REPORTS

locations (~6300 km on a great circle) imply 14. D. W. Ming et al., J. Geophys. Res. 111, E02S12 (2006). 36. A. H. Treiman et al., Earth Planet. Sci. Lett. 204, 323
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subsequent sequestering of at least part of that 20. A. S. Yen et al., J. Geophys. Res. 113, E06S10 (2008). 41. R.V.M. and D.W.M. acknowledge the NASA Johnson Space
atmosphere in carbonate minerals. 21. D. W. Ming et al., J. Geophys. Res. 113, E12S39 (2008). Center and the NASA Mars Exploration Program for
22. G. Klingelhöfer et al., J. Geophys. Res. 108, 8067 (2003). support. R.V.M. acknowledges the NASA Ames
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1. J. L. Gooding, Icarus 33, 483 (1978). laboratory studies, spectral unmixing of Mini-TES spectra, the NASA Mars Data Analysis Program for support. G.K.
2. J. L. Gooding, in The Solar System: Observations and and Pancam multispectral spectroscopy. and I.F. acknowledge support by the German Space
Interpretations, Rubey Volume IV, M. G. Kivelson, Ed. 24. R. Rieder et al., J. Geophys. Res. 108, 8066 (2003). Agency DLR under contract 50QM9902. A portion of
(Prentice Hall, Upper Saddle River, NJ, 1986), 25. J. L. Campbell et al., J. Geophys. Res. 113, E06S11 the research described in this paper was carried out at
pp. 208–229. (2008). the Jet Propulsion Laboratory, California Institute of
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Tables S1 and S2
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E02S07 (2006). 113, E12S44 (2008). Published online 3 June 2010;
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13. S. W. Squyres et al., J. Geophys. Res. 111, E02S11 (2006). (2000). Include this information when citing this paper.

-210) are described, three of which show excep-

Ultrahigh Porosity in tional porosity. In particular, MOF-210 exhibits
the highest BET (Brunauer-Emmett-Teller) and
Metal-Organic Frameworks Langmuir surface area (6240 and 10,400 m2 g−1)
and pore volume (3.60 cm3 g−1 and 0.89 cm3 cm−3
Hiroyasu Furukawa,1 Nakeun Ko,2 Yong Bok Go,1 Naoki Aratani,1 Sang Beom Choi,2 of MOF crystal) yet reported.
Eunwoo Choi,1 A. Özgür Yazaydin,3 Randall Q. Snurr,3 Michael O’Keeffe,1 In the pursuit of MOFs with ultrahigh po-
Jaheon Kim,2* Omar M. Yaghi1,4* rosity, the octahedral Zn4O(CO2)6 has had a
prominent role as a building unit in producing
Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized structures exhibiting exceptional porosity (Scheme
that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 1) (7, 8, 12–14). Joining such units by 4,4′,44″-
unit was joined with either one or two kinds of organic link, 4,4′,4″-[benzene-1,3,5-triyl-tris benzene-1,3,5-triyl-tribenzoate (BTB) and/or 1,4-
(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4′,44″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate benzenedicarboxylate (BDC) linkers produces
(BBC), 4,4′,44″-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and MOF-5, UMCM-2, and MOF-177 (7, 8, 12–14),
BTE/biphenyl-4,4′-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, which heretofore showed the highest BET surface
-205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas area and pore volume among MOFs (Table 1). We
(hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer- sought to test the likelihood of reaching higher po-
Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, rosities by expanding the links in MOF-177 and by
and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal further exploring the role of mixed links in produc-
surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface ing the desired structures. We prepared the expanded
of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials. forms of MOF-177 from 4,4′,4″-[benzene-1,3,5-
triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE) and
ne of the most important properties of organic links should lead to MOFs with ultrahigh 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]

