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Metal−Organic Frameworks Based on Double-Bond-Coupled Di-Isophthalate Linkers with High Hydrogen and Methane Uptakes
Open accessAbstract
Solvothermal reactions of Cu(NO 3 ) 2 with azoxybenzene-3,3′,5,5′-tetracarboxylic acid (H 4 aobtc) or trans -stilbene-3,3′,5,5′-tetracarboxylic acid (H 4 sbtc) give rise to two isostructural microporous metal−organic frameworks, Cu 2 (abtc)(H 2 O) 2 ·3DMA (PCN-10, abtc = azobenzene-3,3′,5,5′-tetracarboxylate) and Cu 2 (sbtc)(H 2 O) 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 m 2 /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 H 2 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 cm 3 (STP)/cm 3 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.
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Self-citation
Metadata
- Authors
- Wang, X.-S., Ma, S., Rauch, K., Simmons, J. M., Yuan, D., Wang, X., Yildirim, T., Cole, W. C., López, J. J., Meijere, A. D., & Zhou, H.-C.
- Venue
- Chemistry of Materials
- Publisher
- American Chemical Society (ACS)
- Published
- 2008-04-15
- Volume
- 20
- Issue
- 9
- Pages
- 3145-3152
- ISSN
- 0897-4756 (ISSN-L)
- 1520-5002
- OpenAlex
- W2046464929
- Cited by
- 260
- References
- 52
- FWCI
- 15.41
- Type
- journal article
- Language
- en
- Open access
- green
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