WO 2008/082087 Al

WO 2008/082087 Al

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date (10) International Publication Number 10 July 2008 (10.07.2008) PCT WO 2008/082087 Al (51) International Patent Classification: Dong-Sin, Apt. 956-2, Yeongtong -dong Yeongtong-gu, COlB 3/00 (2006.01) Suwon-si, Gyeonggi-do 443-810 (KR). YOON, Ji-Hye [KR/KR]; 790-8 Gohyeon-ri, Sinhyeon-eup Geoje-si, (21) International Application Number: Gyeongsangnam-do 656-800 (KR). CHOI, Sang-Beom PCT/KR2007/006166 [KR/KR]; 202-403, Yuseong Mongnyeon Apt. 444, (22) International Filing Date: Sangdae-dong Yuseong-gu, Daejeon 305-313 (KR). 30 November 2007 (30.1 1.2007) OH, You-Jin [KR/KR]; 101-710 Hansin Apt., Sosabon (25) Filing Language: Korean 3-dong Sosa-gu, Bucheon-si, Gyeonggi-do 422-709 (KR). SEO, Min-Jeong [KR/KR]; 137-19, Myeon- English (26) Publication Language: mok 2-dong Jungnang-gu, Seoul 131-819 (KR). KIM, (30) Priority Data: Ja-Heon [KR/KR]; B-203, Jisan Billa, 651-4, Sinhyeon-ri 10-2007-0000570 3 January 2007 (03.01.2007) KR Opo-eup Gwangju-si, Gyeonggi-do 464-895 (KR). WON, Byoung-Ho [KR/KR]; 933-13, Sinjeong 5-dong (71) Applicant (for all designated States except US): INSIL- Yangcheon-gu, Seoul 158-075 (KR). CHOI, Ki-Hang ICOTECH CO., LTD [KR/KR]; A-1 101 Kolontripolis, Geumgok-dong, Bundang-gu, Seongnam-si, Gyeonggi-do [KR/KR]; 409-705 Sinnae Apt., Muk-dong Jungnang-gu, Seoul 131-140 (KR). 463-943 (KR). (74) Agent: HAM, Hyun-Kyung; 14R, Kukdong Building, (72) Inventors; and 60-1, Chungmuro 3-ka, Chung-ku, Seoul 100-705 (KR). (75) Inventors/Applicants (for US only): JUNG, Dong-Hyun [KR/KR]; 134-1801 Hwanggol Maeul 1-danji Apt., Yeong- (81) Designated States (unless otherwise indicated, for every tong 1-dong, Yeongtong-gu, Suwon-si, Gyeonggi-do kind of national protection available): AE, AG, AL, AM, 443-739 (KR). KIM, Min-Kyoung [KR/KR]; 102-1703 AT,AU, AZ, BA, BB, BG, BH, BR, BW, BY,BZ, CA, CH, Dodam Maeul Hyun-Dai I-Park, Jukjeon-dong Suji-gu CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, Yongin-si, Gyeonggi-do 448-984 (KR). KIM, Dae-Jin ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, [KR/KR]; 106-505, Guro Doosan Apt., Guro 4-dong IN, IS, JP, KE, KG, KM, KN, KP, KZ, LA, LC, LK, LR, Guro-gu, Seoul 152-764 (KR). LEE, Tae-Bum [KR/KR]; LS, LT, LU, LY,MA, MD, ME, MG, MK, MN, MW, MX, 104-1402, Hyundai Homecity Apt., 11-1, Mullae-dong MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, 6-ga Yeongdeungpo-gu, Seoul 150-096 (KR). CHOI, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, Seung-Hoon [KR/KR]; 311-904 Cheongmyeong Maeul TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW [Continued on next page (54) Title: COORDINATION POLYMER CRYSTAL WITH POROUS METAL-ORGANIC FRAMEWORKS AND PREPERA- TION METHOD THEREOF (57) Abstract: Disclosed is coordination polymer crystal wit porous metal-organic framework (MOFs), in which, while a crysta state of the coordination polyme crystal is maintained, an additiona material selected from the grou consisting of an organic compound a metal cluster, and an organometalli compound is chemically bonded t the coordination polymer crystal Therefore it is possible easily adsor and store more guest molecule regardless of a change in an ambien temperature or pressure due t the chemically bonded additiona material (such as an organi compound, a metal cluster, and a organometallic compound). (84) Designated States (unless otherwise indicated, for every PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, kind of regional protection available): ARIPO (BW, GH, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FT, Published: COORDINATION POLYMER CRYSTAL WITH POROUS METAL-ORGANIC FRAMEWORKS AND PREPERATION METHOD THEREOF Technical Field The present invention relates to a coordination polymer crystal with porous metal-organic frameworks, which can adsorb/desorb gas or organic molecules, and a method of preparing the same. Background Art Recently, many countries have tried to develop wind power, tidal power, geothermal energy, solar energy, hydrogen gas, etc. as energy sources for replacing depletable fossil fuels. Especially, from among such energy sources, hydrogen gas has the highest energy efficiency per unit mass and no harmful byproducts of combustion, and thus research on the preparation, storage, transportation, etc. thereof has been conducted. In particular, a focus is placed on research on the practical use of a fuel cell and the development of a material for efficiently storing hydrogen gas. Currently, materials capable of storing hydrogen gas include metal hydride, carbon nanotube, carbon compound such as activated carbon, zeolite, metal- organic