O metal-organic frameworks (MOFs) is their

high porosity (fraction of void volume to
total volume) and high specific surface area, which
porosity.
However, difficulties arise when targeting such
MOFs: (i) Expanded links often yield fragile
tribenzoate (BBC) to give MOF-180 and MOF-200,
respectively, and used mixed 4,4′,4″-benzene-1,3,5-

has led to many applications concerned with gas frameworks (9), and (ii) the large void space 1
Center for Reticular Chemistry at the California NanoSystems
storage, separations, and catalysis (1–6). An im- within the crystal framework makes it generally Institute, and Department of Chemistry and Biochemistry, Uni-
portant consideration in maximizing the uptake susceptible to self-interpenetration (two lattices versity of California Los Angeles (UCLA), 607 Charles E. Young
of gases within porous MOF crystals is to grow and interpenetrate each other), precluding Drive East, Los Angeles, CA 90095, USA. 2Department of Chem-
increase the number of adsorptive sites within a high porosity (10, 11). In this report, we present istry, Soongsil University, Seoul 156-743, Korea. 3Department
given material. The simplest way to accomplish four examples of MOFs for which it was possible to of Chemical and Biological Engineering, Northwestern Uni-
versity, Evanston, IL 60208, USA. 4UCLA–Department of En-
this is to use slim organic linkers in which the overcome the two challenges and to obtain ma- ergy (DOE) Institute of Genomics and Proteomics, UCLA, 607
faces and edges of the constituent units (such as terials with the highest porosity yet achieved. Charles E. Young Drive East, Los Angeles, CA 90095, USA.
phenylene rings) are exposed for gas adsorp- Specifically, the synthesis and crystal structures *To whom correspondence should be addressed. E-mail:
tion (7, 8). Thus in principle, expansion of the of the four MOFs (MOF-180, -200, -205, and [email protected] (J.K.); [email protected] (O.M.Y.)

424 23 JULY 2010 VOL 329 SCIENCE www.sciencemag.org

 REPORTS
triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate crystal structures of the four MOFs and report It is a basic tenet of reticular chemistry that,
(NDC) and BTE/biphenyl-4,4′-dicarboxylate their adsorption of nitrogen (77 K, 1 bar), hydrogen in the assembly of variously shaped geometric
(BPDC) links to obtain MOF-205 and 210 (Scheme (77 K, 80 bar), and methane and carbon dioxide units, frameworks with highly symmetric vertices
1 and Table 1). Here, we present the synthesis and (298 K, 80 and 55 bar, respectively). and, ideally, one kind of link (“edge transitive”)
would be most likely to form. In the present case
-OOC of linking octahedral and triangular units, at first
Scheme 1. Zn4O(CO2)6 unit (left) is connected
sight the most favorable net (“net” refers to the
with organic linkers (middle) to form MOFs.
periodic graph that is the underlying topology of
COO- MOF-177 the structure) appears to be pyr (15). Indeed, that
is the observed net in MOF-150 (16) and related
4,4',4''-benzene-1,3,5-triyl-
-OOC tribenzoate (BTB) MOFs; however, these form unwanted (denser)
structures with two interpenetrating networks. This
-OOC is unsurprising because pyr is a net with a self-
dual tiling (the same net from when linkers replace
vertices, and vice versa). The interpenetrating dual
nets have the same connectivity involving alter-
COO- MOF-180 nating octahedra and triangles (Fig. 1, A and B).
C
O We recognized that it is necessary to build a MOF
Zn with expanded organic links that is based on a net
4,4',4''-(benzene-1,3,5-triyl-tris
-OOC (ethyne-2,1-diyl))tribenzoate (BTE) with a very different from its dual so as to avoid
interpenetrating frameworks (Fig. 1, C and D) (7).
In earlier studies, we found that with aro-

