TY - JOUR
T1 - Metal-organic frameworks based on double-bond-coupled Di-isophthalate linkers with high hydrogen and methane uptakes
AU - Wang, Xi Sen
AU - Shengqian, Ma
AU - Rauch, Karsten
AU - Simmons, Jason M.
AU - Yuan, Daqiang
AU - Wang, Xiaoping
AU - Yildirim, Taner
AU - Cole, William C.
AU - López, Joseph J.
AU - De Meijere, Armin
AU - Zhou, Hong Cai
PY - 2008/5/13
Y1 - 2008/5/13
N2 - Solvothermal reactions of Cu(NO3)2 with azoxybenzene-3,3′,5,5′-tetracarboxylic acid (ILaobtc) or transstilbene-3,3′,5,5′-tetracarboxylic acid (H4sbtc) give rise to two isostructural microporous metal-organic frameworks, Cu 2(abtc)(H2O)2·3DMA (PCN-10, abtc = azobenzene-3,3′,5,5′-tetracarboxylate) and Cu2(sbtc)- (H2O)2·3DMA (PCN-11, sbtc = trans-stilbene-3, 3′,5,5′-tetracarboxylate), respectively. Both PCN-10 and PCN-11 possess significant enduring porosity with Langmuir surface areas of 1779 and 2442 m2/g (corresponding to BET surface areas of 1407 or 1931 m 2/g, respectively) and contain nanoscopic cages and coordinatively unsaturated metal centers. At 77 K, 760 Torr, the excess gravimetric (volumetric) hydrogen uptake of PCN-10 is 2.34 wt % (18.0 g/L) and that of PCN-11 can reach 2.55 wt % (19.1 g/L). Gas-adsorption studies also suggest that MOFs containing C=C double bonds are more favorable than those with N=N double bond in retaining enduring porosity after thermal activation, although N=N has slightly higher H2 affinity. The excess gravimetric (volumetric) adsorption at 77 K saturates around 20 atm and reaches values of 4.33% (33.2 g/L) and 5.05% (37.8 g/L) for PCN-10 and PCN-11, respectively. In addition to its appreciable hydrogen uptake, PCN-11 has an excess methane uptake of 171 cm3(STP)/cm3 at 298 K and 35 bar, approaching the DOE target of 180 v(STP)/v for methane storage at ambient temperature. Thus, PCN-11 represents one of the few materials that is applicable to both hydrogen and methane storage applications.
AB - Solvothermal reactions of Cu(NO3)2 with azoxybenzene-3,3′,5,5′-tetracarboxylic acid (ILaobtc) or transstilbene-3,3′,5,5′-tetracarboxylic acid (H4sbtc) give rise to two isostructural microporous metal-organic frameworks, Cu 2(abtc)(H2O)2·3DMA (PCN-10, abtc = azobenzene-3,3′,5,5′-tetracarboxylate) and Cu2(sbtc)- (H2O)2·3DMA (PCN-11, sbtc = trans-stilbene-3, 3′,5,5′-tetracarboxylate), respectively. Both PCN-10 and PCN-11 possess significant enduring porosity with Langmuir surface areas of 1779 and 2442 m2/g (corresponding to BET surface areas of 1407 or 1931 m 2/g, respectively) and contain nanoscopic cages and coordinatively unsaturated metal centers. At 77 K, 760 Torr, the excess gravimetric (volumetric) hydrogen uptake of PCN-10 is 2.34 wt % (18.0 g/L) and that of PCN-11 can reach 2.55 wt % (19.1 g/L). Gas-adsorption studies also suggest that MOFs containing C=C double bonds are more favorable than those with N=N double bond in retaining enduring porosity after thermal activation, although N=N has slightly higher H2 affinity. The excess gravimetric (volumetric) adsorption at 77 K saturates around 20 atm and reaches values of 4.33% (33.2 g/L) and 5.05% (37.8 g/L) for PCN-10 and PCN-11, respectively. In addition to its appreciable hydrogen uptake, PCN-11 has an excess methane uptake of 171 cm3(STP)/cm3 at 298 K and 35 bar, approaching the DOE target of 180 v(STP)/v for methane storage at ambient temperature. Thus, PCN-11 represents one of the few materials that is applicable to both hydrogen and methane storage applications.
UR - http://www.scopus.com/inward/record.url?scp=44349100424&partnerID=8YFLogxK
U2 - 10.1021/cm800403d
DO - 10.1021/cm800403d
M3 - Article
AN - SCOPUS:44349100424
SN - 0897-4756
VL - 20
SP - 3145
EP - 3152
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 9
ER -