TY - JOUR
T1 - A novel bismuth-based metal-organic framework for high volumetric methane and carbon dioxide adsorption
AU - Savage, Mathew
AU - Yang, Sihai
AU - Suetin, Mikhail
AU - Bichoutskaia, Elena
AU - Lewis, William
AU - Blake, Alexander J.
AU - Barnett, Sarah A.
AU - Schröder, Martin
PY - 2014/6/23
Y1 - 2014/6/23
N2 - Solvothermal reaction of H4L (L=biphenyl-3,3′,5,5′- tetracarboxylate) and Bi(NO3)3·(H 2O)5 in a mixture of DMF/MeCN/H2O in the presence of piperazine and nitric acid at 100-°C for 10 h affords the solvated metal-organic polymer [Bi2(L)1.5(H 2O)2]·(DMF)3.5·(H 2O)3 (NOTT-220-solv). A single crystal X-ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non-interpenetrated structure comprising binuclear {Bi2} centres bridged by tetracarboxylate ligands. NOTT-220-solv shows a 3,6-connected network having a framework topology with a {4·62} 2{42·65·88}{6 2·8} point symbol. The desolvated material NOTT-220a shows exceptionally high adsorption uptakes for CH4 and CO2 on a volumetric basis at moderate pressures and temperatures with a CO2 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 CH4 uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH4 uptake for NOTT-220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H2 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 CH4 and CO2 in this porous hybrid material. High density: The 3,6-connected material [Bi2(L)1.5(H2O) 2]·(DMF)3.5·(H2O)3 (NOTT-220-solv; see figure; L=biphenyl-3,3′,5,5′-tetracarboxylate) shows a new framework topology with a {4·62} 2{42·65·88}{6 2·8} point symbol. The desolvated material NOTT-220a shows a maximum CH4 uptake of 287 V(STP)/V at 20 bar, 195 K with a CO 2 uptake of 688 g-L-1 at 1 bar, 195 K.
AB - Solvothermal reaction of H4L (L=biphenyl-3,3′,5,5′- tetracarboxylate) and Bi(NO3)3·(H 2O)5 in a mixture of DMF/MeCN/H2O in the presence of piperazine and nitric acid at 100-°C for 10 h affords the solvated metal-organic polymer [Bi2(L)1.5(H 2O)2]·(DMF)3.5·(H 2O)3 (NOTT-220-solv). A single crystal X-ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non-interpenetrated structure comprising binuclear {Bi2} centres bridged by tetracarboxylate ligands. NOTT-220-solv shows a 3,6-connected network having a framework topology with a {4·62} 2{42·65·88}{6 2·8} point symbol. The desolvated material NOTT-220a shows exceptionally high adsorption uptakes for CH4 and CO2 on a volumetric basis at moderate pressures and temperatures with a CO2 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 CH4 uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH4 uptake for NOTT-220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H2 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 CH4 and CO2 in this porous hybrid material. High density: The 3,6-connected material [Bi2(L)1.5(H2O) 2]·(DMF)3.5·(H2O)3 (NOTT-220-solv; see figure; L=biphenyl-3,3′,5,5′-tetracarboxylate) shows a new framework topology with a {4·62} 2{42·65·88}{6 2·8} point symbol. The desolvated material NOTT-220a shows a maximum CH4 uptake of 287 V(STP)/V at 20 bar, 195 K with a CO 2 uptake of 688 g-L-1 at 1 bar, 195 K.
KW - bismuth
KW - grand canonical monte carlo simulations
KW - metal-organic framework
KW - methane
UR - http://www.scopus.com/inward/record.url?scp=84902981358&partnerID=8YFLogxK
U2 - 10.1002/chem.201304799
DO - 10.1002/chem.201304799
M3 - Article
AN - SCOPUS:84902981358
VL - 20
SP - 8024
EP - 8029
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 26
ER -