Shumin
Li
a,
Liang
Zhao
*a,
Yining
Yao
a,
Zhengying
Gu
a,
Chao
Liu
a,
Wenli
Hu
a,
Ye
Zhang
a,
Qian
Zhao
a and
Chengzhong
Yu
*ab
aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, P. R. China. E-mail: lzhao@chem.ecnu.edu.cn; czyu@chem.ecnu.edu.cn
bAustralian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, Queensland 4072, Australia. E-mail: c.yu@uq.edu.au
First published on 25th November 2022
The integration of two or more different types of metal–organic frameworks (MOFs) into hybrid MOF-on-MOF heterostructures has been widely studied, and the diversity of MOF-on-MOF heterostructures can be effectively increased by exploring the integration strategy of different MOF building blocks. Here, we report the structure regulation of MOF-on-MOF hybrids via controlling the heterogeneous nucleation and homogeneous nucleation growth of guest MOFs. By using ZIF-90 as the host and ZIF-8 as the guest, binary ZIF-90@ZIF-8 complexes can be synthesized. Moreover, the nucleation mode of ZIF-8 depends on the addition sequence of metal ions and ligands of the guest MOF, including heterogeneous nucleation and homogeneous nucleation. Therefore, ZIF-90@ZIF-8 hybrids with a core–shell structure and smooth surface or a core–satellite structure and rough surface are successfully prepared, increasing the structural diversity of MOF-on-MOF materials.
Zeolitic imidazolate frameworks (ZIFs) are considered as a subcategory of MOFs and have been developed rapidly since they combine the properties of both MOFs and zeolites, and have high thermal stability.17 Among various ZIFs, ZIF-818 is one of the most popular members and has attracted great attention in catalysis,19–21 adsorption and separation,22 and electrochemistry.23 In parallel, ZIF-90 has gained increasing research interest as it contains a reactive aldehyde group in the framework with ease of further functionalization.24,25 Recently, Mo and co-workers reported ZIF-8@ZIF-90 as advanced fluorescence-encoding materials.26 However, the synthesis of ZIF-90@ZIF-8 has not been reported. Moreover, MOF-on-MOF binary compositions can be adjusted into core–shell, core–satellite, yolk–shell, hollow multi-shell, asymmetric and film architectures27via various strategies.28–31 For example, Oh's group prepared MOF-on-MOFs with core–shell-type and semitubular morphologies, using the same host MOF and different guest MOFs.28 Liu and co-workers synthesized MOF-on-MOF heterostructures with the growth sites of guest MOFs determined by host MOFs with different morphologies.29 Nevertheless, it has been rarely reported that the architecture of MOF-on-MOFs can be regulated using one host MOF with the same morphology and the same type of guest MOF.
Here, by using ZIF-90 as the host and ZIF-8 as the guest, binary ZIF-90@ZIF-8 complexes with core–shell and core–satellite structures were synthesized for the first time. As shown in Fig. 1, the structures of the hybrids can be regulated by controlling the heterogeneous nucleation and homogeneous nucleation growth of the guest MOF, simply via changing the addition sequence of metal ions and ligands of the guest MOF during the synthesis. When 2-MeIM is introduced before Zn2+, the heterogeneous nucleation and growth of ZIF-8 on ZIF-90 core particles lead to ZIF-90@ZIF-8-A with a core–shell structure and smooth surface. When Zn2+ is added first, ZIF-8 nanoparticles tend to form via homogeneous nucleation in solution, then conjugate with ZIF-90 and generate ZIF-90@ZIF-8-B with a core–satellite structure and rough surface. Different from studies where using host MOFs with different morphologies or different types of guest MOFs are necessary, the structural regulation involves the same host–guest pair in our strategy (ZIF-90 rhombic dodecahedron–ZIF-8).
