Facile Synthesis of Highly Uniform Fe-MIL-88B Particles - Crystal

May 25, 2016 - Highly uniform Fe-MIL-88B micron particles with shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism were obtained ...
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Facile Synthesis of Highly Uniform Fe-MIL-88B Particles Xuechao Cai,†,‡ Jun Lin,*,† and Maolin Pang*,† †

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China ‡ University of the Chinese Academy of Sciences, Beijing 100049, PR China S Supporting Information *

ABSTRACT: Highly uniform Fe-MIL-88B micron particles with shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism were obtained by a surfactant (polyvinylpyrrolidone, PVP) assisted modified solvothermal method. The modified solvothermal method further demonstrated its feasibility to produce highly uniform micron or nanosized MOF, which provides great opportunities for fabrication of new MOFs and investigation their potential applications in versatile research fields.

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ize and shape controlled synthesis of nano or micron sized metal−organic frameworks (MOFs) has attracted great attention in recent years.1−11 The ability to deliberately access monodisperse nano or microsized MOFs offers prospective applications in heterogeneous catalysis, porous membranes, thin-film devices, controlled drug release, and biomedical fields.7−11 It is worth mentioning that the size, uniformity, and monodispersity of the product play important roles in employing MOFs in practical application, for instance, MOFs in nanoscale are a crucial requirement for biomedical utilization, and the uniformity as well as monodispersity will largely influence the gas adsorption or separation kinetics.7−11 To date, several research groups reported size and shape controlled synthesis and self-assembly of highly uniform nano or microsized MOFs particles.12−22 Among the developed synthetic protocols, the modified solvothermal method is regarded as one of the most effective approaches to prepare highly uniform nano or micron sized MOFs.19,20 For the traditional solvothermal method, the reactants were usually added into a vial and reacted under static conditions in an oven at certain temperature for a while, and it is almost impossible to get highly uniform MOF particles due to particle aggregation or the different convective speed in a vial. However, for the modified solvothermal method, the precursors were mixed and sealed in a vial, and then heated on a hot plate with continuous stirring, which largely allows the mixture to react homogeneously, avoids particle aggregation, and permits formation of highly uniform particles. Based on this strategy, we precisely controlled the uniformity and morphology of (In, Ga, Fe)-socMOF, and successfully produced large area 2D superlattices as well as MOF colloidosomes for the first time.19,20 Due to the nontoxic and highly flexible properties, iron(III)based MOFs received considerable interest, especially for MIL53, MIL-101, and MIL-88.23−26 MIL-88B is constructed from oxygen-centered iron(III) carboxylate trimer molecular building blocks, which are linked together through terephthalic acid (1,4-BDC), as shown in Figure 1a. Ferey et al. reported the crystal structures and highly flexible properties of Fe-MIL-88 © XXXX American Chemical Society

Figure 1. (a) Structure of Fe-MIL-88B viewed along a axis (left) and c axis (right). (b) Morphological evolution from hexagonal bipyramids to bipyramidal hexagonal prism by increasing the amount of PVP.

serial MOFs for the first time.25,27 Horcajada et al. investigated the drug delivery properties and biomedical applications for a series of nontoxic and biocompatible iron(III) carboxylate MOFs.27 Metzler-Nolte et al. studied the breathing effect and the loading and delivery of gasotransmitter carbon monoxide properties of Fe-MIL-88B.28,29 Do et al. reported the size and shape controlled synthesis of Fe-MIL-88B-NH2 crystals by using nonionic triblock copolymer F127 and acetic acid as stabilizing and deprotonating agents, respectively.30 Fe-MIL88B rods were synthesized by Oh’s group, and hematite (aFe2O3) and magnetite (Fe3O4) rods were selectively prepared by controlling the calcination conditions of the parent coordination polymers.31 Although Fe-MIL-88 serial MOFs have been produced by several research groups, only nonuniform products were obtained in their studies.25−31 In this work, the modified solvothermal method further demonstrated its feasibility to produce highly uniform Fe-MIL-88B micron particles, and the Received: February 25, 2016 Revised: May 13, 2016

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DOI: 10.1021/acs.cgd.6b00313 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 4. Aspect ratio of Fe-MIL-88B crystals (prepared by adding different amounts of PVP, 0.01 M in DMF).

Figure 2. SEM images of Fe-MIL-88B crystals obtained by adding different amounts of PVP (0.01 M in DMF): (a) 0.2 mL, (b) 0.5 mL, (c) 0.8 mL, (d) 1.2 mL, (e) 1.5 mL, (f) 2.0 mL. Scale bar is 2.5 and 1 μm for low and high magnification (inset) images, respectively.

Figure 3. PXRD patterns of the as-synthesized Fe-MIL-88B particles prepared by adding different amounts of PVP (0.01 M in DMF): (a) 0.2 mL, (b) 0.5 mL, (c) 0.8 mL, (d) 1.2 mL, (e) 1.5 mL, (f) 2.0 mL.

resultant products with shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism were obtained by increasing the amount of surfactant PVP, as shown in Figure 1b. Fe-MIL-88B crystals were produced from the solvothermal reaction between ferric chloride (FeCl3) and 1,4-benzenedicarboxylic acid (1,4-BDC) in N,N′-dimethylformamide (DMF) solution containing PVP. Surfactant was always used to regulate the morphology of nanomaterials including MOFs.7−11 PVP was introduced into the reaction medium as surfactant to regulate the size and shape of Fe-MIL-88B in this study. In order to investigate the effect of the concentration of PVP on the morphological evolution, different amounts of PVP (0.01 M in DMF) from 0 to 2 mL were added into the reaction. Figure 2 shows the representative scanning electron micrographic (SEM) images of the as-synthesized products prepared by adding different amount of PVP (0.01 M in DMF). In fact, nonuniform particles were obtained in the absence of PVP

Figure 5. (a) N2 and (b) CO2 adsorption−desorption isotherms for Fe-MIL-88B particles.

