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A Novel Bismuth‐Based Metal–Organic Framework for High Volumetric Methane and Carbon Dioxide Adsorption
Author(s) -
Savage Mathew,
Yang Sihai,
Suyetin Mikhail,
Bichoutskaia Elena,
Lewis William,
Blake Alexander J.,
Barnett Sarah A.,
Schröder Martin
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304799
Subject(s) - bar (unit) , adsorption , piperazine , chemistry , metal organic framework , carbon dioxide , methane , metal , nitric acid , bismuth , inorganic chemistry , crystallography , organic chemistry , physics , meteorology
Abstract Solvothermal reaction of H 4 L (L=biphenyl‐3,3′,5,5′‐tetracarboxylate) and Bi(NO 3 ) 3 ⋅ (H 2 O) 5 in a mixture of DMF/MeCN/H 2 O in the presence of piperazine and nitric acid at 100 °C for 10 h affords the solvated metal–organic polymer [Bi 2 (L) 1.5 (H 2 O) 2 ] ⋅ (DMF) 3.5 ⋅ (H 2 O) 3 (NOTT‐220‐solv). A single crystal X‐ray structure determination confirms that it crystallises in space group P 2/ c and has a neutral and non‐interpenetrated structure comprising binuclear {Bi 2 } centres bridged by tetracarboxylate ligands. NOTT‐220‐solv shows a 3,6‐connected network having a framework topology with a {4 ⋅ 6 2 } 2 {4 2 ⋅ 6 5 ⋅ 8 8 }{6 2 ⋅ 8} point symbol. The desolvated material NOTT‐220a shows exceptionally high adsorption uptakes for CH 4 and CO 2 on a volumetric basis at moderate pressures and temperatures with a CO 2 uptake of 553 g L −1 (20 bar, 293 K) with a saturation uptake of 688 g L −1 (1 bar, 195 K). The corresponding CH 4 uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH 4 uptake for NOTT‐220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H 2 uptake of NOTT‐220a at 20 bar, 77 K is 42 g L −1 . These gas uptakes have been modelled by grand canonical Monte Carlo (GCMC) and density functional theory (DFT) calculations, which confirm the experimental data and give insights into the nature of the binding sites of CH 4 and CO 2 in this porous hybrid material.