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Catalysts 2020, 10, 1287 20 of 25 production from photocatalytic CO2 reduction are proposed: (1) designing semiconductors with high surface area and porosity to maximize the adsorption of CO2 and intermediates for further C–C bond formation; (2) coupling two semiconductors with proper band structures for the preferred spatial separation of photo-generated electrons and holes to the electron–hole recombination; (3) introducing oxygen vacancies into semiconductors, which facilitate trapping electrons and activating CO2; (4) applying a certain amount of external bias voltage to promote the separation of photogenerated electron–hole pairs; (5) deeply understanding the photocatalytic CO2 reduction process through DFT calculations and advanced in situ techniques for further exploration on highly active catalysts, photoreducing CO2 to ethanol. Author Contributions: This work was designed and presented by Y.S. (Yanfang Song), W.C., W.W. and Y.S. (Yuhan Sun). All authors have read and agreed to the published version of the manuscript. Funding: This work was funded by the National Natural Science Foundation of China (grant number 91745114, 21802160, 21473233), the Ministry of Science and Technology of China (grant number 2016YFA0202800, 2018YFB0604700), Shanghai Sailing Program (grant number 18YF1425700), and the Hundred Talents Program of Chinese Academy of Sciences. Conflicts of Interest: The authors declare no conflict of interest. References 1. Duan, X.; Xu, J.; Wei, Z.; Ma, J.; Guo, S.; Wang, S.; Liu, H.; Dou, S. Metal-Free Carbon Materials for CO2 Electrochemical Reduction. Adv. Mater. 2017, 29, 1701784. [CrossRef] 2. Vasileff, A.; Zheng, Y.; Qiao, S.Z. Carbon Solving Carbon’s Problems: Recent Progress of Nanostructured Carbon-Based Catalysts for the Electrochemical Reduction of CO2. Adv. Energy Mater. 2017, 7, 1700759. [CrossRef] 3. Tans, P.; Keeling, R. NORR/ESRL. Available online: http://www.esrl.noaa.gov/gmd/ccgg/trends/ (accessed on 25 May 2020). 4. Li, K.; Peng, B.; Peng, T. Recent advances in heterogeneous photocatalytic CO2 conversion to solar fuels. ACS Catal. 2016, 6, 7485–7527. [CrossRef] 5. National Renewable Energy Information Management Platform. Available online: http://djfj.renewable.org. cn/ (accessed on 25 May 2020). 6. Asadi, M.; Kim, K.; Liu, C.; Addepalli, A.V.; Abbasi, P.; Yasaei, P.; Phillips, P.; Behranginia, A.; Cerrato, J.M.; Haasch, R.; et al. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science 2016, 353, 467–470. 7. Gao, S.; Lin, Y.; Jiao, X.; Sun, Y.; Luo, Q.; Zhang, W.; Li, D.; Yang, J.; Xie, Y. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 2016, 529, 68–71. [CrossRef] 8. Zhang, L.; Zhao, Z.J.; Gong, J. Nanostructured Materials for Heterogeneous Electrocatalytic CO2 Reduction and Related Reaction Mechanisms. Angew. Chem. Int. Ed. 2017, 56, 11326–11353. [CrossRef] 9. Habisreutinger, S.N.; Schmidt-Mende, L.; Stolarczyk, J.K. Photocatalytic reduction of CO2 on TiO2 and other semiconductors. Angew. Chem. Int. Ed. 2013, 52, 7372–7408. [CrossRef] 10. Li, Y.; Sun, Q. Recent advances in breaking scaling relations for effective electrochemical conversion of CO2. Adv. Energy Mater. 2016, 6, 1600463. [CrossRef] 11. Shih, C.F.; Zhang, T.; Li, J.; Bai, C. Powering the Future with Liquid Sunshine. Joule 2018, 2, 1925–1949. [CrossRef] 12. Kumar, B.; Llorente, M.; Froehlich, J.; Dang, T.; Sathrum, A.; Kubiak, C.P. Photochemical and photoelectrochemical reduction of CO2. Annu. Rev. Phys. Chem. 2012, 63, 541–569. [CrossRef] 13. Jones, J.-P.; Prakash, G.K.S.; Olah, G.A. Electrochemical CO2 Reduction: Recent Advances and Current Trends. Isr. J. Chem. 2014, 54, 1451–1466. [CrossRef] 14. Zhao, G.; Huang, X.; Wang, X.; Wang, X. Progress in catalyst exploration for heterogeneous CO2 reduction and utilization: A critical review. J. Mater. Chem. A 2017, 5, 21625–21649. [CrossRef] 15. Tu, W.; Zhou, Y.; Zou, Z. Photocatalytic conversion of CO2 into renewable hydrocarbon fuels: State-of-the-art accomplishment, challenges, and prospects. Adv. Mater. 2014, 26, 4607–4626. [CrossRef]PDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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