华东理工Angew. Chem. Int. Ed.:以表面活性剂为模板水相中制备介孔Zr基MOFs


【引言】

金属有机骨架(MOFs)材料具有比表面积高、孔径可调、组分多样、表面易功能化等诸多优点,是具有广阔应用前景的多功能材料。然而,大多MOFs材料只具有微孔结构,不利于物质传输和大分子客体的进入,限制了该材料在大分子分离、传感、释放等诸多领域的应用。在MOFs骨架中引入介孔孔道并制备微孔-介孔分解结构是解决这一难题的可行方法之一。

【成果简介】

 近日,华东理工大学顾金楼教授(通讯作者)与李可(第一作者)在Angew. Chem. Int. Ed.发表了题为“Aqueous-Phase Synthesis of Mesoporous Zr-Based MOFs Templated by Amphoteric Surfactants”的文章。该研究以两性表面活性剂为模板,在水相中成功合成了有序介孔结构的Zr基MOFs。

【图文导读】

 图一. 表面活性剂化学结构式

图二. 样品的XRD和BET表征

(a)无模板剂制备的UiO-66-NH2

(b)CAPB为模板制备UiO-66-NH2

(c)OAPB为模板制备UiO-66-NH2

图三. 介孔UiO-66-NH2的TEM表征

(a)和(b)CAPB为模板制备UiO-66-NH2的TEM表征;

(c)和(d)OAPB为模板制备UiO-66-NH2的TEM表征。

图四. 六方介孔UiO-66-NH2MOFs的形成机理

图五. OAPB为模板制备的介孔UiO-66-(OH)2的结果表征

图六. 不同模板剂制备的UiO-66-NH2 MOFs对细胞色素c的吸附量比较

紫外-可见光光谱峰强度和悬浮液中的细胞色素c的量成正相关;(a)无模板剂制备的UiO-66-NH2;(b)CAPB为模板制备UiO-66-NH2;(c)OAPB为模板制备UiO-66-NH2

【小结】

 该工作以简单的水相模板法制备了微/介孔Zr基MOFs材料。表面活性剂不仅起到模板作用,还为金属前驱体提供了锚定位点并引导金属有机框架定向组装。介孔UiO-66-NH2展现出介孔的可调节性及有机框架的稳定性。介孔壁由规则的微孔结晶MOFs构成。这一制备方法为制备新型介孔MOFs材料提供了新的思路。

文献链接:Aqueous-Phase Synthesis of Mesoporous Zr-Based MOFs Templated by Amphoteric Surfactants(Angew. Chem. Int. Ed., 2018 DOI: 10.1002/anie.201800619)

通讯作者简介

顾金楼---上海市浦江人才、上海市青少年科技创新市长奖获得者。华东理工大学无机材料研究所所长、教授、博士生导师。

目前主要从事多孔材料及其在分离与检测、智能药物控释、气体储存与生物治疗等领域的应用研究工作。

近年来,在Advanced Materials, Angewandte Chemie International Edition, Journal of the American Chemical Society, Advanced Functional Materials, Chemistry of Materials, Small, Journal of Physical Chemistry Letters, Chemical Communications, ACS Applied Materials & Interfaces等国际知名杂志上发表SCI学术论文90余篇,单篇最高影响因子19.79,论文他引总计3000余次,H因子达到27。发明专利多项,其中公开号为JP-2008-28019的专利权属已转让于日本松下电器公司。目前主持国家自然科学基金,上海市纳米技术专项基金,上海市教委重点基金,教育部博士点基金等。

教学方面获得:宝钢教育奖、上海市化工区教学奖、上海市优秀研究生论文指导老师、华东理工大学教学竞赛一等奖、最佳教案编写奖,华东理工大学教学新星、华东理工大学优秀研究生论文指导老师等。

参与翻译专著《生物系统纳米技术》一部。

部分研究成果:

  1. Ke Li, Shaoliang Lin, Yongsheng Li, Qixin Zhuang and Jinlou Gu,* Aqueous phase synthesis of mesoporous Zr-based MOFs templated by amphoteric surfactant, Angewandte Chemie International Edition, 2018, In Press.
  2. Zhe Wang, Shuanggang Hu, Jian Yang, Ajuan Liang, Yongsheng Li, Qixin Zhuang and Jinlou Gu,* Nanoscale Zr-based MOFs with tailorable size and introduced mesopore for protein delivery, Advanced Functional Materials, 2018, 201707356.
  3. Pengfei Yang, Fangxin Mao, Yongsheng Li, Qixin Zhuang and Jinlou Gu,* Hierarchical porous Zr-based MOFs synthesized by a facile monocarboxylic acid etching strategy, Chemistry-A European Journal, 2018, 2962-2970.
  4. Zhe Wang, Jian Yang, Yongsheng Li, Qixin Zhuang and Jinlou Gu,* In situ carbothermal synthesis of nZVI functionalized porous carbon from Fe-MOFs for efficient detoxification of Cr(VI), European Journal of Inorganic Chemistry, 2018, 23-30.
  5. Jian Yang, Xiaojing Chen, Yongsheng Li, Qixin Zhuang, Peifeng Liu, and Jinlou Gu,* Zr-based MOFs shielded with phospholipid bilayers: improved biostability and cell uptake for biological applications, Chemistry of Materials2017, 29, 4580-4589.
  6. Zhe Wang, Jian Yang, Yongsheng Li, Qixin Zhuang, and Jinlou Gu,* Simultaneous degradation and removal of Cr(VI) from aqueous solution with Zr-Based MOFs bearing inherent reductive sites, Chemistry-A European Journal, 2017, 15415-15423.
  7. Chao Wu, Xiangyang Zhu, Zhe Wang, Jian Yang, Yongsheng Li, and Jinlou Gu,* Specific recovery and in situ reduction of precious metal from waste to create MOF composites with immobilized nanoclusters, Industrial & Engineering Chemistry Research, 2017, 56, 13975-13982.
  8. Zhe Wang, Ying Huang, Jian Yang, Yongsheng Li, Qixin Zhuang, and Jinlou Gu,* Water-based synthesis of chemically stable Zr-based MOFs using pyridine-containing ligands and their exceptionally high adsorption capacity for iodine, Dalton Transactions, 2017, 46, 7412-7420.
  9. Jian Yang, Zhe Wang, Yongsheng Li, Qixin Zhuang, and Jinlou Gu,* Real-time monitoring of dissolved oxygen with inherent oxygen sensitive centers in metal−organic frameworks, Chemistry of Materials, 2016, 28, 2652-58.
  10. Bing Li, Xiangyang Zhu, Kaili Hu, Yongsheng Li, Jianfang Feng, Jianlin Shi, and Jinlou Gu,* Defect creation in metal-organic frameworks for rapid and controllable decontamination of roxarsone from aqueous solution, Journal of Hazardous Materials, 2016, 302, 57-64.
  11. Jian Yang, Zhe Wang, Yongsheng, Li, Qixin Zhuang, Wenru, Zhao, and Jinlou Gu,* Porphyrinic MOFs for reversible fluorescent and colorimetric sensing of mercury(II) ions in aqueous phase, RSC Advances, 2016, 6, 69807-69814.

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