Metal-organic Frameworks-based Composites and Their Photothermal Applications

doi:10.6023/A21040173

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (8): 967-985.DOI: 10.6023/A21040173 Previous Articles Next Articles

Special Issue: 多孔材料：金属有机框架(MOF)

Review

金属有机框架基复合材料的制备及其光热性能研究

郭彩霞, 马小杰^*(), 王博^*()

北京理工大学化学与化工学院北京 100081

投稿日期:2021-04-22 发布日期:2021-05-26
通讯作者: 马小杰, 王博

作者简介:

郭彩霞, 北京理工大学硕士研究生. 2018年本科毕业于山东师范大学, 现于北京理工大学攻读硕士学位. 主要研究领域为MOF复合材料的制备及光催化性能.

马小杰, 北京理工大学化学与化工学院预聘助理教授, 于兰州大学化学与化工学院取得本科与硕士学位, 中科院化学研究所获得博士学位. 主要从事多孔材料的环境催化研究工作.

王博, 北京理工大学化学与化工学院教授, 2004年于北京大学化学与分子工程学院获理学学士学位, 2006年于美国密歇根大学获化学材料学硕士学位, 2008年于美国加州大学洛杉矶分校获化学材料学博士学位. 王博教授主要从事新型纳米多孔材料、开放框架聚合物理论与设计及其在关键分离过程、环境防护等领域的应用研究.

基金资助:
国家自然科学基金(21625102); 国家自然科学基金(21801017); 国家自然科学基金(21490570); 国家自然科学基金(21674012); 北京市科委科技计划项目(Z181100004418001); 北京理工大学科研基金项目资助

Metal-organic Frameworks-based Composites and Their Photothermal Applications

Caixia Guo, Xiaojie Ma(), Bo Wang()

School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

Received:2021-04-22 Published:2021-05-26
Contact: Xiaojie Ma, Bo Wang
Supported by:
National Natural Science Foundation of China(21625102); National Natural Science Foundation of China(21801017); National Natural Science Foundation of China(21490570); National Natural Science Foundation of China(21674012); Beijing Municipal Science and Technology Project(Z181100004418001); Beijing Institute of Technology Research Fund Program

Metal-organic frameworks (MOFs) are a growing class of organic-inorganic hybrid crystalline porous materials, showing high levels of structural and chemical diversity. They have a wide range of applications in gas adsorption and separation, catalysis, sensing, biomedicine and other fields. Due to their intriguing properties such as high porosity, adjustable pore size and tunable surface functionality, MOFs have been gaining popularity as a promising platform for integration of various organic/inorganic functional nanomaterials in a predictable and controllable way. The combination of MOFs and functional components offers a possibility to generate synergetic effect between functional units, thus leading to the creation of multifunctional materials with performance superior to each individual components. In this review, we summarized recent research progress on controllable synthesis of MOF composites. There are basically two strategies, including “bottle in ship” and “ship in bottle”. Following that, preparation methods including solution infiltration, deposition, solid grinding and template synthesis, were discussed in detail. Light-to-heat conversion materials have always been a research focus due to their important applications in solar powered water evaporation and near-infrared (NIR) excited bioimaging and noninvasive cancer treatment. MOFs can not only show intrinsic structure-dependent photoresponse activity, but also serve as porous supports to facilitate the stabilization and spatial distribution of photothermal nanoparticles. Recently, MOF composites with photothermal effects have aroused increasing attention in the fields like tumor diagnosis and treatment, bacterial disinfection and synergistic catalysis. This review mainly focused on the recent research progress on photothermal MOF composites. We discussed the integration of functional MOFs with various inorganic/organic photothermal nanoparticles (e.g. Au, Pt, porphyrin, polydopamine etc.), along with the structure and photothermal application of the composites. Research about MOFs based light-to-heat conversion is at the stage of rapid development. Finally, we also give a prospect to the future development of multifunctional and photothermal MOF composites.

Key words: metal-organic framework, composite material, photothermal effect, tumor treatment, synergistic catalysis

Cite this article

Caixia Guo, Xiaojie Ma, Bo Wang. Metal-organic Frameworks-based Composites and Their Photothermal Applications[J]. Acta Chimica Sinica, 2021, 79(8): 967-985.

