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Fu et al. In situ Catalytic Transformation SCHEME 11 | ILs used in CO2 capture and conversion. been utilized. Recently, the breakthrough is made by Jazzar and Bertrand group. By combining the copper catalyst and Lewis pair, hydrogenation of carbon dioxide into formate is realized (Romero et al., 2018). Latter, X. Hu and Y. Wu group reports the first catalytic hydrogenation process of CO2 to formate using transition metal free catalyst (B(C6 F5 )3 /M2 CO3 , M = Na, K, and Cs) (Zhao et al., 2019). These results open new vistas in the field of FLPs facilitated CO2 capture and hydrogenation. CATALYST DESIGN FOR DIRECT CONVERSION OF DILUTED CO2 In addition to the CO2 capture and transformation strategy, there are also examples that the CO2 from waste streams can be directly converted by designing catalysts that tolerate to the contaminants in the waste streams such as exogenous water, nitrogen, SO2, amine etc. For example, Williams et al. reports the synthesis of poly(cyclohexylene carbonate) using the power station generated CO2 facilitated by the homogeneous dinuclear Zn or Mg catalysts, which is stable in the presence of contaminants from gas streams (Chapman et al., 2015) (Scheme 13). D’Elia and Basset group develops the combination of early transition metal halides (Y, Sc, Zr) and TBAB to quantitatively convert CO2 from diluted streams and produce cyclic organic carbonates (Barthel et al., 2016). The features of metal-organic frameworks (MOFs) to selectively capture and catalyze CO2 conversion make them a new type of platform for diluted CO2 transformation. Recently, Hong group design and synthesize an acid-base resistant Cu(II)-MOF which can convert CO2 from simulated post-combustion flue gas into corresponding cyclic carbonates (Liang et al., 2017). In direct conversion of diluted CO2, the stability of the catalysts to the contaminants in the gas streams is crucial to the success of the process. CONCLUSION AND OUTLOOK The past 10 years have witnessed great advances in CO2 capture and in situ conversion. Different CO2 absorbents including inorganic and organic bases, NHCs, and NHOs, ILs, FLPs and polymeric functional materials have been employed in this field. As an emerging field, much effort is still desired to explore the potential conversion of the captured CO2. Considering amines and CO2 can be involved in diverse reactions, it is hoped that the conversion of ammonia carbamate can be further extended to other valuable products besides isocyanates, carbamates and ureas. On the other hand, although the hydrogenation of CO2 captured by inorganic/organic bases and the combination of base and alcohol has been investigated, the hydrogenation of CO2 captured by ILs and/or FLPs remains sporadic and underexplored. In light of the successful electrochemical reduction of IL-captured CO2 and hydrogenation of CO2 in ILs (Zhang et al., 2008, 2009; Wesselbaum et al., 2012; Scott et al., 2017), it is reasonable to conclude that the captured CO2 by IL can be hydrogenated by designing appropriate catalyst. Besides, the breakthrough in FLP-mediated CO2 hydrogenation opens new possibilities for FLP-based CO2 capture and transformation (Romero et al., 2018; Zhao et al., 2019). Another important transformation pathway for CO2 adducts derived from reacting with amines, NHCs, NHOs and ILs is transcarboxylation reaction in the synthesis of cyclocarbonates, oxazolidinones and quinazoline-2,4-(1H,3H)-diones. It is foreseeable that the application of these transcarboxylating reagents will be investigated continuously with the emergence of new CO2 conversion reactions. Frontiers in Chemistry | www.frontiersin.org 11 July 2019 | Volume 7 | Article 525PDF Image | CO2 Capture and in situ Catalytic Transformation
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