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Photoresponsive metal-organic polyhedra in metal-organic frameworks: Achieving “real” responsiveness

金属有机框架中的光响应金属有机多面体: 实现“真正”的响应

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Abstract

Photoresponsive metal-organic polyhedra (PMOPs) show controllable properties in a broad range of applications, such as adsorption, catalysis, and molecule inclusion. However, the aggregation of bulk PMOPs leads to their inaccessibility of inside nanocages and low regulatory efficiency by light. Herein, a new PMOP (PM2L4) with pendant azobenzene units was synthesized and dispersed into the pores of the metal-organic framework (MOF, PCN-333). The obtained PM2L4@MOF composites show improved CO2 uptake and photoresponsive efficiency. Upon visible-light irradiation, the azobenzene groups stay in the trans state where CO2 molecules can freely enter the nanospace of PM2L4. Nevertheless, upon ultraviolet (UV)-light irradiation, the azobenzene groups transform to the cis state, which hinders the entrance of CO2 to the nanospace of PM2L4. In addition, UV/visible light irradiation can facilitate the reversible cis-/trans-isomerization of the azobenzene groups of PM2L4. The adsorption variation of CO2 captured by PM2L4@MOF composite under light is 15.5%, which is much higher than that of bulk PM2L4 (5.9%). We believe that the findings of this study will provide insights into the potential of PMOPs and may inspire the development of exquisite strategies to efficiently control adsorption processes.

摘要

光响应金属有机多面体(PMOP)在吸附、 催化和分子包裹等应用中显示出可控的性质, 但PMOP的聚集导致分子无法进入其内部的纳米笼并且光调节效率低. 本工作合成了一种具有偶氮苯侧基的新型光响应MOP (PM2L4), 并将其分散到金属有机框架(MOF, PCN-333)的孔道中. 制备的PM2L4@MOF复合材料显示出明显改善的CO2捕获能力和光响应效率. 在可见光照射下, 偶氮苯基团处于反式构型, CO2分子可以自由进入PM2L4的纳米空间. 在紫外光照射下, 偶氮苯基团转变为顺式构型并阻碍CO2进入PM2L4. 在紫外/可见光的交替照射下, PM2L4的偶氮苯基团能够实现可逆的顺式-反式转化. 在光照调节下, PM2L4@MOF复合材料对CO2的吸附变化为15.5%, 远高于聚集态的PM 2 L 4(5.9%).

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Acknowledgements

This work was supported by the National Science Fund for Distinguished Young Scholars (22125804), the National Natural Science Foundation of China (22078155), and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions.

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Authors and Affiliations

  1. State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), College of Chemical Engineering, Nanjing Tech University, Nanjing, 211816, China

    Sheng-Tao Wang  (汪声涛), Peng Tan  (谈朋), Wen-Qiang Weng  (翁文强), Long Zheng  (郑龙), Xiao-Qin Liu  (刘晓勤) & Lin-Bing Sun  (孙林兵)

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  1. Sheng-Tao Wang  (汪声涛)
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  2. Peng Tan  (谈朋)
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  3. Wen-Qiang Weng  (翁文强)
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  4. Long Zheng  (郑龙)
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  5. Xiao-Qin Liu  (刘晓勤)
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  6. Lin-Bing Sun  (孙林兵)
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Contributions

Author contributions Sun LB and Tan P supervised all data collection, analysis and interpretation; Wang ST and Weng WQ designed and performed the experiments; Weng WQ and Zheng L characterized the materials and discussed the results with help from Liu XQ; Sun LB, Tan P, and Wang ST were responsible for the major part of writing. All authors discussed the results and commented rsions of the manuscript.

Corresponding authors

Correspondence to Peng Tan  (谈朋) or Lin-Bing Sun  (孙林兵).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Sheng-Tao Wang is currently a graduate student under the supervision of Prof. Lin-Bing Sun and Prof. Xiao-Qin Liu at the State Key Laboratory of Materials-Oriented Chemical Engineering and Nanjing Tech University. His research interest focuses on the design and fabrication of photoresponsive porous materials as well as their applications in adsorption and catalysis.

Peng Tan is an associate professor at Nanjing Tech University. He received his PhD degree from Nanjing Tech University under the guidance of Prof. Xiao-Qin Liu and Prof. Lin-Bing Sun in 2017. His research interest focuses on the design and fabrication of functional nanoporous materials, including porous carbons, zeolites, mesoporous silicas, metal-organic frameworks, and stimuli-responsive nanoporous composites, as well as their applications in adsorption and separation.

Lin-Bing Sun is a full professor at the State Key Laboratory of Materials-Oriented Chemical Engineering and Nanjing Tech University. He received his PhD degree from Nanjing University in 2008. From 2011 to 2012, he worked as a postdoctoral fellow at Texas A&M University. His current research interests mainly focus on the synthesis of porous functional materials (such as metal-organic frameworks, zeolites, and mesoporous silicas) as well as their applications in adsorption and catalysis.

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Wang, ST., Tan, P., Weng, WQ. et al. Photoresponsive metal-organic polyhedra in metal-organic frameworks: Achieving “real” responsiveness. Sci. China Mater. 66, 2726–2732 (2023). https://doi.org/10.1007/s40843-022-2428-7

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  • DOI: https://doi.org/10.1007/s40843-022-2428-7

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