Fig. 2 SEM (a, c and e) and TEM (b, d and f) images of (a and b) ZIF-90, (c and d) ZIF-90@ZIF-8-A, (e and f) ZIF-90@ZIF-8-B. The scale bar is 200 nm. |
Then, using ZIF-90 nanoparticles as the host, ZIF-90@ZIF-8-A and B heterostructures were synthesized (Fig. 1). SEM (Fig. 2c) and TEM (Fig. 2d) images reveal that ZIF-90@ZIF-8-A shows a well-defined rhombic dodecahedral morphology with a smooth surface and uniform size distribution, similar to that of the host ZIF-90. However, the average diameter of ZIF-90@ZIF-8-A is increased to 278 nm, indicating the heterogeneous nucleation and growth of ZIF-8 on ZIF-90. In contrast, ZIF-90@ZIF-8-B shows a rough surface as evidenced from SEM (Fig. 2e) and TEM (Fig. 2f) images, different from ZIF-90@ZIF-8-A with a smooth surface. The average size of ZIF-8 nanoparticles is estimated to be ∼25–30 nm in diameter.
The XRD patterns of the synthesized ZIF-90@ZIF-8-A and ZIF-90@ZIF-8-B nanoparticles are shown in Fig. 3a. It is noted that due to the isostructural nature of ZIF-90 and ZIF-8, the XRD patterns of all the particles, including ZIF-90@ZIF-8-A, ZIF-90@ZIF-8-B, ZIF-90 and ZIF-8, showed diffractions at the same positions except for slight differences in relative intensity. It is noted that both ZIF-8 and ZIF-90 have zinc atoms, and their compositional difference is in the ligands. In ZIF-8, the ligand 2-MeIM does not contain oxygen, in contrast to 2-ICA in ZIF-90 which contains an aldehyde group. To provide information on the composition distribution in the binary MOF composites, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and elemental mapping (Zn and O) images of ZIF-90@ZIF-8-A were taken as an example, using ZIF-90 as a control sample. In the case of ZIF-90, from the HAADF-STEM image (Fig. S1a†), Zn and O mappings (Fig. S1b†) and the superimposed elemental image (Zn + O, Fig. S1c†), Zn and O are evenly distributed over the entire nanoparticle range. However, for ZIF-90@ZIF-8-A (Fig. S1d–f†), a Zn-rich outer layer (red color) is evident in comparison with ZIF-90, consistent with the ZIF-8 layer formed on the outer surface of ZIF-90 in the ZIF-90@ZIF-8-A heterostructure.
To further differentiate ZIF-90 and ZIF-8 in the composites, the FTIR spectra of the two ZIF-90@ZIF-8 nanoparticles and ZIF-90 were also recorded. In addition, ZIF-8 nanoparticles were synthesized and used in the FTIR study to verify the successful modification of ZIF-8 on the ZIF-90 surface. As shown in the TEM images (Fig. S2a and b†), ZIF-8 with an estimated particle size of about 300 nm was synthesized. The XRD pattern of ZIF-8 is consistent with the simulated result, further confirming the successful synthesis of ZIF-8 (Fig. S3†).35 From the FTIR spectra (Fig. 3b), both ZIF-90@ZIF-8 composites display one band at around 1675 cm−1 corresponding to the CO stretching of 2-ICA (also observed in ZIF-90),24 and another peak at 759 cm−1 originating from the stretching vibration of the C–H group in 2-MeIM (also observed in ZIF-8).36 Collectively, the XRD, SEM, TEM and FTIR results indicate that core–shell structure ZIF-90@ZIF-8-A with a smooth surface and core–satellite structure ZIF-90@ZIF-8-B with a rough surface have been successfully synthesized.
