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Processes 2020, 8, 548 18 of 22 to synthesize cyclic carbonate is in integrating the epoxidation and cycloaddition reaction of CO2, because a common catalyst used for a cycloaddition reaction such as TBAB deactivates a catalyst used for epoxidation reaction. The advancement of this cycloaddition reaction provides insight into utilizing CO2 directly from waste source CO2 such as flue gas [18]. The perspective of utilizing a waste source of carbon dioxide used for the reaction with epoxides has received more attention recently in the industrial production of cyclic and polymeric carbonate. In reality, the objective of this novel reaction is to utilize industrial sources of CO2, which comprises impurities such as hydrogen sulfide, carbon monoxide, sulfur oxide, nitrogen oxide, and water [65]. These compounds theoretically would impact the catalyst activity due to catalyst poisoning. In the perspective of the industrial use for novel catalytic application in CO2/epoxide coupling to produce either cyclic or polymeric carbonates, there should be more upcoming research investigating the effect of carbon dioxide purity on catalyst performance. This endorses the viability of this reaction as pathway by employing waste CO2 as precursor. 6. Conclusions The cycloaddition of CO2 with epoxides is a sustainable pathway for the fixation of CO2 into valuable products, considering the industrial applications of cyclic and polymeric carbonates. The development of homogeneous and heterogeneous catalysts, including homogeneous organocatalyst (e.g., organic salt, ionic liquid, deep eutectic solvents), metal salts, organometallic (e.g., mono-, bi-, and tri-metal salen complexes and non-salen complexes) and heterogeneous supported catalysts, and metal organic framework for this reaction will enable the reaction of CO2 with many types of epoxides. Under their catalytic systems, all classes of these catalysts from recent development can exhibit CO2 cycloaddition to cyclic carbonates at CO2 pressures of 1 bar and reaction temperatures less than around 50 ◦C. However, these conditions usually satisfy only terminal epoxide substrates while are still challenging for internal epoxide substrates. This includes renewable terminal epoxides such as unsaturated fatty acid esters termed as oleochemical carbonates. The utilization of bio-based epoxides derived from renewable sources also improves reaction sustainability. There are only a few industrial bio-based epoxides that have been widely produced, for instance, reaction of glycerol to epichlorohydrin by Dow and Solvay. The proposed green pathway for the generation of sustainable epoxide precursors from biomass feedstock could fulfil the implementation of the biorefinery concept. Although bio-based resources are considered as the decent alternative, the major challenge lies in the cost and availability that should fulfil the desired market size for the demand for cyclic or polymeric carbonate products. Apart from what was mentioned above, the one-pot strategy combining epoxidation and cycloaddition may offer several advantages, especially for the process and cost sustainability of the pathway. The direct conversion enables a safer way in the handling of epoxides, which are extremely flammable, toxic, and corrosive, while increasing the efficiency of the process. However, the reaction needs a robust multi-functional catalyst to promote epoxidation and cycloaddition with CO2. In order to minimize the energy penalty for CO2 capture and storage, utilization of CO2 directly from a waste source such as flue gas is of interest; however, the limitations of CO2 concentration and the presence of reactive impurities are a challenge. Lastly, CCU cannot mitigate the enormous amount of CO2 emissions, however, CO2 cycloaddition can be seen as a reasonably competent alternative to CO2 transformation, offsetting the high value-added nature by extending material use defer CO2 back to the atmosphere when compared to commodities and fuels such as urea, methanol, and methane. Author Contributions: Conceptualization, K.K., M.A.A.M.S., and W.K.; writing—original draft preparation, M.A.A.M.S.; writing—review and editing, K.K., W.K., J.W.L., P.L.S., and S.A.; supervision, W.K.; project administration, M.K.L.; funding acquisition, K.K. All authors have read and agreed to the published version of the manuscript. Funding: This research was funded by the Thailand Research Fund (TRF) and Office of the Higher Education Commission (grant no. MRG6180262), and King Mongkut’s Institute of Technology Ladkrabang (KMITL) (grant no. KREF046209).PDF Image | Green Pathway Utilizing CO2 Cycloaddition Reaction Epoxide
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