Structural and selective gas adsorption studies of polyoxometalate and tris(ethylenediamine) cobalt(III) based ionic crystals

Chandan Dey, Raja Das, Pradip Pachfule, Pankaj Poddar, Rahul Banerjee

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)

Abstract

Seven new ionic solids built on polyoxometalate anions and [Co(en) 3]3+ cations, namely, [Co(en)3Mo 8O26(H3O)(Cl)](DMF)4(H2O) (Co-Mo8-DMF), [α-PW12O40][Co(en) 3]·6DMF (Co-W12P-DMF), [α-PW 12O40][Co(en)3]·6DEF (Co-W 12P-DEF), [α-PMo12O40][Co(en) 3]·5.5DMF (Co-Mo12P-DMF), [α-PMo 12O40][Co(en)3]·6DEF (Co-Mo 12P-DEF), [α-SiW12O40][Co(en) 3]3/2[Cl]1/2·6DMF·3H 2O (Co-W12Si-DMF), and [α-SiW12O 40][Co(en)3]·6DEF (Co-W12Si-DEF), have been synthesized from nonaqueous (DMF/DEF) media and characterized by single-crystal X-ray diffraction. We attempt to understand if [Co(en) 3]3+ cations used in these reaction systems play a crucial role in controlling the assembly of these crystals. These ionic solids, after removal of the DMF or DEF molecules, are found to exhibit size selective H 2 adsorption properties over N2. The amount of hydrogen adsorption was influenced by POM anion types and their orientations. CoMo 12P-DEF has the highest (0.9 wt %) H2 uptake, and CoW 12P-DEF has the lowest (0.4 wt %) uptake among the series when the adsorbate pressure approached 1 atm.

Original languageEnglish
Pages (from-to)139-146
Number of pages8
JournalCrystal Growth and Design
Volume11
Issue number1
DOIs
Publication statusPublished - 05 Jan 2011
Externally publishedYes

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