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-OOC

matic tritopic linkers of the sort used here a closely

related net (qom) is produced in MOF-177 (Fig. 1F)
(7), in which alternating octahedral Zn4O(CO2)6
+ COO- MOF-200 and triangular BTB units produce one of the most
porous structures yet reported, and for which the
interpenetrating dual net involves direct links
between octahedral units and between triangular
Zn4O(CO2)6 4,4',4''-(benzene-1,3,5-triyl-tris
-OOC units (Fig. 1, C to E). However, it is impossible to
(benzene-4,1-diyl))tribenzoate (BBC)
create a MOF with such linkages, and an inter-
-OOC penetrating pair of MOFs does not appear.
COO- Accordingly, an isoreticular non-interpenetrating
expansion of MOF-177 was targeted by using BTE
COO- + MOF-205 or BBC to make the highly porous materials MOF-
180 and -200 (Fig. 1, G and H) (17). The unit cell
COO-
-OOC
BTB 2,6-naphthalenedicarboxylate
volumes of MOF-180 and -200 are respectively
(NDC) 1.9 and 2.6 times greater than that of MOF-177,
-OOC with void volumes of 89 and 90% of the crystal
volume (Table 1). The cage sizes for MOF-180 and
COO- -200 are 15 by 23 and 18 by 28 Å, respectively,
which is on the border of micropores and meso-
COO- + MOF-210 pores. The bulk density for MOF-200 is 0.22 g cm−3,
implying that the qom net is advantageous to re-
COO- duce the dead space and increase the gas storage
-OOC capacity per unit volume in a closed tank. This den-
BTE biphenyl-4,4'-dicarboxylate
(BPDC)
sity is the lowest for MOF structures, and of any
other crystals at room temperature except for those
of the least dense covalent organic frameworks (18).
Table 1. Porosity data of highly porous MOFs. ABET, ALang, and Ageo are the BET, Langmuir, and On the basis of our effective use of the qom
geometric surface areas, respectively. Vp is the measured pore volume. ND, no data; H2T2DC, thieno net for the successful synthesis of the non-
[3,2-b]thiophene-2,5-dicarboxylic acid. interpenetrating MOF-180 and MOF-200, we rec-
ognized that other MOFs of nets without self-dual
Void Crystal
RCSR ABET ALang Ageo* Vp tilings could be made if we used mixed organic
Compound Linker volume density 2 −1 2 −1 2 −1 3 −1 Reference
code −3 (m g ) (m g ) (m g ) (cm g ) links of mixed connectivity. We used both
(%) (g cm )
tritopic H3BTB and ditopic H2NDC in a reaction
MOF-5 pcu BDC 79 0.59 3800 4400 3390 1.55 (14) with Zn ions to produce Zn4O(CO2)6 units and
MOF-177 qom BTB 83 0.43 4500 5340 4740 1.89 (22) make MOF-205 (Fig. 2A) (17). Its structure
MOF-180 qom BTE 89 0.25 ND ND 6080 ND This work belongs to a cubic space group Pm 3n and con-
MOF-200 qom BBC 90 0.22 4530 10400 6400 3.59 This work sists of one type of Zn4O(CO2)6 octahedral unit
MOF-205 ith-d BTB,NDC 85 0.38 4460 6170 4680 2.16 This work whose vertices are connected to four BTB and
MOF-210 toz BTE,BPDC 89 0.25 6240 10400 5850 3.60 This work two NDC links [after this work was completed,
UMCM-2 umt BTB,T2DC 83 0.40 5200 6060 4360 2.32 (13) the same compound was independently reported
MIL-101c mtn-e BDC 83 0.44 4230 5900 2880 2.15 (23, 24) as DUT-6 (19)]. The topology of MOF-205 (ith-d)
*See section S6 in (17). is of considerable intrinsic interest; all the rings of

