Chem. Mater. 2007, 19, 3681-3685
3681
Raman Spectroscopic Investigation of CH4 and N2 Adsorption in Metal-Organic Frameworks Diana Y. Siberio-Pe´rez, Antek G. Wong-Foy, Omar M. Yaghi,† and Adam J. Matzger* Department of Chemistry and the Macromolecular Science and Engineering Program, The UniVersity of Michigan, 930 North UniVersity AVenue, Ann Arbor, Michigan 48109-1055 ReceiVed February 27, 2007. ReVised Manuscript ReceiVed April 18, 2007
The adsorption behavior of CH4 and N2 (298 K, 30 bar) in a series of isoreticular metal-organic frameworks (IRMOFs) was investigated by Raman spectroscopy. For CH4, the ν1 vibrational mode shifted to lower frequency by 7.6, 8.4, 11.0, 10.3, and 10.1 cm-1 from 2917 cm-1 when adsorbed to IRMOF-1, -6, -8, -11, and -18, respectively. Along this same series, the adsorbed N2 stretch exhibited smaller shifts of 2.7, 3.1, 4.2, 4.1, and 3.7 cm-1. These shifts arise because of interactions within the framework pores, and not with the outer crystal surface. In all cases, Raman spectra at pressures up to 30 bar showed that saturation of the sorption sites does not occur. The observed shifts of the vibrational modes for each gas indicate different chemical environments within different IRMOFs, pointing to the important role the linkers play in the adsorption of gases.
1. Introduction Metal-organic frameworks (MOFs) are extended crystalline porous structures with extraordinary surface areas that enable unprecedented adsorption phenomena.1-3 A MOF consists of a metal ion or metal cluster linked together by organic units to give a well-defined periodic structure.4,5 By systematically varying the organic linker, we can synthesize a series of MOFs with controlled chemical and physical properties without altering the underlying topology. Such a series has been created on the basis of the cubic topology of MOF-5, wherein a Zn4O cluster is used in conjunction with the linear organic linker benzene-1,4-dicarboxylate,1 giving rise to isoreticular metal-organic frameworks (IRMOFs). As the parent structure, MOF-5 is designated as IRMOF-1.2 The high surface areas and tunable porosities exhibited by IRMOFs make them attractive for adsorption processes. The application of IRMOFs as media for gas storage has become especially appealing because of the possibility of these serving as hosts to alternative fuels such as CH4 or H2. The difference in adsorption affinities of IRMOFs for these and other gases has been reported.2,6 Given the emerging applications of IRMOFs as gas storage materials, * To whom correspondence should be addressed. Phone: 734-615-6627. Fax: 734-615-8553. E-mail:
[email protected]. † Current address: Department of Chemistry and Biochemistry, California NanoSystems Institute and Center for Reticular Materials Research, University of California, Los Angeles, CA 90024.
(1) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 1999, 402, 276-279. (2) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keefe, M.; Yaghi, O. M. Science 2002, 295, 469-472. (3) Chae, H. K.; Siberio-Pe´rez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O’Keeffe, M.; Yaghi, O. M. Nature 2004, 427, 523527. (4) Rosi, N. L.; Eddaoudi, M.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. CrystEngComm 2002, 401-404. (5) Rowsell, J. L. C.; Yaghi, O. M. Microporous Mesoporous Mater. 2004, 73, 3-14. (6) Rowsell, J. L. C.; Millward, A. R.; Park, K. S.; Yaghi, O. M. J. Am. Chem. Soc. 2004, 126, 5666-5667.
it is important to develop an understanding of the adsorbate/ adsorbent behavior in the pores, an area that remains largely unexplored in MOFs. Within each framework, there are two distinct sites where the gas molecules may adsorb: the metal cluster and the organic linker. A series of low temperature and pressure inelastic neutron scattering (INS)7,8 and X-ray diffraction9 experiments have implicated the metal cluster as primary binding sites. Computational studies10,11 have corroborated these observations and led to the prevailing belief that adsorption to the linkers is a minor contributor to gas uptake. Here, we investigate this hypothesis with Raman spectroscopy at room temperature and elevated pressure to determine if this behavior holds under conditions more relevant to storage applications. This analysis method is a powerful technique for probing the adsorbate/adsorbent interactions offering facile detection of perturbations to the vibrational modes of the gaseous guest created by interactions with the framework.12 In the present paper, we investigate the Raman spectra of CH4 and N2 adsorbed in samples of IRMOF-1, -6, -8, -11, and -18 (Figure 1). This series, which is built from a common metal cluster motif, offers a range (7) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127-1129. (8) Rowsell, J. L. C.; Eckert, J.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 14904-14910. (9) Rowsell, J. L. C.; Spencer, E. C.; Eckert, J.; Howard, J. A. K.; Yaghi, O. M. Science 2005, 309, 1350-1354. (10) Yildirim, T.; Hartman, M. R. Phys. ReV. Lett. 2005, 95. (11) Dailly, A.; Vajo, J. J.; Ahn, C. C. J. Phys. Chem. B 2006, 110, 10991101. (12) The utility of this approach for studying porous materials including zeolites and carbon nanotubes has been demonstrated: (a) Smudde, G. H.; Slager, T. L.; Coe, C. G.; MacDougall, J. E.; Weigel, S. J. Appl. Spectrosc. 1995, 49, 1747-1755. (b) Mellot, C. F.; Davidson, A. M.; Eckert, J.; Cheetham, A. K. J. Phys. Chem. B 1998, 102, 25302535. (c) Huang, Y. N.; Havenga, E. A. Langmuir 1999, 15, 66056608. (d) Kortus, J.; Irmer, G.; Monecke, J.; Pederson, M. R. Modell. Simul. Mater. Sci. Eng. 2000, 8, 403-411. (e) Huang, Y. N.; Leech, J. H.; Havenga, E. A.; Poissant, R. R. Microporous Mesoporous Mater. 2001, 48, 95-102. (f) Williams, K. A.; Pradhan, B. K.; Eklund, P. C.; Kostov, M. K.; Cole, M. W. Phys. ReV. Lett. 2002, 88.
10.1021/cm070542g CCC: $37.00 © 2007 American Chemical Society Published on Web 06/27/2007
3682 Chem. Mater., Vol. 19, No. 15, 2007
Siberio-Pe´ rez et al.
Figure 1. Dicarboxylic acid forms of the linkers used for the synthesis of IRMOF-1, -6, -8, -11, and -18.
of pore sizes, surface areas, and chemical environments across which to compare the binding of gases to determine if the linker contributes substantially to gas sorption behavior. IRMOF-1, -6, and -18 are similar in the dimensions of the pores, but differ in the nature of functional groups adorning the interior: hydrogen atoms on the benzene ring in IRMOF1, methyl groups for IRMOF-18, and a cyclobutenyl group for IRMOF-6. The influence of expanded pore size is investigated with the remaining two IRMOFs, which relate to IRMOF-1 by substitution of the benzene ring with naphthalene (IRMOF-8) or 4,5,9,10-tetrahydropyrene (IRMOF-11). 2. Experimental Section IRMOF-1, -6, -8, -11, and -18 were synthesized as detailed earlier.2,6 Microcrystalline samples were placed in a high-pressure Raman cell (HPRC) containing a chamber capable of simultaneously holding multiple samples. The HPRC was evacuated to
