南京大学学报(自然科学版) ›› 2019, Vol. 55 ›› Issue (5): 840–849.doi: 10.13232/j.cnki.jnju.2019.05.018

• • 上一篇    下一篇

混合配体法合成氨基MIL⁃101(Cr)及其二氧化碳吸附和除湿性能

马益平1,严浩军1,王琼京1,赵亚云2,张秋菊2,孔春龙2()   

  1. 1. 宁波市电力设计院有限公司，宁波，315200
    2. 中国科学院宁波材料技术与工程研究院，宁波，315201
  • 收稿日期:2019-02-27 出版日期:2019-09-30 发布日期:2019-11-01
  • 通讯作者: 孔春龙 E-mail:kongchl@nimte.ac.cn
  • 基金资助:
    宁波市电力设计院科技研发项目

Tailored synthesis of amine⁃functionalized MIL⁃101(Cr) for CO2 and H2O capture via a mixed linker method

Yiping Ma1,Haojun Yan1,Qiongjing Wang1,Yayun Zhao2,Qiuju Zhang2,Chunlong Kong2()   

  1. 1. Ningbo Electric Power Design Institute, Ningbo, 315200, China
    2. Ningbo institute of Material Technology and Engineering, Chinese Academy of Science, Ningbo, 315201, China
  • Received:2019-02-27 Online:2019-09-30 Published:2019-11-01
  • Contact: Chunlong Kong E-mail:kongchl@nimte.ac.cn

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摘要：

报道一种原位合成氨基功能化金属框架材料(Metal?Organic Framework，MOF)的方法.该方法采用混合配体使2?氨基对苯二甲酸部分替换金属有机骨架材料MIL?101(Cr)中的对苯二甲酸，以实现材料的氨基功能化.实验结果表明，对苯二甲酸是引导组装MIL?101框架时必不可少的成分，并且2?氨基对苯二甲酸在MOF框架中的含量可以通过化学计量比来调控.氨基功能化MIL?101(Cr)的比表面积大，热稳定性高，空气中分解温度高达300 ℃以上.氨基功能化MIL?101(Cr)的颗粒形貌和纯MIL?101(Cr)总体类似，但是颗粒表面变得粗糙.此外，该功能化材料还表现出优异的CO2和水蒸气吸附能力：30 ℃ 4 MPa下，CO2吸附量可达19 mmol·g-1，CO2/N2理想分离系数达16以上.还在常温下测试了其在密闭容器中对水蒸气的吸附性能，将湿度从71%降低至38%，可作为电力开关柜和端子箱等的潜在除湿装置.

关键词: 金属有机框架材料, 混合配体, 氨基功能化MIL?101(Cr), 水热合成, CO2捕获, 除 湿

Abstract:

A pure phase amine?functionalized metal?organic framework (MOF) was successfully synthesized via a mixed linker method. In particular,partial isomorphic substitution of terephthalic acid in MIL?101(Cr) linker by 2?aminoterephthalic acid is reported. We show that terephthalic acid is dispensable to induce the assembly of frameworks and the content of 2?aminoterephthalic acid linker in the resulting frameworks can be readily controlled by modifying the reaction stoichiometry. The as?prepared amine?functionalized MIL?101(Cr) had a large Brunauer?Emmett?Teller (BET) surface area and high thermal stability,with a decomposition temperature above 300 ℃ in air. The scanning electron microscopy (SEM) reveals that the morphology of amine?functionalized MIL?101(Cr) is similar to the pristine MIL?101(Cr) but the surface becomes rougher. In addition,they exhibited excellent CO2 capture capacity up to 19 mmol·g-1 at a pressure of 4 MPa and a temperature of 30 ℃,as well as high CO2/N2 ideal selectivity up to 16. The excellent CO2 storage capacities as well as high thermal stability make this material a very attractive candidate for CO2 capture. On the other hand,at room temperature,the adsorption performance of H2O in a closed container was tested,and results showed the relative humidity decreased from 71% to 38% in an hour,indicating that the materials could be potentialy used in dehumidification device for electric power switch cabinet and terminal box.

Key words: metal?organic framework, mixed linker, amine?functionalized MIL?101(Cr), hydrothermal synthesis, CO2 capture, dehumidification

中图分类号: 

  • TQ028.8

图1

氨基功能化MIL?101(Cr)合成路线"

图2

（a）元素分析测定NH2?MIL?101?A (A),NH2?MIL?101?B (B),NH2?MIL?101?C (C)和NH2?MIL?101?D (D)中C,H,N的含量；(b)上述四种材料的照片"

图3

未功能化的MIL?101和功能化材料的红外光谱"

图4

NH2?MIL?101?A,NH2?MIL?101?B,NH2?MIL?101?C和NH2?MIL?101?D的PXRD图与MIL?101(Cr)的模拟标准图对比"

图5

粉末样品NH2?MIL?101?A (a),NH2?MIL?101?B (b),NH2?MIL?101?C (c)和NH2?MIL?101?D (d)的SEM图"

图6

四种样品在空气中的TGA图（加热速率为5 ℃?min-1）"

图7

77 K下，NH2?MIL?101?A，NH2?MIL?101?B，NH2?MIL?101?C和NH2?MIL?101?D的N2吸附等温线"

图8

30 ℃时，NH2?MIL?101?A，NH2?MIL?101?B，NH2?MIL?101?C和NH2?MIL?101?D的CO2,N2和CH4的吸附等温线"

图9

0.1 MPa时，材料NH2?MIL?101?A (A)，NH2?MIL?101?B (B)，NH2?MIL?101?C (C)和NH2?MIL?101?D (D)的CO2/CH4和CO2/N2的理想选择系数"

图10

30 ℃时，NH2?MIL?101?A在不同压力下对CO2/CH4和CO2/N2的理想选择性"

图11

常温除湿性能图"

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