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Fig. & Tab. 31

Figure 1. (a~c) Schematic illustration of photothermal mechanisms; (d) schematic illustration of the photothermal MOF composites

Figure 2. Schematic illustration of synthetic strategies and photothermal applications (photothermal tumor treatment, photothermal-disinfection, photothermal synergistic catalysis) for MOF composites

Figure 3. Schematic illustration of synthetic methods for MOF composites

Figure 4. Schematic illustration for the preparation methods. Adapted from the literature [45]

Figure 5. Synthesis route to MIL-101@MS composites prepared in anhydrous ethanol. The coordinatively unsaturated metal sites (CUSs) of MIL-101 are exposed by removing coordinated water in MIL-101. Color key: chromium (teal), nitrogen (purple), sulfur (dark yellow), carbon (gray), oxygen (red), hydrogen atoms are omitted for clarity. Adapted from the literature [50]

Figure 6. Schematic representation of immobilization of the AuNi nanoparticles by the MIL-101 matrix using the DSM combined with a liquid-phase CCR strategy. Adapted from the literature [54]

Figure 7. The four pulses of an ALD reaction cycle. Adapted from the literature [74]

Figure 8. Synthesis procedure of Pd@ZIF-8 via the mechanochemistry-assisted approach. Adapted from the literature [90]

Figure 9. Schematic illustration for the oriented growth of Cu2O@HKUST-1 and random growth of Cu2O/HKUST-1 composites. Adapted from the literature [101]

Figure 10. Schematic illustration of the synthesis of AuNS@MOF-ZD2 nanoprobes, and application for T1-weighted MR imaging and photothermal therapy specifically toward MDA-MB-231 tumor (TNBC). Adapted from the literature [98]

Figure 11. (a) TEM images of yolk-shell structured Au@MOF; (b) in vivo DOX, Au@MOF, and Au@MOF-DOX were injected intravenously to the tumor-bearing mice and treated with or without 1064 nm laser irradiation. The average body weight of tumor-bearing mice in each group during the treatment periods; (c) the relative tumor volumes (normalized) of tumor-bearing mice in each group; (d) the representative photographs of tumor-bearing mice after different treatments. Adapted from the literature [97]

Figure 12. Schematic illustration of fabricating LA-AuNR/ZIF-8 JNPs. Adapted from the literature [96]

Figure 13. (a) Schematic illustration for the preparation of PUA-Ce6 and its application on combination of PTT and potential enhanced PDT by converting intratumor H2O2 into O2 for tumor therapy; (b) fluorescent images of MCF-7 cells incubated with PBS or PUA-Ce6 nanoparticles with or without 670 and 808 nm laser irradiation, each for 5 min separately (stained by Calcein-AM/PI, green for live and red for dead); (c) the corresponding UV-vis-NIR absorbance spectra of PUA aqueous solution at different reaction times; (d) tumor volume curves change of mice after different treatments (5 mice per group). Adapted from the literature [95]

Figure 14. Stepwise assembly of BQ and catalase in MOF layers and its application as tandem catalyst for enhanced therapy against hypoxic tumor cells. Adapted from the literature [114]

Figure 15. (a) Field-dependent magnetization loop of the Fe3O4/ZIF-8-Au25 sample; (b) T2-weighted MR images of Fe3O4/ZIF-8-Au25 nanocomposite recorded using a 3T MR scanner; (c) MR imaging for in vivo mapping using Fe3O4/ZIF-8-Au25 sample. MR images were taken before (left) and after (right) injection of IZA. Adapted from the literature [32]

Figure 16. (a) Schematic illustration of synthetic procedure of CSD-MOFs and (b) schematic representation: CSD-MOFs@DOX as an effective multi-model therapeutic agents for synergistic tumor therapy. Adapted from the literature [132]

Figure 17. Synthesis and mechanism for cancer therapy of TCPC-UiO by light activation. (a) Synthesis of TCPC-UiO NMOF and schematic description of heat and singlet oxygen generation under laser irradiation; (b) photophysical mechanism for cancer therapy under light activation (Phos., phosphorescence; NRR, nonradiative recombination; ISC, intersystem crossing) of a combination therapy utilizing a single light source in vivo guided by CT/thermal/photoacoustic imaging. Adapted from the literature [143]

