Metal−Organic Frameworks Based on Double-Bond-Coupled Di-Isophthalate Linkers with High Hydrogen and Methane Uptakes
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- 作者：Xi-Sen Wang ; Shengqian Ma ; Karsten Rauch ; Jason M. Simmons ; Daqiang Yuan ; Xiaoping Wang ; Taner Yildirim ; William C. Cole ; Joseph J. Ló ; pez ; Armin de Meijere ; Hong-Cai Zhou
- 刊名：Chemistry of Materials
- 出版年：2008
- 出版时间：May 13, 2008
- 年：2008
- 卷：20
- 期：9
- 页码：3145 - 3152
- 全文大小：1203K
- 年卷期：v.20,no.9(May 13, 2008)
- ISSN：1520-5002
文摘
Solvothermal reactions of Cu(NO3)2 with azoxybenzene-3,3′,5,5′-tetracarboxylic acid (H4aobtc) or trans-stilbene-3,3′,5,5′-tetracarboxylic acid (H4sbtc) give rise to two isostructural microporous metal−organic frameworks, Cu2(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 m2/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
ges/entities/dbd_2.gif">C double bonds are more favorable than those with Nges/entities/dbd_2.gif">N double bond in retaining enduring porosity after thermal activation, although Nges/entities/dbd_2.gif">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.