Defense Date

2011

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Hani El-Kaderi

Abstract

A new class of porous polymers has been designed and successfully synthesized by thermal dehydrogenation of several polytopic arylamine-borane adducts and has been designated Borazine-Linked Polymers (BLPs). The polymers reported are constructed of linear, triangular, and tetrahedral amine building units to form 2D and 3D frameworks. The boron sites of the pores are aligned with hydrogen atoms contrasted with the recently reported halogenated BLPs which consist of pore channels aligned with bromine or chlorine atoms. One of the reported BLPs, BLP-2(H), was proven to be crystalline by PXRD, matching the experimental pattern to theoretical patterns calculated from modeled structures. BLPs were found to be thermally stable by thermogravimetric analysis, decomposing at temperatures ~450 ºC. Infrared spectroscopy and 11B MAS NMR spectra confirm the formation of borazine as reported in previous borazine-containing polymers and 13C CP MAS spectra confirmed that the structural integrity of the amine building units were maintained and incorporated in the framework of BLPs. Nitrogen isotherms revealed that BLPs exhibit high surface areas ranging from 1132-2866 m2/g (Langmuir) and 400-2200 m2/g (Brunauer-Emett-Teller, BET) with pore sizes from 7-14 Å. Hydrogen, methane, and carbon dioxide measurements were performed at low pressure (up to 1 atm) and were found to be among the best of organic polymers. High pressure isotherms (up to 40 bar) were also taken at various temperatures ranging from 77-298 K. Isosteric heats of adsorption were calculated using the virial method at low pressures. Gas storage performance of BLPs at 40 bar were found to be: 14.7-42.5 mg/g for H2 uptake at 77 K; 348.9-717.4 mg/g for CO2 uptake at 298 K; and 40.8-116.1 mg/g for CH4 uptake at 298 K. The CO2/CH4 selectivity of BLPs at 298 K up to 40 bar was calculated using the Ideal Adsorbed Solution Theory (IAST) to determine their performance as carbon capture and sequestration materials. Additionally, non-borazine containing nanoporous organic polymers (NPOFs) consisting of all carbon and hydrogen atoms were also synthesized and subjected to low pressure hydrogen storage measurements. The results show that though NPOFs generally exhibit higher surface areas (SALang = 2423-4227 m2/g), the H2 storage capacity of BLPs is superior.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

December 2011

Included in

Chemistry Commons

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