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1、会计学1MOFs金属有机材料的制备金属有机材料的制备(zhbi)与应与应用用第一页，共23页。22nnMOFsMOFs材料简介材料简介nn制备方法制备方法(fngf)(fngf)nn应用领域应用领域nn小结与展望小结与展望nn参考文献参考文献目 录 一 二 三 四 五第1页/共22页第二页，共23页。MOFsMOFs材料材料(cilio)(cilio)简介简介320世纪(shj)90年代中期，第一代MOFs材料被合成出来孔径和稳定性受到一定(ydng)限制1999年，Yaghi等人合成具有三维开放骨架结构的MOF-5去除孔道中的客体分子后仍然保持骨架完整2002年，Yaghi科研组合成IRMO
2、F系列材料实现MOF材料从微孔到介孔的成功过渡2008年，Yaghi研究组合成出上百种ZIF系列类分子筛材料金属离子有机配体配位自组装周期性网状骨架的多孔材料第2页/共22页第三页，共23页。44MOFsMOFs材料材料(cilio)(cilio)简介简介比表面积大孔道(kngdo)可调控可功能化气体储存(chcn)吸附分离催化光学材料磁性材料药物传输 第3页/共22页第四页，共23页。5制备制备(zhbi)(zhbi)方法方法5第4页/共22页第五页，共23页。制备制备(zhbi)(zhbi)方法方法原位溶剂热法原位溶剂热法6自组装膜修饰(xish)基底Hermes, S. et al. J
3、. Am. Chem. Soc. 2005, 127, 13744-13745设备简单对合成条件(tiojin)敏感自组装层影响膜性能基底Au自组装膜MOF-5第5页/共22页第六页，共23页。7制备制备(zhbi)(zhbi)方法方法晶种法晶种法把晶体(jngt)的成核和生长过程分离开 更好地控制晶体(jngt)的生长和膜的微结构Liu, Y., et al. J. Membr. Sci. 2011, 379, 46-51.第6页/共22页第七页，共23页。8制备制备(zhbi)(zhbi)方法方法晶种法晶种法8Falcaro, P. et al. Nat. Commun., 2011, 2
4、, 237.MOF晶种-磷锌矿晶体(jngt)合成晶膜制备(zhbi)三维表面成膜选择性催化功能化-磷锌矿具有促使MOF-5成核的特殊功能第7页/共22页第八页，共23页。9制备方法制备方法(fngf)(fngf)微波法微波法9Yoo, Y. et al. Microporous Mesoporous Mater., 2009, 123, 100-106Yoo, Y. et al. Chem. Commun., 2008, 21, 2441-2443微波(wib)快速结晶溶剂(rngj)热二次生长微波法30s微波辅助快速晶种法节约制备时间晶体颗粒较小第8页/共22页第九页，共23页。10制备制
5、备(zhbi)(zhbi)方法方法分层法分层法10Shekhah, O. Materials, 2010, 3, 13021315Shekhah, O. et al. Nat. Mater., 2009, 8, 481-484高度有序、均匀、平整的MOF膜实现晶体的高度取向(q xin)性合成其他方法无法得到的MOF结构分层法图解(tji)第9页/共22页第十页，共23页。1111应用领域应用领域气体气体(qt)(qt)储存储存11氢气二氧化碳甲烷突破(tp)DOE储氢目标： 7.5wt.%Furukawa, H. et al. J. Materi. Chem., 2007, 17, 3197
6、-3204Gassensmith, J. J. et al. J. Am. Chem. Soc., 2011, 133, 1531215315; Ma, S. et al. J. Am. Chem. Soc. 2008, 130, 1012-1016超过(chogu)DOE室温体积CH4储存目标（180v/v）28%CO2MOF-177CD-MOF-2PCN-14第10页/共22页第十一页，共23页。12应用领域应用领域吸附吸附(xf)(xf)分离分离12Liu, X.-L. et al. Angew. Chem. Int. Ed. 2011, 50, 1-5ZIF-8吸附异丁醇过程中的“ga
7、te-opening”效应+表面(biomin)超疏水性优先透过醇类大分子而阻止水分子的高性能ZIF-8纳米复合膜分离(fnl)系数：34.9-40.1透量：6.4-8.6 kgh-1m-2第11页/共22页第十二页，共23页。13应用领域应用领域催化催化(cu hu)(cu hu)13方法特点利用骨架自身活性位MOF中的活性金属位或活性结构模块，可直接作为催化剂使用，但该法易导致骨架坍塌引入活性物质合成过程中引入具有催化活性的金属纳米粒子，即将MOF作为一种高比表面积的载体使用后合成法先合成MOF材料，再向MOF中引入活性基团或者活性物质在MOF中构建(u jin)特殊催化位点的方法第12页