(Figure S2, SI), and highly uniform products with different morphologies were prepared by adding 0.2 to 2.0 mL of PVP. As shown in Figure 2a, when a small amount of PVP (0.2 mL) was added, truncated hexagonal bipyramids with an average size of 1.78 μm in length and 1.78 μm in width were obtained. By increasing the amount of PVP to 0.5 mL, the length and width of the hexagonal bipyramids increased to 2.39 and 1.94 μm, respectively (Figure 2b). Interestingly, when we further B

DOI: 10.1021/acs.cgd.6b00313 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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PVP, 0.01 M in DMF). As shown in Figure 5a, the fully reversible nitrogen sorption isotherm measured at 77 K confirms permanent microporosity for the Fe-MIL-88B particles. The BET and Langmuir surface areas of Fe-MIL88B were 209.83 and 328.99 m2/g, respectively, and the total pore volume was 0.42 cm3/g. As shown in Figure 5b, the CO2 uptake capacity was also measured at 273 and 298 K, respectively, and the maximum uptake was 39.04 cm3/g. In summary, a facile modified solvothermal strategy was used to prepare highly uniform and monodisperse Fe-MIL-88B micron particles. The morphology and aspect ratio of crystals were adjusted by changing the amount of PVP in the reaction system, and a shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism was observed by increasing the amount of PVP. This surfactant-assisted modified solvothermal method further demonstrated its feasibility to produce highly uniform micron or nanosized MOF, which provides great opportunities for fabrication of new MOFs and investigation their potential applications in versatile research fields.

increased the amount of PVP to 0.8 mL, a very narrow platform appeared on the bottom of the hexagonal bipyramids structure, and bipyramidal hexagonal prism instead of hexagonal bipyramids was formed (Figure 2c). The width of platform increased with increasing the amount of PVP gradually. By adding 2.0 mL of PVP (Figure 2f), the width of the platform was 1.60 μm, and the size of the particles reached 5.38 and 2.63 μm in length and width, respectively. More SEM images could be found in Figures S2−S7 (SI). Figure 3 shows the powder X-ray diffraction (PXRD) patterns for the as-synthesized products in the presence of different amounts of PVP. The diffraction peaks agreed well with that of the calculated PXRD patterns for Fe-MIL-88B, which indicated that pure phase of Fe-MIL-88B was obtained by our method. PVP is an amphiphilic, nonionic polymer, which is usually used as surfactant or capping agent to stabilize or regulate the size and shape of nanoparticles.32−35 In this work, PVP played an important role in controlling the size and shape of Fe-MIL88B particles (Figure 2 and Figure S2−S8, SI). Fe-MIL-88B particles could be prepared in the absence of PVP; however, the small nanoparticles aggregated extensively onto the large particles due to the high surface energy. When a small amount of PVP (0.2 mL) was added, highly uniform and monodispersed Fe-MIL-88B particles were formed. This should be attributed to the interactions between PVP and metal ions (Fe3+) through coordination binding with O and N atom of the pyrrolidone ring.32−35 It could be found from the infrared spectra for PVP-protected Fe-MIL-88B particles that two peaks at 1685 and 1660 cm−1 were observed, which should be assigned to the CO stretching mode for the PVP amide unit (Figure S8, SI). Therefore, it is indicated that the amide moiety of PVP is weekly coordinated to Fe3+ during nucleation and crystal growth processes of Fe-MIL-88B, which could stabilize the dissolved metallic salts through steric and electrostatic effects, and also decreased the number of nucleation points. Consequently, PVP effectively prevents particle aggregation and forming highly monodispersed large Fe-MIL-88B crystals.32−35 As shown in Figure 4, the aspect ratio (length/width) of the particles were increased from 1.00 to 2.05 by increasing the amount of PVP, and the shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism was observed accordingly. This is because the long-chain PVP molecules were probably oriented along the [001] direction, and the capping effect of PVP is more favorable in the [001] direction than others, i.e., the interaction between PVP and the newly formed {010} facets is much stronger than with those of {011} facets, which resulted in the different growth rate of the crystal facets, and forming bipyramidal hexagonal prism crystals by increasing the amount of PVP.36,37 Therefore, it can be concluded from the above results that PVP indeed can be used as surfactant and capping agent to regulate the morphology of Fe-MIL-88B particles in this study. The as-synthesized Fe-MIL-88B particles were found to be thermally stable up to about 275 °C, characterized by thermogravimetric analysis (TGA, Figure S9, SI). The TGA curves exhibited a major weight loss in the range of 430−700 °C, which indicated the structure totally decomposed at around 430 °C. As our preliminary effort in application of these highly uniform Fe-MIL-88B particles, low-pressure gas adsorption measurements were conducted on the exchanged and fully evacuated Fe-MIL-88B particles (prepared by adding 0.5 mL

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b00313. Experimental procedures, additional SEM images, IR spectra, and TGA curve (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This project is financially supported by the National Natural Science Foundation of China (NSFC 21471145), and “Hundred Talents Program” of Chinese Academy of Science. We greatly appreciated Ms. B. Liu and Prof. Y. L. Liu in Jilin University for their assistance in gas adsorption test.

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DOI: 10.1021/acs.cgd.6b00313 Cryst. Growth Des. XXXX, XXX, XXX−XXX