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Design and Synthesis of Carbazolic Porous Organic Frameworks for Gas Storage, Separation, and Catalysis
In recent decades, novel porous materials of porous organic frameworks (POFs), have received attentions thanks to their outstanding properties such as excellent porosity and rich strategies for post-synthetic functionalization. Due to its rich chemical and optoelectronic properties, introducing carbazole as the functional group into organic porous materials is an effective approach to expand possible applications of POFs. In the first portion of this work, a series of Cz-POFs were synthesized via FeCl3 promoted oxidative polymerization. Using bulky, dendritic building blocks with high connectivity, the porosity of Cz-POFs was significantly enhanced by 2-3 times. Cz-POFs exhibit excellent H2 and CO 2 uptake, CO2/N2 and CO2/CH4 selectivities, showing great promise for gas storage and separation. In the second portion, we introduced carbazole at the 3,3’-positions of the chiral BINOL-derived phosphoric acid. A porous heterogeneous BINOL-derived chiral phosphoric acid BiCz-POF-1 was prepared via oxidative polymerization. BiCz-POF-1 displays remarkable catalytic activity and enantioselectivity toward transfer hydrogenation reactions with good recyclability. The third portion of this research focused on design, preparation and catalytic application of an oligomeric BINOL-derived chiral phosphoric acid based on TRIP, CzTRIP-P. CzTRIP-P was proved to be a recyclable, homogeneous asymmetric catalyst for the enantioselective catalysis of [2+3] cycloaddition. Moreover, CzTRIP-P could be applied in catalysis of transfer hydrogenation of 2-quinoline and direct arylation of trifluoromethyl ketone, exhibiting a comparable catalytic performance with the monomer counterpart. In the fourth portion of this work, we applied carbazolic POFs as the precursor of electrocatalyst for oxygen reduction reaction (ORR). A metalloporphyrin based POFs, FeOCzP, was designed and synthesized. After pyrolysis, the material displayed a higher porosity than most of POFs material reported as ORR catalyst. A more positive half-wave potential than Pt/C in basic media was achieved with pyrolyzed FeOCzP. In the fifth portion of this research, NHPI/O 2/P(Cz-BP) catalytic system showed excellent efficiency for the oxidation of secondary benzylic alcohol under light irradiation. The substrate scope covered several secondary benzylic alcohols with different functional groups incorporated.
Zhang, Xiang, "Design and Synthesis of Carbazolic Porous Organic Frameworks for Gas Storage, Separation, and Catalysis" (2017). ETD collection for University of Nebraska - Lincoln. AAI10616941.