framework (MOF) , etc. Especially, the MOF has been noticed due to a higher specific surface area than those of other materials, and accordingly, the C possibility of reversibly storing hydrogen. The MOF is a kind of organic-inorganic hybrid compound, in which a metal and an organic ligand are three-dimensionally linked via the organic ligand functioning as a linker. Specifically, as shown in FIG. 1 , the MOF refers to a material in which the organic ligand is coordinated to at least two metals, and each of the coordinated metals is coordinated in a chain-like manner to at least one other organic ligand, thereby forming many tiny spaces, i.e. a network structure with pores, inside the framework. Such a MOF is prepared by various preparation methods. For example, the MOF can be prepared through a substitution reaction of organic ligand ions by using metal salts as a metal source. Specifically, in such preparation, zinc nitrate [Zn (NO3)2] as the metal source, and a dicarboxylic acid-based compound a s the ligand are mainly used so as to prepare the framework (O.M. Yaghi et al. Science, 2003, vol. 300, p . 1127; WO 02/088148). Also, an isoreticular metal-organic framework (IRMOF) can be prepared by using zinc as the metal source to thereby form core zinc oxide (Zn4O ) and by using an organic ligand such as a dicarboxylic group. In addition, metal ions such as Cu and Fe (instead of zinc) as a core, and a tridentate or multidentate organic ligand can be used to prepare a MOF. A s described above, in a prior art, various organic ligands and metals have been used to prepare MOFs having various structures in such a manner that a MOF can store as much hydrogen as possible. However, it has been known that such a conventional MOF cannot store a large amount of hydrogen gas at an ambient temperature and an atmospheric pressure, so the storage capacity of the hydrogen gas does not reach a required level. In other words, in the conventional MOF, hydrogen gas is adsorbed to only some spaces, from among the whole spaces for adsorbing hydrogen gas, and most of the spaces remain empty. Thus, the storage of hydrogen gas is not efficient. In addition, when an ambient pressure or temperature changes, the conventional MOF reversibly physically adsorbing hydrogen gas can not keep its stable storage of the hydrogen gas. Accordingly, in storing and/or transporting the hydrogen gas by using the MOF, expensive equipment has been required to maintain a fixed temperature or pressure. Therefore, Matthew J . Rosseinsky et al. provided Ni2 (bipy) 3 (NO3)4, that is, a MOF which can irreversibly physically adsorb hydrogen, in V Hysteretic Adsorption and Desorption of Hydrogen by Nanoporous Metal-Organic Frameworks" (Science, Vol. 306, p .1012). However, this MOF has a two-dimensional structure (like a structure of graphite) , not a three-dimensional structure, and thus is less suitable for a material for storing hydrogen due to instability in the structure (for example, the structure may be easily broken) . Disclosure of the Invention A s described above, when a coordination polymer crystal with porous metal-organic frameworks (MOFs) physically adsorbs and stores a guest molecule, it is not easy to adsorb the guest molecule because a pore size within the crystal is larger than the size of the guest molecule (e.g., hydrogen gas, etc.). In addition, since the storage state of the guest molecule is sensitive to changes in an ambient temperature or pressure, the efficiency of storing the guest molecule is decreased. Accordingly, the present invention has b en made to solve the above-mentioned problems. We have found that while a coordination polymer crystal with porous MOFs is maintained, an additional material such an organic compound, a metal cluster, or an organometallic compound is chemically bonded to the coordination polymer crystal, and thus, it is possible to adjust the pore size, and at the same time to prevent the stored guest molecules from releasing according to a change in an ambient temperature or pressure. It is an object of the present invention to provide a coordination polymer crystal which can continuously store more guest molecules, and a method of the same. According to an aspect of the present invention, there is provided a coordination polymer crystal with porous metal-organic frameworks (MOFs) , in which, while a crystal state of the coordination polymer crystal is maintained, an additional material selected from the group including an organic compound, a metal cluster, and an organometallic compound is chemically bonded to the coordination polymer crystal.

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