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Design and Synthesis of Carbazolic Porous Organic Frameworks for Gas Storage, Separation, and Catalysis

Xiang Zhang, University of Nebraska - Lincoln

Abstract

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.^

Subject Area

Chemistry

Recommended Citation

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.
http://digitalcommons.unl.edu/dissertations/AAI10616941

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