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REPORTS
the underlying net are 5-rings, and it forms a face- These uptake values in MOF-200 and -210 are the BET method applied to nitrogen adsorption
transitive tiling of dodecahedra [512] and tetrahedra well beyond those observed for other crystalline isotherms provides physically meaningful values
[54] in the ratio 1:3 (Fig. 2C). The dual structure (ith) porous solids (7, 13, 14, 22–24). Further, the mea- for the surface areas of MOFs (25).
is an edge-transitive net with tetrahedral and sured values are near the values predicted on the Given the exceptional properties of such
icosahedral vertices and very different from the basis of the structure, indicating that these materials materials, it is expected that MOFs with ultra-
original net. are well activated. Because of the successful sam- high surface area would exhibit exceptional gas
Attempts at isoreticular expansion of MOF- ple activation, extremely high BET (and Langmuir) storage capacity. Accordingly, this series of
205 by use of the linkers BTE and BPDC surface areas were obtained: 4530 (10,400), 4460 MOFs was subjected to high-pressure hydrogen
produced a different but related material (termed (6,170), and 6240 (10,400) m2 g−1 for MOF-200, (77 K) and methane (298 K) adsorption so as to
MOF-210) (Fig. 2B). MOF-210 was prepared -205, and -210, respectively (25). The BET surface examine their potential utility in the storage of gas-
from a solvothermal reaction of H3BTE, H2BPDC, area of MOF-210 is the highest reported for crys- eous fuels (Fig. 3, B and C, and table S12). In
and zinc(II) nitrate hexahydrate (17). Similar to the talline materials. It has recently been shown that hydrogen isotherms, these MOFs reach saturation
discovery of MOF-177 (7), this proved to be ser-
endipitous: Rather than the 12-face tile of ith-d,
the new topology has 30-face tiles, and the full tiling
consists of [46.524], [43.56], and [54] in the ratio
1:2:3 (Fig. 2D). It is hard to envisage how the con-
nectivity is determined; however, we believe the
subtle difference in the link length ratio (for exam-
ple, 0.76 for MOF-210 and 0.79 for UMCM-2)
may be important. The dimension of the largest
cage in MOF-210 is 26.9 by 48.3 Å, which com-

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prises 18 Zn4O units with 14 BTE and 6 BPDC
links. The estimated bulk density (void space) is
0.25 g cm−3 (89%), which is almost the same as
that for MOF-180.
Considering the bulk density and void space
calculated from the crystal structure analyses,
MOF-200 and -210 are promising candidates to
realize ultrahigh surface area. Before gas adsorp-
tion measurements, grand canonical Monte Carlo
(GCMC) simulations were performed to calcu-
late nitrogen adsorption isotherms (17). Predicted
isotherms (Fig. 3A) show unusual steps attributed
to the micropore filling at P/P0 = 0.12 and 0.26
(for MOF-200 and -210, respectively), and total
nitrogen uptakes in MOF-200 and -210 reaching
2650 and 2300 cm3 g−1, respectively. The BET
and Langmuir surface areas determined from
these calculated isotherms are respectively 6260
and 12,040 for MOF-200 and 6580 and 10,450
m2 g−1 for MOF-210; these are much higher than
values reported previously for other porous crystals.
To assess the architectural stability and po-
rosity of these low-density MOFs, and to con-
firm the calculations, we measured nitrogen
adsorption isotherms on the guest free samples
of MOF-200, -205, and -210. Preliminary trials
revealed that the solvent exchange followed by
pore evacuation under vacuum was not effective
to activate MOF-200 and -210 without losing the
porosity. Thus, these crystals were fully ex-
changed with liquid CO2, they were kept under
supercritical CO2 atmosphere, and then their
pores were bled of CO2 in order to yield activated
samples (20, 21). Successful guest removal was
confirmed by powder x-ray diffraction measure-
ments and elemental analyses (21). As shown in
Fig. 3A, all MOF samples show distinctive steps
(P/P0 = 0.14, 0.09, and 0.27 for MOF-200, -205,
and -210, respectively), and the profiles for Fig. 1. Connectivity of pyr and qom (6,3)-coordinated nets. For pyr (A), pairs of pyr nets can naturally
MOF-200 and -210 are nearly the same as the interpenetrate (B). In contrast, qom is not self-dual (C to E); the connectivity of the net of the dual tiling
predicted isotherms. The maximum nitrogen up- for qom (D) is very different from the original (C). Crystal structures of MOF-177 (F), MOF-180 (G), and
take capacities at 77 K in MOF-200, -205, and -210 MOF-200 (H) are found in qom net (C). The yellow ball is placed in the structure for clarity and to indicate
are 2340, 1410, and 2330 cm3 g−1, respectively. space in the cage. Zn, blue, tetrahedral; O, red; and C, black. Hydrogen atoms are omitted for clarity.

