物理化学学报 >> 2008, Vol. 24 >> Issue (08): 1493-1497.doi: 10.3866/PKU.WHXB20080828

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金属-有机骨架材料MOF-5的改进与吸附甲烷的巨正则蒙特卡罗模拟

曾余瑶; 张秉坚   

  1. 浙江大学化学系, 杭州 310027
  • 收稿日期:2008-02-26 修回日期:2008-04-09 发布日期:2008-08-06
  • 通讯作者: 张秉坚 E-mail:zbj@mail.hz.zju.cn

Designed Metal-Organic Frameworks Based on MOF-5 and Their Methane Adsorption Calculation by Grand Canonical Monte
Carlo Method

ZENG Yu-Yao; ZHANG Bing-Jian   

  1. Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
  • Received:2008-02-26 Revised:2008-04-09 Published:2008-08-06
  • Contact: ZHANG Bing-Jian E-mail:zbj@mail.hz.zju.cn

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摘要： 根据金属-有机骨架材料(MOFs)的设计思想, 在MOF-5(对苯二甲酸为桥联配体, Zn4O金属簇为中心的配位化合物)的基础上设计了10 种以Zn4O 金属簇为中心(Corner), 以不同基团单取代的对苯二甲酸(BDC)衍生物为桥联配体(Linker)的多孔材料. 用巨正则蒙特卡罗(GCMC)模拟方法, 计算了这些材料在298 K、1-10 MPa条件下对甲烷的吸附量, 讨论了不同取代基与甲烷吸附量的关系.结果发现, 在298 K、3.5 MPa 时甲烷的吸附量主要取决于吸附热, 并且以硝基取代的配体构成的MOF分子吸附甲烷效果最好. 在此基础上, 进一步设计了以四硝基取代对苯二甲酸为桥联配体的MOF-4NO2, 该结构在相同条件下对甲烷的超额吸附量为209 cm3·cm-3, 总吸附量达到228 cm3·cm-3, 比美国能源部(DOE)提出的甲烷吸附材料应用要求标准高26%.

关键词: 甲烷, 金属-有机骨架材料, 吸附, 巨正则蒙特卡罗

Abstract: 10 metal-organic framework molecules (MOFs) were designed based on the idea that the corners of those MOFs are consistent with that of MOF-5 (the complex with 1,4-benzenedicarboxylate as linker and Zn4O cluster as corner) but their linkers were changed into derivatives of 1,4-benzenedicarboxylate (BDC). Then, methane adsorption of new MOFs was calculated by grand canonicalMonte Carlo (GCMC) method at 298Kand 1-10 MPa, and the adsorption amounts were correlated with different substituent groups. The results show that the isosteric heat of adsorption is the most important factor at 298 K and 3.5 MPa, and the adsorption amount is highest when the linker of MOFs is —NO2. At last, a designed MOF, which has 4 nitro groups on the BDC, was constructed and the corresponding methane adsorption amount was also calculated at the same conditions. The calculated amount of excess adsorption reaches 209 cm3·cm-3 and the calculated total adsorption attains 228 cm3·cm-3, which is 26% higher than the amount of DOE’s requirement for methane storage materials.

Key words: Methane, Metal-organic framework, Adsorption, GCMC