8、/共22页第十三页，共23页。14应用领域应用领域催化催化(cu hu)(cu hu)14Wang, C. et al. J. Am. Chem. Soc. 2011, 133, 13445-13454催化剂TOF（h-1）MOF 14.8MOF 21.9MOF 30.4转化率（%）MOF 5MOF 6Ar=H5986Ar=Br6268Ar=OCH39697光催化剂TOF（h-1）MOF-40.8水氧化(ynghu)和光催化剂MOF UiO-67Ir、Re或Ru的复合物分子(fnz)催化与MOF材料相结合为光催化提供一种新的异相催化剂第13页/共22页第十四页，共23页。15应用领域应用领域发
9、光发光(f un)(f un)材料材料15选择(xunz)合适的配体或金属离子，可使MOFs具有发光性能生色(shngs)团溶剂不同结构不同荧光性不同Bauer, C.A. et al. J. Am. Chem. Soc., 2007, 129, 7136第14页/共22页第十五页，共23页。16应用领域应用领域其他其他(qt)(qt)磁性材料磁性材料(c xn ci lio) (c xn ci lio) 顺顺磁性、反磁性磁性、反磁性传传感器感器 客体影响客体影响MOFsMOFs光学和磁学性能光学和磁学性能药药物物传输传输 药药物包埋物包埋孔口修孔口修饰饰官能官能团团在不在不同的外界条件下打开
10、或关同的外界条件下打开或关闭闭孔口孔口药药物控制物控制释释放放16第15页/共22页第十六页，共23页。17总结总结(zngji)(zngji)及展望及展望17功能化材料(cilio)MOFS晶体尺寸(ch cun)、形状和取向的可控生长高质量连续生长、均相无缺陷的MOFs膜不同领域的科学家相互合作开发MOF的综合性能第16页/共22页第十七页，共23页。18参考文献参考文献1. C. Wang, Z. Xie, K. E. deKrafft et al. 1. C. Wang, Z. Xie, K. E. deKrafft et al. Doping MetalOrganic Framewo
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20、immons et al. 9. S. Ma, D. Sun, D. M. Simmons et al. Metal-Organic Framework from an Anthracene DerivativeMetal-Organic Framework from an Anthracene DerivativeContaining Nanoscopic Cages Exhibiting High Methane UptakeContaining Nanoscopic Cages Exhibiting High Methane Uptake. J. Am. Chem. Soc. 2008,
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26、of Metal-Organic Open Framework Selective Nucleation and Growth of Metal-Organic Open Framework Thin Films on Patterned COOH/CF3-Terminated Self-Assembled Monolayers on Au(111)Thin Films on Patterned COOH/CF3-Terminated Self-Assembled Monolayers on Au(111). J. Am. Chem. Soc. 2005, . J. Am. Chem. Soc
27、. 2005, 127, 13744-13745127, 13744-13745第18页/共22页第十九页，共23页。谢谢谢谢(xi (xi xie)xie)！第19页/共22页第二十页，共23页。21附图附图(f t)(f t)21Wang, C. et al. J. Am. Chem. Soc. 2011, 133, 13445-13454第20页/共22页第二十一页，共23页。附图附图(f t)(f t)22Wang, C. et al. J. Am. Chem. Soc. 2011, 133, 13445-13454第21页/共22页第二十二页，共23页。内容(nirng)总结会计学。制备方法原位溶剂(rngj)热法。MOF晶种-磷锌矿。-磷锌矿具有促使MOF-5成核的特殊功能。高度有序、均匀、平整的MOF膜。CD-MOF-2。ZIF-8吸附异丁醇过程中的“gate-opening”效应+表面超疏水性。kgh-1m-2。溶剂(rngj)不同结构不同荧光性不同。22第二十三页，共23页。