426 23 JULY 2010 VOL 329 SCIENCE www.sciencemag.org

 REPORTS
Fig. 2. Crystal structures of uptakes, and the saturation pressure increases
MOF-205 (A) and MOF-210 with an increase in the cavity size. The surface
(B). The yellow and orange balls excess hydrogen uptake in MOF-210 (86 mg g−1)
are placed in the structure for is higher than those in MOF-5, MOF-177,
clarity and to indicate space in UMCM-2, and NOTT-112 (13, 14, 22, 26, 27).
the cage. Atom colors are the The total uptake that a material can store is more
same as in Fig. 1. Tiling of (C) relevant to the practicability of using H2 as a fuel,
ith-d and (D) toz nets. but it cannot be measured experimentally. There-
fore, we estimated this value using the pore vol-
ume and the density of hydrogen at 77 K (22).
The calculated gravimetric hydrogen density in
MOF-210 (176 mg g−1) exceeds that of typical
alternative fuels (methanol and ethanol) and
hydrocarbons (pentane and hexane). MOF-200
and -205 also show large total hydrogen uptake
(163 and 123 mg g−1, respectively); again, these
values are higher than MOF-177 (22).
Methane uptake was measured at 298 K
and up to 80 bar (Fig. 3C); under the present
experimental conditions, all isotherms were not
saturated. Although the excess methane uptake
in MOF-200, -205, and -210 (234, 258, and 264

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mg g−1 at 80 bar, respectively) were smaller
than that in PCN-14 (253 mg g−1 at 290 K and
35 bar, respectively) (28), the calculated total
uptakes (446, 394, and 476 mg g−1 for MOF-200,
-205, and -210, respectively) were more than 50%
greater than those of PCN-14. Moreover, the cor-
responding volumetric methane densities in the
present MOFs are respectively 2, 3, and 2.5 times
greater than volumetric bulk density (grams per
liter) of methane at the same temperature and
pressure (table S12). Because the isotherms are
nearly linear up to 80 bar, these materials can
deliver most of the sorbed methane in the pres-
sure range between 10 to 200 bar.
Large storage volumes should also be desir-
able for short-term CO2 storage. High-pressure
CO2 isotherms for all three MOFs were collected
and are presented in Fig. 3D. These MOFs show
A 3000 B 100
N2, 77 K H2, 77 K sigmoidal isotherms, and the pressure for the
2500 80 steep rise reflects the pore size of the MOFs. An
N2 uptake (cm3 g-1)

H2 uptake (mg g-1)

2000
isotherm for MOF-205 is saturated at a pressure
MOF-200 (simulated)
MOF-210 (simulated)
60 of 37 bar, whereas the saturation pressure for MOF-
1500 200 and -210 are ~50 bar. In contrast to hydrogen
40 MOF-210 and methane uptakes, the amounts of excess CO2
1000 MOF-200
MOF-200 MOF-177
MOF-205 uptake are directly related to the total pore volume.
The CO2 uptake value of 2400 mg g−1 in both
20 MOF-177
500 MOF-210 MOF-5
MOF-5 (14)
MOF-205
MOF-5
0 0 MOF-200 and -210 exceeds those of any other po-
0 0.2 0.4 0.6 0.8 1.0 0 20 40 60 80 rous material, such as MOF-177 and MIL-101c(Cr)
P/P0 Pressure / bar
(1470 and 1760 mg g−1, respectively) (24).
C 300 D 3000
The ultrahigh surface areas exhibited by
CH4, 298 K CO2, 298 K
250 2500 MOF-200 and -210 are near the ultimate limit for
CO2 uptake (mg g-1)
CH4 uptake (mg g-1)

