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Metal Microporous Aromatic Polymers with Improved Performance for Small Gas Storage.

Chemistry (Weinheim an der Bergstrasse, Germany) (2015-07-28)
Xian Fu, Yindong Zhang, Shuai Gu, Yunlong Zhu, Guipeng Yu, Chunyue Pan, Zhonggang Wang, Yuehua Hu
ABSTRACT

A novel metal-doping strategy was developed for the construction of iron-decorated microporous aromatic polymers with high small-gas-uptake capacities. Cost-effective ferrocene-functionalized microporous aromatic polymers (FMAPs) were constructed by a one-step Friedel-Crafts reaction of ferrocene and s-triazine monomers. The introduction of ferrocene endows the microporous polymers with a regular and homogenous dispersion of iron, which avoids the slow reunion that is usually encountered in previously reported metal-doping procedures, permitting a strong interaction between the porous solid and guest gases. Compared to ferrocene-free analogues, FMAP-1, which has a moderate BET surface area, shows good gas-adsorption capabilities for H2 (1.75 wt % at 77 K/1.0 bar), CH4 (5.5 wt % at 298 K/25.0 bar), and CO2 (16.9 wt % at 273 K/1.0 bar), as well as a remarkably high ideal adsorbed solution theory CO2 /N2 selectivity (107 v/v at 273 K/(0-1.0) bar), and high isosteric heats of adsorption of H2 (16.9 kJ mol(-1) ) and CO2 (41.6 kJ mol(-1) ).

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Methanesulfonic acid, ≥99.0%
Sigma-Aldrich
Ferrocene, 98%
Sigma-Aldrich
1,2-Dichlorobenzene, anhydrous, 99%
Sigma-Aldrich
Cyanuric chloride, 99%
Sigma-Aldrich
Methanesulfonic acid solution, 70 wt. % in H2O
Sigma-Aldrich
Methanesulfonic acid solution, 4 M (with 0.2% (w/v) tryptamine)
Sigma-Aldrich
1,2-Dichlorobenzene solution, NMR reference standard, 5% in acetone-d6 (99.9 atom % D), NMR tube size 5 mm × 8 in.