Template-free synthesis to micro-meso-macroporous hierarchy in nanostructured MIL-101(Cr) with enhanced catalytic activity

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  • ReceivedApr 30, 2020
  • AcceptedJun 22, 2020
  • PublishedSep 24, 2020


Funded by

the Fundamental Research Funds for the Central Universities(19lgzd16)

the National Key R&D Program of China(2017YFC1103800)

a joint National Natural Science Foundation of China-DFG(NSFC-DFG)




Hubei Provincial Natural Science Foundation of China(2016CFA033)

Hunan Provincial Natural Science Foundation of China(2018JJ3122)

the S&T Program of Hunan Province


the Science Research Project of Hunan Provincial Department of Education(18B294)


This work was supported by the National Key R&D Program of China (2017YFC1103800), a joint National Natural Science Foundation of China-Deutsche Forschungsgemeinschaft (NSFC-DFG) project (NSFC 51861135313, DFG JA466/39-1), Program for Changjiang Scholars and Innovative Research Team in University (IRT_15R52), the National Natural Science Foundation of China (51802094, U1663225, U1662134, 21711530705 and 21706199), International Science & Technology Cooperation Program of China (2015DFE52870), Hubei Provincial Natural Science Foundation of China (2016CFA033) and Hunan Provincial Natural Science Foundation of China (2018JJ3122), the S&T Program of Hunan Province, China (2018RS3084), the Science Research Project of Hunan Provincial Department of Education (18B294) and the Fundamental Research Funds for the Central Universities (19lgzd16).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Zhao T and Li S carried out all the experiments; Xiao YX, Chang G, and Tian G took part in the characterization; Janiak C conceived the project and revised the paper; Yang XY conceived the project, provided the idea, designed and guided the experiments, and supported scientific and technological platform. All authors contributed to the general discussion.

Author information

Tian Zhao completed his PhD under the supervision of Prof. Christoph Janiak at the University of Düsseldorf and then moved to Wuhan University of Technology as a postdoctoral research associate, working on metal-organic frameworks (MOFs) in the group of Prof. Xiao-Yu Yang. His research mainly focuses on the design, syntheses and applications of hierarchically porous materials.

Christoph Janiak is a full professor for bio-inorganic chemistry and catalysis at the University of Düsseldorf, with research interests in the synthesis and properties of metal- and porous-organic frameworks (MOFs, COFs), metal nanoparticles, ionic liquids and catalysis. Until 2018 he was a visiting professor at Wuhan University of Technology in China.

Xiao-Yu Yang received his PhD from Jilin University (co-educated at FUNDP of Belgium). After a postdoctoral fellowship at the FUNDP, he worked as a “Chargé de Recherches” at the FNRS in Belgium. He is currently working as full professor at Wuhan University of Technology and visiting professor at Harvard University. His research is aimed at hierarchical assembly techniques, novel porous systems, and hierarchical structured materials for the applications in energy, environment, catalysis and bioengineering.


Supplementary information

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


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  • Figure 1

    (a–c) SEM and TEM (inset) images of (hierarchically porous) HP-MIL-101(Cr) under various magnifications. (d, g) HRTEM images of HP-MIL-101(Cr). (e, f) Magnified regions of I and II in (d), respectively.

  • Figure 2

    (a) Small-angle and wide-angle PXRD patterns of HP-MIL-101(Cr) and O-MIL-101(Cr); the photographs of the materials are given in the insets (for enlarged photos see Fig. S4). (b) Nitrogen sorption isotherms of HP-MIL-101(Cr) and MIL-101(Cr). The inset curves depict the BJH PSD (filled data points for adsorption, open data points for desorption).

  • Figure 3

    Schematic illustration of the formation mechanism of HP-MIL-101(Cr) with monocarboxylic acid. (a) The replacement of acetate with the terephthalate ligand. (b) The nanofusion procedure of crystal nucleus. (c) Micro-phase separation progress with high concentration at high temperature (the scale bar is 1 μm).

  • Table 1   Summary on catalytic reactions




    TOF (mmol g−1 min−1)f

    Conversion (%)



    Indene oxidation reactionb









    1-Dodecene oxidation reactionb









    Methanolysis of styrene oxidec















    Dibenzoxanthene synthesisd








































    Samples were dried in the vacuum oven over night. b) Mole ratio: (indene or 1-dodecene)/H2O2=4:1, 70°C, get 2-(carboxymethyl) benzoic acid and undecanoic acid, respectively. c) Molar ratio: styrene oxide/methanol=1:200, ambient temperature, get 2-phenyl-2-methoxyethanol. d) Mole ratio: benzaldehyde/2-naphthol=1:2, 80°C. e) Mole ratio: 2-naphthol/benzaldehyde/acetamide=1:1:1.4, 130°C. f) TOF of the catalyst=(molar conversion of substrate)/(mass of MIL-101(Cr)×reaction time) or (moles of substrate consumed)/(mass of PTA×reaction time), depending on the reactions.


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