MOF-200
MOF-210 solid materials. To appreciate this, it is useful to
200 2000 MOF-205
MOF-177 note that all these compounds have a volume-
MOF-5
150 1500 specific surface area in the range of 1000 to 2000
MOF-210
m2 cm−3 = 1 × 109 to 2 × 109 m−1, and for a
100 1000
MOF-205
MOF-177
cube of edge d the external surface area/volume
50 MOF-200 500 is 6d2/d3 = 6/d. Thus, for a monodisperse powder
MOF-5
of cubic nanoparticles to have external surface that
0 0
0 20 40 60 80 0 10 20 30 40 50 60 is equal to that of these MOFs the cube edge
Pressure / bar Pressure / bar would have to be only 3 to 6 nm, which is a size
Fig. 3. (A) Low-pressure N2 isotherms of MOF-5, -177, -200, -205, and -210 at 77 K. Simulated far too small to practically realize in stable dry
isotherms of MOF-200 and -210 were overlaid. P/P0, relative pressure. High-pressure H2 isotherms were powders and therefore impossible to access the full
measured at 77 K (B), and (C) CH4 and (D) CO2 isotherms were measured at 298 K of the same MOFs. surface area of such particles. This analysis

www.sciencemag.org SCIENCE VOL 329 23 JULY 2010 427

REPORTS
emphasizes that MOFs are truly “nanomaterials” 15. M. O’Keeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi, Hydrogen Energy R&D Center, one of the 21st Century
in the sense that they can be designed to give Acc. Chem. Res. 41, 1782 (2008). Frontier R&D Programs (the Ministry of Education,
16. H. K. Chae, J. Kim, O. D. Friedrichs, M. O’Keeffe, Science and Technology of Korea to J.K.), and the
volume-specific surface areas that are equal to the O. M. Yaghi, Angew. Chem. Int. Ed. 42, 3907 (2003). Defense Threat Reduction Agency (HDTRA1-08-C-005 to
external surface areas of nanometer-sized particles. 17. Materials and methods are available as supporting R.Q.S.). We thank N. W. Ockwig (Sandia National
material on Science Online. Laboratories) for his initial work, S. Khan (UCLA) for his
References and Notes 18. H. M. El-Kaderi et al., Science 316, 268 (2007). help in single-crystal x-ray structure collection and
1. U. Mueller et al., J. Mater. Chem. 16, 626 (2006). analysis of MOF-200, Y. K. Park and E. Jo (Soongsil
19. N. Klein et al., Angew. Chem. Int. Ed. 48, 9954 (2009).
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Soc. 129, 14176 (2007). DOE (DE-FG36-05GO15001 to O.M.Y.). We thank the Include this information when citing this paper.

OAE1a is the result of volcanogenic CO2-related

Calcareous Nannoplankton Response ocean acidification (7, 10, 17).
We analyzed calcareous nannofossil assem-
to Surface-Water Acidification Around blages from two drill sites in the Tethys (Cismon
core) and Pacific [Deep Sea Drilling Project
Oceanic Anoxic Event 1a (DSDP) site 463] Oceans (fig. S1) (18). At both
sites, nannofossil changes integrated with geo-
Elisabetta Erba,1* Cinzia Bottini,1 Helmut J. Weissert,2 Christina E. Keller2 chemical and cyclochronological data (15, 19)
identify and date the effects of acidification on cal-
Ocean acidification induced by atmospheric CO2 may be a major threat to marine ecosystems, particularly to careous nannoplankton. Shortly before magnetic
calcareous nannoplankton. We show that, during the Aptian (~120 million years ago) Oceanic Anoxic Event chron M0 (Fig. 1), at 121.3 Ma (19), nannoconid
1a, which resulted from a massive addition of volcanic CO2, the morphological features of calcareous abundance declined and nannofossil paleofluxes
nannofossils traced the biological response to acidified surface waters. We observe the demise of heavily (tracing nannoplankton carbonate production and
calcified nannoconids and reduced calcite paleofluxes at the beginning of a pre-anoxia calcification crisis. accumulation) decreased as response to a major
Ephemeral coccolith dwarfism and malformation represent species-specific adjustments to survive lower injection of volcanogenic CO2. Later, a sharp nan-
pH, whereas later, abundance peaks indicate intermittent alkalinity recovery. Deepwater acidification noconid crisis at 120.25 Ma was part of a global
occurred with a delay of 25,000 to 30,000 years. After the dissolution climax, nannoplankton and carbonate calcification failure of planktonic and benthic cal-
recovery developed over ~160,000 years under persisting global dysoxia-anoxia. cifiers in pelagic and neritic settings under excess
CO2 in the ocean-atmosphere system (17). During
he dissolution of an atmospheric CO2 sur- adapt to increased acidity; however, past examples the 1-million-year-long interval between these two

