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MOFとは 金属有機構造体（__MOF__：Metal Organic Frameworks）は、金属と有機リガンドが相互作用することで、活性炭やゼオライトをはるかに超える高表面積を持つ多孔質の配位ネットワーク構造をもつ材料で、ガス吸着や分離技術、センサーや触媒などへの応用が期待されている三次元ミクロポーラス材料です1-3。 最もよく研究されている2つのMOF、「__MOF-5__」5と「__HKUST-1__」6,10は1999年に初めて報告されました。MOF-5は、有機リンカーとしてテレフタル酸ジアニオンを持つZn(II)クラスターで構成されます（__図1左__）。表面への多層ガス吸着が可能で、MOF-5のBET表面積は約3,500 m2/gです。HKUST-1（別名：Basolite® C 300、[__688614__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/688614)）は、トリメシン酸トリアニオンでリンクされたpaddlewheel型Cu(II)ダイマーで構成され、その表面積は約1,900 m2/gです（__図1右__）。既知材料のなかで最も高表面積な物質の1つである「MOF-177（Basolite® Z377、[__794325__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/794325)」7は、MOF-5と同じ金属クラスターと、非直線的な構造の、H3BTBと呼ばれることもあるトリトピック（tritopic）カルボン酸の1,3,5-tris(4’-carboxyphenyl)benzene（[__686859__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/686859)）から構成されます（__図2__）。MOF-177は、MOF-5と同じ条件下（*N,N*-ジエチルホルムアミド、100℃）で合成され、そのBET表面積は4,750 m2/gに達します8。  __図1__代表的なMOFの合成方法  __図2__MOF-177（[794325](https://www.sigmaaldrich.com/product/aldrich/794325)）の結晶構造 一般に、MOFは、塩基の存在下でソルボサーマル条件または水熱条件の下で合成されます。多くのMOFは、純粋な*N,N*-ジエチルホルムアミド（DEF）または*N,N*-ジメチルホルムアミド（DMF）溶媒中で調製されますが、これらは高温で分解して緩やかにアミン塩基を生成し、これがリンカーの有機官能基を脱プロトン化して金属有機クラスターを生成します。 1,3,5-tris(4’-carboxyphenyl)benzene（H3BTB、[__686859__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/686859)）はMOFのビルディングブロックであり、近年、表面積が非常に広いMOFを作るリンカーとして使用されています。77 Kで7.5 %という極めて高い水素吸蔵能力を持つ水素吸着材料「__MOF-177__、[__794325__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/794325)」（表面積：約 5000 m2/g）は、そのようなMOFの一例です4。さらに、かご状有機分子による多孔性材料も報告されています9。 また、従来の方法とは対照的に、「二次構造単位を制御・利用する手法（CSA：Controlled SBU Approach）」と呼ばれる、あらかじめ調製したSBU（secondary building unit）前駆体に対して単純かつ様々な置換反応を行うことで、試行錯誤による材料探索を行わずにMOFを合成することも可能です。一般的な手法とは異なり、CSAは目的に適した金属中心を含むMOFを作製することのできる簡便な方法であり、化学安定性、触媒活性、磁性、極性などの性質を制御した、構造の類似した多様なMOFを得ることができます。（CSAの詳細はレビュー「[__MOF用無機二次構造単位（SBU）前駆体__](https://www.sigmaaldrich.com/JP/ja/technical-documents/technical-article/materials-science-and-engineering/batteries-supercapacitors-and-fuel-cells/mof-sbu)」をご参考ください。） アルドリッチでは高性能MOF（MOF-1778,11、UMCM-1505、meso-MOF-16、NOTT-1017など）の合成に最適な金属塩、金属クラスター二次構造単位（SBU）、[有機リンカー化合物](https://www.sigmaaldrich-jp.com/structure/?recommend_id%5B0%5D=1454)を販売しております。 ## ＜MOFと他の材料との比較＞ - __ゼオライト__：MOFはほぼ一桁高い表面積をもち、死容量がありません。また、高い吸着容量と低い脱離エネルギーをもち、その構造は非常に多彩です。金属原子は原子レベルで分散し、触媒活性を示します。 - __シリカ__：MOFは非常に高い表面積と優れた吸着特性を持っています。 - __アルミナ__：親水性MOFは一桁以上の高表面積と低い脱離エネルギーを持ち、水に対して可逆的に安定です。 * * * __MOF合成に用いられる代表的な高純度金属塩類__ （その他の高純度無機塩類の製品リストは[__こちら__](https://www.sigmaaldrich-jp.com/structure/periodic_table/)） - Zn(NO3)2・6H2O, 99.999% （[230006](https://www.sigmaaldrich.com/JP/ja/product/aldrich/230006)） - Ni(NO3)2・6H2O, 99.999% （[203874](https://www.sigmaaldrich.com/JP/ja/product/aldrich/203874)） - Mg(NO3)2・6H2O, 99.999% （[203696](https://www.sigmaaldrich.com/JP/ja/product/aldrich/203696)） - Cu(NO3)2・xH2O, 99.999% （[229636](https://www.sigmaaldrich.com/JP/ja/product/aldrich/229636)） - Cu(NO3)2・2.5H2O, ≧99.99% （[467855](https://www.sigmaaldrich.com/JP/ja/product/aldrich/467855)） - Co(NO3)2・6H2O, 99.999% （[203106](https://www.sigmaaldrich.com/JP/ja/product/aldrich/203106)） - Al(NO3)3・9H2O, 99.997% （[229415](https://www.sigmaaldrich.com/JP/ja/product/aldrich/2294154)） __代表的なBasolite®の金属イオンとリンカーの種類__  ### Basoliteシリーズのまとめ15-18  製品名金属有機リンカー応用例表面積 (m2/g)細孔容量 (cm3/g)文献 [__688738__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/688738)Basolite A100 (MIL-53)AlTerephthalate- Gas adsorption: H2 gas \- Separation, Electrochemical, Biomedical Apprication1590 (Langmuir)ー12,14 [__688614__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/688614)Basolite C300 (HKUST-1, Cu-BTC, MOF-199)Cu1,3,5-Benzenetricarboxylate- Gas adsorption: CO2, N2, O2, H2 Gas, Natural gas etc. \- Catalysis (Lewis acid) \- Separations, Purification1958 (Langmuir)ー10,14 [__690872__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/690872)Basolite F300 (Fe-BTC)Fe1,3,5-Benzenetricarboxylate- Catalysis (solid Lewis acids)1040 (BET)ー13,14 [__691348__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/691348)Basolite Z1200 (ZIF-8)Zn2-Methylimidazolate- Gas Adsorption: H2, CO2, N2, CH4 gas \-Sensors, Separation, Purification, Composites, Catalyst1810 (Langmuir)0.63614 [__794325__](https://www.sigmaaldrich.com/JP/ja/product/aldrich/794325)Basolite Z377 (MOF-177)ZnBenzenetribenzoate- Gas adsorption: H2, CO2, N2 gas, large organic molecules \- Separations, Electrochemical Apprication5000 (BET)1.5911 ## 関連製品 申し訳ございませんが、想定外のエラーが発生しました。 Response not successful: Received status code 500   ## References 01. For a review issue regarding MOF applications see: *Chem. Soc. Rev*., __2009__, *38*, 1201. 02. Fundamentals of H2 binding and reactivity on transition metals underlying hydrogenase function and H2 production and storage. Kubas, G. J., *Chem. Rev.,*, __2007__ *107*, 4152. 03. Understanding inflections and steps in carbon dioxide adsorption isotherms in metal-organic frameworks. Walton, K. S., et al., *J. Am. Chem. Soc.*, __2008__ *130*, 406. 04. Exceptional H2 saturation uptake in microporous metal-organic frameworks. Wong-Foy, A. G., et al., *J. Am. Chem. Soc.*, __2006__ *128*, 3494. 05. Wong-Foy, A. G.; Lebel, O.; Matzger, A. J. *J. Am. Chem. Soc.*, __2007__, *129*, 15740. 06. Wang, X.-S.; Ma, S.; Sun, D.; Parkin, S.; Zhou, H.-C. *J. Am. Chem. Soc.*, __2006__, *128*, 16474. 07. Lin, X.; Telepeni, I.; Blake, A. J.; Dailly, A.; Brown, C. M.; Simmons, J. M.; Zoppi, M.; Walker, G. S.; Thomas, K. M.; Mays, T. J.; Hubberstey, P.; Champness, N. R.; Schröder, M. *J. Am. Chem. Soc.*, __2009__, *131*, 2159. 08. Chae, H. K.; Siberio-Pérez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O'Keef e, M.; Yaghi, O. M. [*Nature* __2004__, *427*, 523](https://doi.org/10.1038/nature02311). 09. T. Tozawa, J. T. A. Jones, S. I. Swamy, S. Jiang, D. J. Adams, S. Shakespeare, R. Clowes, D. Bradshaw, T. Hasell, S. Y. Chong, C. Tang, S. Thompson, J. Parker, A. Trewin, J. Bacsa, A. M. Z. Slawin, A. Steiner, A. I. Cooper, *Nature Mater.* __2009__, *8*, 973. 10. Chui S.S.-Y. et al. [*Science* __1999__, 283, 5405, 1148](https://science.sciencemag.org/content/283/5405/1148). 11. H. Furukawa, M. A. Miller and O. M. Yaghi, [*J. Mater. Chem.*, __2007__, *17*, 3197–3204](https://doi.org/10.1039/B703608F). 12. T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille and G. Férey, [*Chem.-Eur. J.*, __2004__, *10*, 1373–1382](https://doi.org/10.1002/chem.200305413). 13. Hu X. et al. [*RSC Adv.*, __2016__, *6*, 114483-114490](https://doi.org/10.1039/C6RA22738D). 14. A. U. Czaja, N. Trukhan and U. Muller, [*Chem. Soc. Rev.*, __2009__, *38*, 1284–1293](https://doi.org/10.1039/B804680H). 15. U. Mueller et al. Metal–organic frameworks — prospective industrial applications. [*J. Mater. Chem.*, __2006__, *16*, 626-636](https://doi.org/10.1039/B511962F). 16. D. Farrusseng et al. Metal–Organic Frameworks: Opportunities for Catalysis. [*Angew. Chem. Int. Ed.* __2009__, *48*, 7502-7513](https://doi.org/10.1002/anie.200806063). 17. P. Silva et al. Multifunctional metal–organic frameworks: from academia to industrial applications. [*Chem. Soc. Rev.*, __2015__, *44*, 6774.](https://doi.org/10.1039/C5CS00307E) 18. C. Pettinari et al. Application of metal−organic frameworks. [*Polym. 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