Date of Award

2014-01-01

Degree Name

Doctor of Philosophy

Department

Chemistry

Advisor(s)

Luis A. Echegoyen

Abstract

Three new boronate-ester based covalent organic frameworks (CoPc-PorDBA, CoPc-BPDA and HHTP-PorDBA), an imine-linked porphyrin porous polymer (CuPor-BPDC) and imine and benzothiazole based porous polymers (IBTP), and a triazole based phthalocyanine "click" polymer (Pc-POP) were synthesized. The CoPc-PorDBA and CoPc-BPDA COFs exhibited high BET surface areas (1087, 1315 m2 g-1, respectively) whereas HHTP-PorDBA showed a low BET surface area of 205 m2 g-1. The H2 storage capacities of CoPc-BPDA and CoPc-PorDBA range between 0.8-1.2wt% at 77K, 1bar and the CH4 storage capacities range between 0.4-0.8wt% at 298K, 1bar. These materials also had good thermal stabilities up to 350° C. The BET surface areas of Porous polymers CuPor-BPDC, IBTP, and Pc-POP, are 428 m2 g-1, 442 m2 g-1, and 115 m2 g-1, and showed CO2 capture capacities of 5.5 wt%, 7.8 wt%, and 11.9 wt%, respectively, at 273 K/1 bar with selectivities for CO2/CH4 adsorption ranging between 5.4-6.4 . The chemical connectivity and composition of the COFs (CoPc-PorDBA, CoPc-BPDA, HHTP-PorDBA) and of the polymers (CuPor-BPDC, IBTP, Pc-POP) were characterized by several methods such as infrared spectroscopy, powder X-ray diffraction (PXRD), solid-state 13C CP-MAS NMR, surface area measurements, solid-state UV-Vis, and thermogravimetric and elemental analysis.

Language

en

Provenance

Received from ProQuest

File Size

155 pages

File Format

application/pdf

Rights Holder

Venkata Neti

Included in

Chemistry Commons

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