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22 Chapter 4. Non-Aqueous PEC System Figure 4.3: CO2 reduction mechanism on a lead electrode. Adapted from Gennaro et al. (1996). above), the oxidation of carbonate species by the photogenerated holes (h+) that occurs on the dark side of the device represents an interesting potential method for oxygen formation in a full cell based on this concept. However, it is likely that a greater efficiency will be derived from a coupled PV-electrolyzer system than a direct photo-absorbing PEC system, so system-level considerations will most likely point to development of alternative anodes. Carbonate oxidation to give O2 may be considered to be the reverse of the cathode process occurring in a carbonate fuel cell: 12O2+CO2+2e– −−→CO32- These fuel cells operate at high efficiencies (60%) using a molten carbonate salt (Na and K carbonates) at temperatures above 600◦C. This high temperature requirement is mainly imposed by the melting point of the electrolyte salts; the requirement for molten salts comes from the dominance of side-reactions (e.g., water splitting) if aqueous solutions are employed instead. Hence, it is reasonable to project that a low-temperature variant could be designed whereby efficient CO32- oxidation to O2 may be achieved if a suitable solvent is found that is capable of dissolving substantial quantities of carbonate salt while remaining stable at the operating potential of the oxidation process. Solutions of alkali metal carbonates (e.g., Li2CO3) in ionic liquids therefore represent an interesting material for investigation in this context. 4.2.3 Electrolyte: Organic Solvent and/or Ionic Liquid A non-aqueous electrochemical process necessarily requires a non-aqueous electrolyte. We consider two broad classes of solvents that may be suitable for the system under consideration: polarPDF Image | ISRU Challenge Production of O2 and Fuel from CO2
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