test) is Figure 9. The diffraction peaks in the XRD graph belong to Cu (JCPDS number: 00-04-0836), Figure 9. The diffraction peaks in the XRD graph belong to Cu (JCPDS numb Cu2O (JCPDS number: 00-050-0667), and Graphite (JCPDS number: 00-041-1487) crystalline 0836), Cu2O (JCPDS number: 00-050-0667), and Graphite (JCPDS number: 00- phases. It evidences the reduction of the CuO catalyst to Cu1+ and Cu0 under the here crystalline phases. It evidences the reduction of the CuO catalyst to Cu1+ and C employed CO2 co-electrolysis conditions. The increase of Nafion content to 45% stabilises 1+ 0 the here employed CO2 co-electrolysis conditions. The increase of Nafion conte the Cu /Cu interface, contributing to the dimerization of *CO adsorbed intermediate to stabilises the Cu1+/Cu0 interface, contributing to the dimerization of *CO adsor promote C2+ products. It agrees with previous literature works that have revealed that it is mediate to promote C2+ products. It agrees with previous literature works that possible to induce C-C coupling if this interface is stabilised [43,44]. Besides, it is possible vealed that it is possible to induce C-C coupling if this interface is stabilised [4 to realise that the selectivity towards alcohols is 19-fold higher in this case (2% FE ethanol) sides, it is possible to realise that the selectivity towards alcohols is 19-fold high than for the same catalyst (Cu-06 at 4 mg cm−2) with 30% of Nafion and at the same applied case (2% FE ethanol) than for the same catalyst (Cu-06 at 4 mg cm−2) with 30% potential (see Figure 5). By comparing Figures 6 and 9, conclusions can be drawn about and at the same applied potential (see Figure 5). By comparing Figure 9 and the selectivity. The coexistence of the oxide-derived copper (Cu1+) and Cu0 in the bulk conclusions can be drawn about the selectivity. The coexistence of the oxide-der could be responsible for the improved selectivity to C products. Simultaneously, the H 1+ 0 2+ 2 per (Cu ) and Cu in the bulk could be responsible for the improved selectiv productivity was decreased by ~3-fold (from ~30 to 8 mmol h−1 gcat−1) by increasing the products. Simultaneously, the H2 productivity was decreased by ⁓3-fold (from Nafion content from 30% to 45%, which could be also attributed to the presence of high- index facets of Cu, such as (400), (331), and (420). Indeed, in a recent work, Philip et al. [45] have demonstrated the suppression of H2 evolution due to the increased amount of these high-index Cu facets. 2.3.5. Considerations about the Obtained Results Some considerations about the apparent inconsistency of some results should be done. Indeed, as can be observed, in some cases, the overall FE exceeds 100%, while, in other cases, this value is less than 50%. It has also been observed in previous studies by different authors [46,47]. A possible cause could be the experimental uncertainty in measuring the inlet and outlet real flow rates of the gaseous streams. A slight variation of these values might significantly impact the processed data, with particular reference to the efficiencies beyond 100%. When FE is far below 100%, a possible reason may be the oxidation of liquid products that travel to the anolyte through the membrane. As suggested by Gabardo et al. in their work, a control experiment based on the verification of the oxidation levels of possible products in the anolyte can be performed [48]. Otherwise, analysing the distribution of the liquid products in the two liquid chambers of the flow cell would allow having important qualitative information. Relative to the latter case, traces of m b a d p S i e s e 0 n b 3 o i iPDF Image | Gas Diffusion Electrode Systems for the Electro CO2 Conversion
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