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Catalysts 2020, 10, 1287 8 of 25 Catalysts 2020, 10, x FOR PEER REVIEW 8 of 25 Although numerous efforts have already been devoted to discover the intermediates and products Although numerous efforts have already been devoted to discover the intermediates and involved in the CO2 reduction process, the various proposed mechanisms of ethanol production products involved in the CO2 reduction process, the various proposed mechanisms of ethanol indicate that more definitive studies are required. production indicate that more definitive studies are required. 3. The Advances of CO2 Reduction to Clean Fuel Ethanol 3. The Advances of CO2 Reduction to Clean Fuel Ethanol Considering the fact that the linear CO2 molecule is fully oxidized and extremely stable, it Considering the fact that the linear CO2 molecule is fully oxidized and extremely stable, it is is rather difficult to convert CO2 into fuels, especially for ethanol production involving multiple rather difficult to convert CO2 into fuels, especially for ethanol production involving multiple electron–protons. Therefore, whether using electricity, sunlight or both of them as input energy, it electron–protons. Therefore, whether using electricity, sunlight or both of them as input energy, it demands the corresponding specific catalysts to accelerate the CO2 reduction reaction. Essentially, demands the corresponding specific catalysts to accelerate the CO2 reduction reaction. Essentially, the performance of CO2 reduction depends on the properties of the applied catalysts. In the following the performance of CO2 reduction depends on the properties of the applied catalysts. In the part, recent important progress in material exploration for CO2 conversion to ethanol will be discussed following part, recent important progress in material exploration for CO2 conversion to ethanol will in three categories, namely electrocatalysts, photocatalysts and photoelectrocatalysts, as shown in be discussed in three categories, namely electrocatalysts, photocatalysts and photoelectrocatalysts, Scheme 3. as shown in Scheme 3. Scheme 3. IIlllusttrrattiionsofftthecattallyssttssandttheccorrresspondiingssttrrattegiiessfforracchiieviingellccttrroccattallyttiicc,, photocatalyticandphotoelectrocatalyticCO conversionintocleanfuelethanol,respectively. photocatalytic and photoelectrocatalytic CO2 conversion into clean fuel ethanol, respectively. 3.1. Electrocatalytic CO2 Reduction to Ethanol 3.1. Electrocatalytic CO2 Reduction to Ethanol Since the pioneering work on CO2 electroreduction to HCOOH over mercury cathodes was Since the pioneering work on CO2 electroreduction to HCOOH over mercury cathodes was reported in 1954 [48], much research has been done on electrocatalytic CO2 conversion into reported in 1954 [48], much research has been done on electrocatalytic CO2 conversion into fuels fuels [10,15,18]. However, studies on the ethanol production from CO2 electroreduction have increased [10,15,18]. However, studies on the ethanol production from CO2 electroreduction have increased in in the last five years. In this process, theoretically, electrons are released from water oxidation at the the last five years. In this process, theoretically, electrons are released from water oxidation at the anode and travel through an external wire to the catalysts’ surface at cathode to reduce CO2 to various anode and travel through an external wire to the catalysts’ surface at cathode to reduce CO2 to products. The ethanol production is a combination of the oxidation reaction at anode and reduction various products. The ethanol production is a combination of the oxidation reaction at anode and reaction at cathode involving twelve electron–protons. As the catalysts for CO2 electroreduction, metals reduction reaction at cathode involving twelve electron–protons. As the catalysts for CO2 and metallic complexes have been extensively investigated [18,49]. Among these metal-containing electroreduction, metals and metallic complexes have been extensively investigated [18,49]. Among catalysts, Cu-based catalysts have been reported as the most promising electrodes that are possibly these metal-containing catalysts, Cu-based catalysts have been reported as the most promising capable of catalyzing the reduction of CO2 to clean fuel ethanol [50,51]. The unique catalytic electrodes that are possibly capable of catalyzing the reduction of CO2 to clean fuel ethanol [50,51]. property of Cu originates from its moderate binding energy for CO intermediates, as evidenced by The unique catalytic property of Cu originates from its moderate binding energy for CO Density functional theory (DFT) calculations. The currently identified Cu-based catalysts those can intermediates, as evidenced by Density functional theory (DFT) calculations. The currently electroreduce CO2 to ethanol include modified Cu (morphology, size, facet, doping, organic additives, identified Cu-based catalysts those can electroreduce CO2 to ethanol include modified Cu et al.), Cu-based alloys, Cu/carbon composites and Cu-based metal-organic porous materials (Table 2). (morphology, size, facet, doping, organic additives, et al.), Cu-based alloys, Cu/carbon composites and Cu-based metal-organic porous materials (Table 2). Moreover, metal-free nitrogen-doped carbon materials have also been reported recently to be capable of ethanol production from CO2.PDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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