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−1 −1 μmol·g ·h under simulated sunlight irradiation [104]. When the two-dimensional g-C3N4 nanosheets with few-layer thickness were used as the support of Pd to ensure equivalent charge migrations to various Pd facets, the selectivity of CO2 photoreduction to ethanol strongly depends on the shapes of Pd nanocrystals on the C3N4 nanosheets [105]. The optimal ethanol production rate was achieved on Pd nanotetrahedrons loaded on g-C3N4 nanosheets with a Pd loading of 5.8 wt%, Catalysts 2020, 10, 1287 17 of 25 though the value only arrived at 2.18 μmol·g−1·h−1. Therefore, it still remains challenging to selectively photocatalyze CO2 reduction to ethanol over g-C3N4. Figure 9. (A) N2 sorption isotherms and Barrett–Joyner–Halenda (BJH) pore size distribution curves Figure 9. (A) N2 sorption isotherms and Barrett–Joyner–Halenda (BJH) pore size distribution curves (inset) of u-g-C3N4 and m-g-C3N4. (B) The ethanol or methanol yields in the function of irradiation (inset) of u-g-C3N4 and m-g-C3N4. (B) The ethanol or methanol yields in the function of irradiation time over u-g-C3N4 and m-g-C3N4 under visible-light irradiation. Reproduced with permission [102]. time over u-g-C3N4 and m-g-C3N4 under visible-light irradiation. Reproduced with permission [102]. Copyright 2013, The Royal Society of Chemistry. Copyright 2013, The Royal Society of Chemistry. 3.2.3. Others 3.2.3. Others Apart from TiO2 and g-C3N4, some other photocatalysts have also been reported. In a recent Apart from TiO2 and g-C3N4, some other photocatalysts have also been reported. In a recent report of simultaneously loaded CuO and Pt nanoparticles on reduced HCa2Ta3O10 perovskite report of simultaneously loaded CuO and Pt nanoparticles on reduced HCa2Ta3O10 perovskite nanosheets for sunlight-driven conversion of CO2, ethanol was formed as a significant product at a nanosheets for sun−l1igh−t1-driven conversion of CO2, ethanol was formed as a significant product at a rate of 113 μmol·g ·h [106]. This can be ascribed to their unique structure. Pt nanoparticles with rate of 113 μmol·g−1·h−1 [106]. This can be ascribed to their unique structure. Pt nanoparticles with good contact with perovskite nanosheets could serve as excellent trapping sites for photogenerated good contact with perovskite nanosheets could serve as excellent trapping sites for photogenerated electrons with a high transfer rate. Meanwhile, the introduction of CuO nanoparticles not only electrons with a high transfer rate. Meanwhile, the introduction of CuO nanoparticles not only significantly improves the electron–hole separation through the formation of a p–n junction, but also enhances the adsorption of CO2 and stabilizes C1 intermediates, thus favoring C-C coupling to form ethanol. In another work, Wang et al. reported the synthesis of BiVO4/RGO nanocomposites for CO2 photoreduction, which exhibited improved ethanol formation (5.15 μmol·g−1·h−1) in comparison to pure BiVO4 (3.61 μmol·g−1·h−1) [107]. This improvement was attributed to the effective charge transfer of photo-generated electron from BiVO4 to RGO and improved light absorption. In a later study, porous TaON microspheres were synthesized for CO2 photoreduction via facile nitridation of uniform amorphous Ta2O5 sphere formed by hydrothermal treatment [108]. Under the visible light, the conversion of CO2 to ethanol was improved with a rate of 2.03 μmol·g−1·h−1, which is attributed to the porous spherical architecture of TaON that provided more active sites, enhanced trapping of incident illumination, and promoted charge transfer/separation. Besides this, some other semiconductors, such as Ag@AgBr/CNT [109], red Ag/AgCl [110], Sr3Ti(2−x−y)FexSyO(7−z)Nz [111] and Zn0.8Cd0.2S [112], have been used to produce ethanol from photocatalytic CO2 reduction (Table 3). More effort is still required to improve these photocatalytical systems. Table 3. Summary of the main photocatalysts with the capability to convert CO2 into ethanol. Photocatalyst TiO2-Rh long nanowires TiO2-Pd nanowires TiO2 /Ni(OH)2 composite nanofibers 1.5 wt%Ni2+–TiO2 5%GQDs/V-TiO2 23.2% AgBr/TiO2 g-C3N4 derived from urea g-C3N4 derived from melamine Light Source UV light (λ < 400 nm) UV light (λ < 400 nm) Simulated sunlight UV light (λ < 400 nm) Simulated sunlight Visible light λ > 420 nm Visible light λ > 420 nm Visible light λ > 420 nm Reaction Medium 0.5 M Na2SO4 0.5 M Na2SO4 H2O vapor H2O vapor 8 H2O mg/L MB and 0.01 M NaOH 0.2 M KHCO3 1.0 M NaOH 1.0 M NaOH EtOH Yield Ref. (μmol·g−1 ·h−1 ) 12.1 [97] 13 [97] 0.37 [98] 13.2 [99] 5.65 [100] 13.28 [101] 4.5 [102] 3.6 [102]PDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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