The ZIF-90@ZIF-8 hybrids with core–shell and core–satellite structures obtained in our work are unique in composition compared with reported MOF-on-MOFs with core–shell structures such as ZIF-8@ZIF-67,37 Fe-MIL-88B@Fe-MIL-88C31 and IRMOF-3@MOF-5,38 or MOF-on-MOFs with core–satellite structures such as MIL-125@ZIF-8,29 PCN-222@PCN-608, PCN-222@NU-1000, PCN-222@PCN-134, Zr-BTB@PCN-134,30 and MIL-88B@UIO-66.39 Although the composition of ZIF-90@ZIF-8 is identical to that of reported ZIF-8@ZIF-90,26 the spatial arrangement is different which could have implications for future applications. For example, it is well known that ZIF-90 is relatively hydrophilic while ZIF-8 is hydrophobic.40,41 It can be inferred that the surface hydrophilicity/hydrophobicity of ZIF-90@ZIF-8 and ZIF-8@ZIF-90 could be different due to the nanostructure difference. Moreover, the structural regulation of the same host–guest pair (ZIF-8 on rhombic dodecahedron ZIF-90) has been achieved in our work, leading to core–shell and core–satellite structures. This is also different from a reported ZIF-8@ZIF-90 with only a core–shell structure,26 or other reports of MOF-on-MOFs with core–satellite structures by changing the type and morphology of the host MOF.28,29
To understand the formation mechanism of the ZIF-90@ZIF-8-A and ZIF-90@ZIF-8-B heterostructures, the intermediate structures at different reaction time points were monitored. In the case of ZIF-90@ZIF-8-A, a 2-MeIM solution was firstly added into a ZIF-90 solution and stirred for 5 min before Zn2+ addition (Fig. 4a). The reaction time was counted after the addition of Zn2+ precursors. The rhombic dodecahedral morphology is well kept at reaction times of 2, 5 and 20 min as confirmed by TEM observations (Fig. 4b–d). However, the average diameters of nanoparticles gradually increased to 24 nm, 31 nm and 41 nm at 2, 5, and 20 min, respectively. This observation indicates that by adding 2-MeIM first and then Zn2+ to react with ZIF-90, a layer of ZIF-8 is selectively grown on the surface of ZIF-90 by heterogeneous nucleation, leading to the formation of the ZIF-90@ZIF-8-A heterostructure.
To understand the interfacial interaction that drives the heterogeneous nucleation of ZIF-8 on ZIF-90, ZIF-90 was immersed in 2-MeIM solution, and then washed with methanol three times to remove free 2-MeIM physically adsorbed on surfaces and in frameworks. The solid sample was collected and labelled as ZIF-90/M. The FTIR spectrum of ZIF-90/M is presented in Fig. 5. The characteristic peak of CO at 1675 cm−1 for ZIF-90 was retained after soaking in 2-MeIM solution. In addition, the appearance of a new peak at 1101 cm−1 (marked with a blue dashed line) and a shoulder at ∼936 cm−1 (indicated by an arrow) suggests the presence of 2-MeIM in ZIF-90/M. Compared with the corresponding peaks at 1111 cm−1 (C–C–H formation vibration) and 942 cm−1 (–CH3 in-plane bending vibration and C–C–H formation vibration) of 2-MeIM (marked with a red dashed line),42 these new peaks have a certain red shift. These observations suggest that the added 2-MeIM can coordinate with the exposed Zn central atoms on ZIF-90, causing the weakening of –CH3 and C–C–H bonds.43 Furthermore, our observation is in accordance with a literature report by Fan and co-workers. It is shown that the hydrolase-mimicking activity associated with the Zn–N node in ZIF-90 can be inhibited by acetate and EDTA,44 suggesting that there exist coordination unsaturated Zn atoms in ZIF-90 that can bind to one of the two N atoms in the imidazole ring of the added 2-MeIM in our synthesis. Presumably, the subsequently added Zn2+ preferentially coordinates with the remaining N atom in the 2-MeIm bond to the ZIF-90 surface, leading to the heterogeneous nucleation of ZIF-8 on the ZIF-90 surface.
In the synthesis of ZIF-90@ZIF-8-B, Zn2+ was added into ZIF-90 solution under stirring for 5 min, and then 2-MeIM was introduced to allow ZIF-8 formation (Fig. 6a). After another 2 min of reaction, tiny nanoparticles with a diameter of about 27 nm appeared in the solution (Fig. 6b), indicating that ZIF-8 nanoparticles tend to form via homogeneous nucleation in methanol solution under such an addition sequence. With the increase of reaction time to 5 min, smaller-sized nanoparticles gradually adhered onto the surface of ZIF-90 (Fig. 6c). When the reaction time was prolonged to 20 min, ZIF-90@ZIF-8-B with a rough surface structure became dominant (Fig. 6d). Presumably, when Zn2+ was added first, ZIF-90 had no coordination effect on Zn2+; thus, Zn2+ tended to interact with the later added 2-MeIM via homogeneous nucleation in solution, leading to the formation of ZIF-8 nanoparticles. It is suggested that there exists electrostatic interaction between the negatively charged ZIF-90 nanoparticles and positively charged ZIF-8 hosts;45 hence, core–satellite structure ZIF-90@ZIF-8-B with a rough surface is formed, which is different from core–shell structure ZIF-90@ZIF-8-A with a smooth surface.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2ce01272c |
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