Figure 18. Schematic illustration to show the fabrication process of Mn-IR825@PDA-PEG. Adapted from the literature [144]

Figure 19. Schematic representation of the synthesis procedure, HA conjugation, ICG loading, and multimodal imaging-guided PTT of MIL-100(Fe) NPs. Adapted from the literature [147]

Figure 20. Schematic illustration of the synthetic strategy for PPy@MIL-100(Fe) NCs as pH/NIR-responsive drug carriers for dualmode imaging and synergistic chemo-photothermal therapy in vitro. Adapted from the literature [150]

Figure 21. Illustration of PPy@MIL-53/DOX synthesis for photothermal-chemotherapy and MRI of tumors. Adapted from the literature [151]

Figure 22. (a) Preparation procedure of MCH NPs and (b) schematic illustration of MCH NPs for PAI-guided chemo-/photothermal combinational tumor therapy. Adapted from the literature [154]

Figure 23. (a) The schematic representation of the preparation of MCP, MCP-PEG, and MCP PEG-RGD NPs; (b) T1-weighted MR images and R1 map of MRI phantom images of MCP-PEG NPs at different Mn concentration; (c) tumor growth curves of mice after different treatments (n=6). Adapted from the literature [155]

Figure 24. (a) Schematic illustrations for the preparation of 2D TRB-ZnO@G nanosheets; (b) schematic illustration of the NIR-triggered phase-to-size transformation of TRB-ZnO@G, and the corresponding formation of micrometer-aggregations with wrapped and killed bacteria. Adapted from the literature [179]

Figure 25. (a) Schematic illustration of the core-shell structure of PB@MOF; (b) schematic illustration of the bacteria killing processes with the PB@MOF under dual light irradiation; (c) schematic illustration of rational photocatalytic mechanism for PB@MOF heterojunction photocatalysts. Adapted from the literature [180]

Figure 26. (a) Proposed reaction mechanism for the hydrolysis of DMNP by GF@UiO-66-NH2; (b) infrared photograph of GF@UiO-66-NH2 in dry state and in its aqueous suspension under the simulated solar light (0.6 W•cm-2); (c) hydrolysis kinetic linear fitting curves of DMNP in the presence of GF@UiO-66-NH2 under different light irradiations. Adapted from the literature [25]

Figure 27. Schematic illustration of the fabrication procedures for Dpa@UiO-66-NH2 CSNs and their fabrics for photothermally enhanced detoxification of CWA simulants. Adapted from the literature [24]

Figure 28. (a) Photographs showing a stand-alone flexible UiO-66-NH2/PAN fibrous mat with a large area and its corresponding SEM image; (b) percentage conversion of DMNP to p-nitrophenoxide using UiO-66-NH2/PAN, mixture/PAN, and Dpa@UiO-66-NH/PAN fibrous mats in the filter test under different light irradiation conditions. Error bars are the standard deviation in triplicate readings. Adapted from the literature [24]

Figure 29. Steps for the preparation of PDA-mediated MOF fabrics: PDA coating on electrospun PA-6 nanofibers by dopamine polymerization and solvothermal growth of Zr-MOF UiO-66-NH2 on PA-6@PDA nanofibers. Adapted from the literature [26]

Figure 30. (a) Self-assembly of Pd NCs@ZIF-8 and plasmon-driven selective catalysis of the hydrogenation of olefins; (b) recyclability of Pd NCs@ZIF-8 and Pd NCs for the hydrogenation of 1-hexene; (c) conversions of the hydrogenation of various alkenes over Pd NCs@ZIF-8 and Pd NCs. Reaction conditions in (b) and (c): 100 mW•cm-2 full-spectrum irradiation, room temperature. Adapted from the literature [100]

Figure 31. Schematic illustration showing the selective oxidation of alcohols over Pt/PCN-224(M) under visible-light irradiation. Adapted from the literature [195]

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金属有机框架基复合材料的制备及其光热性能研究

Metal-organic Frameworks-based Composites and Their Photothermal Applications

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