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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 Catalysts 2020, 10, 1287 19 of 25 efficient production of ethanol through photoelectrocatalytic route and even industrialization has a long way to go. Figure 10. (A) Schematic illustration of ZIF-8 formation on Ti/TiO2NT. (B) Photoelectrocatalytic CO2 Figure 10. (A) Schematic illustration of ZIF-8 formation on Ti/TiO2NT. (B) Photoelectrocatalytic CO2 reduction reactor used in all experiments: (a) 125W mercury vapor lamp; (b) quartz window; (c) working reduction reactor used in all experiments: (a) 125W mercury vapor lamp; (b) quartz window; (c) electrode; (d) reference electrode; (e) counter electrode; (f) septum; (g) manometer; (h) headspace; working electrode; (d) reference electrode; (e) counter electrode; (f) septum; (g) manometer; (h) (i) supporting electrolyte; (j) magnetic bar. (C) Linear scanning voltammograms of the electrodes headspace; (i) supporting−1electrolyte; (j)−m1 agnetic bar. (C) Linear scanning voltammograms of the at a scan rate of 10 mV·s in 0.1 mol·L Na2SO4: (a) both electrodes in the dark; (b) Ti/TiO2NT electrodes at a scan rate of 10 mV·s−1 in 0.1 mol·L−1 Na2SO4: (a) both electrodes in the dark; (b) without CO2; (c) Ti/TiO2NT with CO2; (d) Ti/TiO2NT-ZIF-8 without CO2; (e) Ti/TiO2NT-ZIF-8 with Ti/TiO2NT without CO2; (c) Ti/TiO2NT with CO2; (d) Ti/TiO2NT-ZIF-8 without CO2; (d) CO2. (D) Concentrations of ethanol generated on Ti/TiO2NT-ZIF-8 electrode by photoelectrocatalytic Ti/TiO2NT-ZIF-8 with CO2. (D) Concentrations of ethanol generated on Ti/TiO2NT-ZIF-−81electrode CO2 reduction for 3 h with bias potentials of −0.7 V and +0.1 V vs. Ag/AgCl, in 0.1 mol·L Na2SO4. by photoelectrocatalytic CO2 reduction for 3 h with bias potentials of −0.7 V and +0.1 V vs. Ag/AgCl, Reproduced with permission [116]. Copyright 2018, Elsevier. in 0.1 mol·L−1 Na2SO4. Reproduced with permission [116]. Copyright 2018, Elsevier. 4. Conclusions and Perspectives 4. Conclusions and Perspectives In conclusion, recent research has indicated the feasibility of producing ethanol from CO2 by electrochemical, photochemical and photoelectrochemical processes using solar energy and/or In conclusion, recent research has indicated the feasibility of producing ethanol from CO2 by renewable electricity over advanced catalysts. Despite the challenges ahead, it is promising to develop electrochemical, photochemical and photoelectrochemical processes using solar energy and/or highly efficient and economical catalytic systems that use renewable energy to selectively convert renewable electricity over advanced catalysts. Despite the challenges ahead, it is promising to CO into clean fuel ethanol over active catalysts in the near future, thus realizing the sustainable dev2elop highly efficient and economical catalytic systems that use renewable energy to selectively development of human beings. convert CO2 into clean fuel ethanol over active catalysts in the near future, thus realizing the In future studies, more effort should be directed towards the following strategies to boost the sustainable development of human beings. performance of electrocatalysts for CO -to-ethanol conversion: (1) introducing edges by nanostructuring In future studies, more effort sh2ould be directed towards the following strategies to boost the with cubes, quantum dots, etc., introducing defects by doping and making pores, or introducing grain performance of electrocatalysts for CO2-to-ethanol conversion: (1) introducing edges by boundaries by controlled electrochemical growth, into the catalyst surfaces to increase the active sites; nanostructuring with cubes, quantum dots, etc., introducing defects by doping and making pores, or (2) designing nanostructured catalysts with special morphologies, such as multi-hollow, core-shell and introducing grain boundaries by controlled electrochemical growth, into the catalyst surfaces to nanoporous structures, which can confine the CO intermediates for further C–C coupling and ethanol increase the active sites; (2) designing nanostructured catalysts with special morphologies, such as formation; (3) employing metal or nonmetal doping strategies to chemically modify the structures of multi-hollow, core-shell and nanoporous structures, which can confine the CO intermediates for catalysts; (4) exploring composite materials with synergetic effect as the potential catalysts for CO further C–C coupling and ethanol formation; (3) employing metal or nonmetal doping strategies to2 reduction to realize the cascade reaction; (5) using certain catalysts with high overpotentials towards chemically modify the structures of catalysts; (4) exploring composite materials with synergetic HER to suppress HER, which would compete electrons with CO electroreduction reaction in the effect as the potential catalysts for CO2 reduction to realize the c2ascade reaction; (5) using certain result of low efficiency; (6) incorporating suitable molecular catalysts to reduce the overpotentials of catalysts with high overpotentials towards HER to suppress HER, which would compete electrons CO2-to-ethanol conversion by stabilizing the intermediates; (7) designing and optimizing flow cell system using gas-diffusion-electrode to improve the current density to commercially relevant levels; (8) designing catalysts with typical structure models for density functional theory (DFT) calculation and using operando techniques to study the reaction mechanism of CO2 reduction. In spite of the great efforts, it still seems quite challenging to efficiently photoreduce CO2 to desirable products. Although CO2 could be reduced to ethanol using some certain semiconductor catalysts by photochemical route, the yield and selectivity of ethanol was extremely low and hard to practice on a commercial scale. In the following, several strategies that may promote the ethanolPDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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