Di-ionic multifunctional porous organic frameworks for efficient CO2 fixation under mild and co-catalyst free conditions,Green Chemistry

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Di-ionic multifunctional porous organic frameworks for efficient CO2 fixation under mild and co-catalyst free conditions
Green Chemistry ( IF 9.3 ) Pub Date : 2018-09-18 , DOI: 10.1039/c8gc01867g
Dingxuan Ma _{1,

2,

3,

4,

5} , Jixin Li _{6,

7,

8,

9,

10} , Kang Liu _{1,

2,

3,

4,

5} , Baiyan Li _{6,

7,

8,

9,

10} , Chunguang Li _{6,

7,

8,

9,

10} , Zhan Shi _{6,

7,

8,

9,

10}

Affiliation

Conversion of CO₂ into value-added chemicals is currently considered to be a significant field in the energy industry mainly due to its environmental and economic benefits. Porous organic frameworks (POFs), as a new class of advanced porous materials, have demonstrated great potential in catalysis, because the functionality and spatial arrangement of their active sites can be precisely managed. We report herein a new strategy for the construction of di-ionic multifunctional POF materials using multiple building blocks with different ion exchange functional sites to construct di-ionic POFs. Based on this strategy, a new di-ionic POF material, POF-DI, was prepared for the first time, which could serve as a substrate material for the preparation of a series of di-ionic multifunctional POF heterogeneous catalysts, POF-Zn²⁺-Cl⁻, POF-Zn²⁺-Br⁻ and POF-Zn²⁺-I⁻ by a feasible post-synthesis ion exchange method. Because of the synergetic role of dual functional ionic sites including Zn²⁺ cations as the Lewis acid site and halogen anions (Cl⁻, Br⁻ or I⁻) as the nucleophile, POF-Zn²⁺-Cl⁻, POF-Zn²⁺-Br⁻ and POF-Zn²⁺-I⁻ demonstrate excellent catalytic performance in the cycloaddition of CO₂ and epoxides under mild and co-catalyst free conditions. Moreover, such di-ionic multifunctional POF heterogeneous catalysts can be easily recovered and recycled several times without leaching or loss of activity. Overall, our work could not only open a new route for the development of novel POF catalysts for CO₂ conversion, but also advance di-ionic POFs as a new kind of platform for multifunctional material design.

中文翻译：

用于在温和无助催化剂条件下有效固定CO _2的双离子多功能多孔有机骨架

CO ₂转化率目前，将增值化学品纳入增值化学品领域被认为是能源行业的重要领域，这主要是因为其具有环境和经济效益。作为新型一类高级多孔材料，多孔有机骨架（POF）在催化方面显示出巨大潜力，因为可以精确管理其活性部位的功能和空间排列。我们在此报告了使用具有不同离子交换功能位点的多个构件来构建双离子POF的双离子多功能POF材料的构造的新策略。基于这种策略，首次制备了一种新型的双离子POF材料POF-DI，可作为制备一系列双离子多功能POF多相催化剂POF-Zn ²的底物材料。^+-氯^-，POF-Zn系²⁺ -Br^-和POF-Zn系²⁺ -I^-由一个可行的合成后的离子交换方法。因为双功能离子部位含有Zn的协同作用的²⁺阳离子作为路易斯酸位点和卤素阴离子（氯^-，溴^-或I^-作为亲核试剂，POF-Zn系）²⁺ -Cl^-，POF-Zn系^{2 +} -Br^-和POF-Zn系²⁺ -I^-表明在CO的环加成优异的催化性能₂以及在无助催化剂的温和条件下的环氧化物。而且，这样的双离子多功能POF多相催化剂可以容易地回收和循环几次，而不会浸出或失去活性。总体而言，我们的工作不仅可以为开发用于CO ₂转化的新型POF催化剂开辟一条新的道路，而且可以推动将离子型POF用作多功能材料设计的新型平台。

更新日期：2018-11-27

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