T plus [that is, over 500 parts per million

(ppm)] in the ocean lowers pH and reduces
the CaCO3 saturation state, consequently acceler-
of ocean acidification occurred over tens of thou-
sands of years, giving time for life to adjust to CO2
concentrations as high as 2000 to 3000 ppm (7).
events, the geological record reveals subtle effects of
ocean acidification traced only by nannofossils, and
specifically by the heavily calcified nannoconids,
ating carbonate dissolution in the deep sea (1). The The early Aptian [121 to 118 million years with trivial effects on other coccoliths and appa-
effect of modern surface-water acidification on ago (Ma)] represents a case history of excess CO2 rently no evidence in the lithologic and geochem-
organisms with CaCO3-based skeletons or tests, derived from a major volcanic episode, namely ical records. Although the negative carbon isotopic
such as calcareous nannoplankton, remains elusive the emplacement of the Ontong Java Plateau event (CIE) at the beginning of global anoxia
(2–6). Throughout Earth’s history, there is evidence (OJP) (8, 9), which is marked by changes in the (~120 Ma) coincides with the drop in carbonate
of large CO2 releases, greenhouse conditions, ocean evolutionary rates, species richness, abundance, content, there was an increase in relative abundance
acidification, and major changes in biota, partic- and calcite production of calcareous nanno- of Biscutum constans, Zeugrhabdotus erectus, and
ularly in marine calcifiers (7). In many cases, the plankton (10–12). These changes occurred dur- Discorhabdus rotatorius, represented by dwarfed
geological record indicates that ocean biota can ing Oceanic Anoxic Event 1a (OAE1a) (~120 specimens (Fig. 1). Size variation was species-
Ma), which was a time of severe global warming specific at both sites, because B. constans displays
1
Dipartimento di Scienze della Terra “Ardito Desio,” Università (13, 14). Although global anoxia and enhanced the most pronounced morphometric decrease (a
degli Studi di Milano, via Mangiagalli 34, 20133 Milano, Italy. organic matter burial are the most striking and volume/mass reduction of 50 to 60% for single
2
Department of Earth Sciences, Geology, Eidgenössische Tech-
nische Hochschule (ETH)–Zentrum, Sonneggstrasse 5, CH-8092 intriguing paleoceanograhic phenomena during coccoliths), whereas Z. erectus diminishes in size
Zürich, Switzerland. this event, OAE1a sediments reveal a sequence to a lesser extent (a volume/mass reduction of 30
*To whom correspondence should be addressed. E-mail: of CO2 pulses (15) and weathering changes (16). to 40% for single coccoliths). D. rotatorius also
[email protected] For example, the cutoff of carbonates during exhibits smaller-than-normal sizes throughout the

428 23 JULY 2010 VOL 329 SCIENCE www.sciencemag.org

Ultrahigh Porosity in Metal-Organic Frameworks
Hiroyasu Furukawa, Nakeun Ko, Yong Bok Go, Naoki Aratani, Sang Beom Choi, Eunwoo Choi, A. Özgür Yazaydin, Randall Q.
Snurr, Michael O'Keeffe, Jaheon Kim and Omar M. Yaghi

Science 329 (5990), 424-428.

DOI: 10.1126/science.1192160originally published online July 1, 2010

Network Approaches to Highly Porous Materials

Metal-organic frameworks (MOFs), in which inorganic centers are bridged by organic linkers, can achieve very
high porosity for gas absorption. However, as the materials develop larger void spaces, there is also more room for
growing interpenetrating networks−−filling the open spaces not with gas molecules but with more MOFs. Furukawa et al.
(p. 424, published online 1 July) describe the synthesis of a MOF in which zinc centers are bridged with long, highly

Downloaded from http://science.sciencemag.org/ on July 18, 2018

conjugated organic linkers, but in which the overall symmetry of the networks created prevents formation of
interpenetrating networks. Extremely high surface areas and storage capacities for hydrogen, carbon dioxide, and
methane were observed.

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