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Energies 2020, 13, 420 6 of 96 pure hydrogen without contaminants allows the direct utilization in fuel cells. Cycles are generally composed of two or three steps and involve metal oxide redox reactions. Two-step thermochemical cycles require high temperature, but also the efficiency of the overall reaction is high. The difference of temperature of oxidation and reduction reactions is the thermodynamic driving force for two-step Energies 2020, 13, x FOR PEER REVIEW 6 of 95 thermochemical water splitting. In the first step, the metal oxide (MO ) is thermally dissociated to the metal form or ox In the first step, the metal oxide (MOox) is thermally dissociated to the metal form or the lower- the lower-valence metal oxide (MO ), and oxygen is released (see Figure 2). The reaction is red valence metal oxide (MOred), and oxygen is released (see Figure 2). The reaction is highly endothermic highly endothermic and requires high temperatures [67]. and requires high temperatures [67]. Figure2.Schemeofatwo--sttepttherrmoccheemicicaallccyycclelefoforrHH2OOanadndCCOO2 spslpitltitntignugsuinsginmgemtaeltaolxoidxeidine 22 in a redox system. In the activation step, the metal oxide (MOox) is thermally decomposed via an a redox system. In the activation step, the metal oxide (MOox) is thermally decomposed via an endothermic reaction that requires high-temperature heat provided by concentrated solar power (CSP). endothermic reaction that requires high-temperature heat provided by concentrated solar power In the oxidation step, the reduced metal oxide (MOred) reacts with steam and carbon dioxide producing (CSP). In the oxidation step, the reduced metal oxide (MOred) reacts with steam and carbon dioxide syngas(H andCO).Finally,MOoxisrecycled. producing2 syngas (H2 and CO). Finally, MOox is recycled. 1 High-temperature reduction (activation step): High-temperature reduction (activation step): MO →MO +1O MO → MO +2 O (2) (2) ox red22 In the second exothermal step, the hydrolysis of the reduced metal oxide and water splitting In the second exothermal step, the hydrolysis of the reduced metal oxide and water splitting occurs. Pure hydrogen and the primary metal oxide are produced. The pure metal oxide is recycled occurs. Pure hydrogen and the primary metal oxide are produced. The pure metal oxide is recycled back to the solar reduction reactor, closing the material cycle. back to the solar reduction reactor, closing the material cycle. Low-temperature oxidation with H2O (H2 generation step): Low-temperature oxidation with H2O (H2 generation step): MO + HO → MO + H (3) Similarly,syngascouldbeobtMaiOnered+byHin2tOro→duMcinOgoxa+mHix2tureofCO2 andH2Ointhereact(o3)r vessel. CO2/H2O thermochemical cycles are a possible route for the utilization of the carbon dioxide captured from other processes. Low-temperature oxidation with CO2 (CO generation step) MO + CO → MO + CO (4) The previous reactions may be classified as oxide type and are the most investigate nowadays, but other two types of reaction are developed: the hydride type and the hydroxide type [81]. Hydride type: MH → M + H (5) 1PDF Image | Green Synthetic Fuels
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