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Catalysts 2020, 10, 1287 18 of 25 ZnO/g-C3N4 Ag3PO4/g-C3N4 5.8wt%Pd/g-C3 N4 Reduced Cu/Pt–HCa2 Ta3 O10 BiVO4 /RGO TaON microspheres Ag@AgBr/CNT Red Ag/AgCl Sr3 Ti(2−x−y) Fex Sy O(7−z) Nz Zn0.8 Cd0.2 S Simulated sunlight Simulated sunlight Visible light λ > 420 nm Simulated sunlight Simulated sunlight Visible light λ > 420 nm Visible light λ > 420 nm Visible light λ > 420 nm UV visible region (300–700 nm) H2O 1.5 0.5 M Na2SO4 1.3 H2O vapor 2.18 H2O vapor 113 0.1 M NaOH 5.15 1.0 M NaHCO3 2.03 0.2 M KHCO3 2.94 0.1 M NaHCO3 44.6 0.2 M NaOH 9.9 1.0 M NaHCO3 6 [103] [104] [105] [106] [107] [108] [109] [110] [111] [112] Visible light λ > 400 nm 3.3. Photoelectrocatalytic CO2 Reduction to Ethanol Table 3. Cont. Photoelectrochemical reduction of CO2 has been investigated following its first discovery by Halman in 1978 [113]. Employing semiconductors, such as GaP, silicon and CdTe, as the photocathodes [12,14], the conversion of CO2 into hydrocarbons, especially ethanol, can be realized in the presence of water under illumination and bias potential. In spite of the increasing researches on photoelectroreduction of CO2 in the last five years, the reports on clean fuel ethanol formation were extremely rare. For instance, a Cu/Cu2O electrode prepared by electrochemical deposition method catalytically reduces CO2 to ethanol with the maximum yield of 5.0 ppm in 0.1 mol L−1 Na2CO3 under the bias potential of 0.2 V vs. Ag/AgCl and UV-Vis irradiation [35]. Equipped with Pt-reduced graphene oxides (RGO)/Cu foam cathode and TiO2 nanotube photoanode, the phoelectrochemical cell exhibited an ethanol production rate of 105 nmol h−1 cm−2 under the potential of 2 V and UV-Vis irradiation, which was even significantly higher than that of the simple sum of electrochemical and phochemical processes (82 nmol h−1 cm−2) [114], indicating the synergetic effect of electrochemical and phochemical reductions. Importantly, ethanol was observed as the main product over the boron-doped g-C3N4 electrodes with or without coupling with Au, Rh or Ag [115]. The yield of ethanol was maximized on boron-doped g-C3N4/Au electrode with a value of around 150 nmol under the bias potential of −0.4 V vs. Ag/AgCl and simulated solar irradiation. Afterwards, ZIF-8 was incorporated into Ti/TiO2 nanotubes electrode to increase the photocurrent, resulting in the ethanol formation of up to 10 mmol L−1 under the bias potential of 0.1 V vs. Ag/AgCl and UV-Vis irradiation for three hours (Figure 10) [116]. According to the results mentioned above, highly efficient production of ethanol through photoelectrocatalytic route and even industrialization has a long way to go.PDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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