Controllable Synthesis of Highly Uniform Nanosized HKUST-1

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Controllable Synthesis of Highly Uniform Nanosized HKUST-1 Crystals by LSS method Xuechao Cai, Zhongxi Xie, Maolin Pang, and Jun Lin Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01695 • Publication Date (Web): 04 Jan 2019 Downloaded from http://pubs.acs.org on January 7, 2019

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Crystal Growth & Design

Controllable Synthesis of Highly Uniform Nanosized HKUST-1 Crystals by LSS method

Xuechao Cai,a,b Zhongxi Xie,a,c Maolin Pang a,* and Jun Lin,a,*

a.

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China.

b. University of the Chinese Academy of Sciences, Beijing 100049, PR China. c. University of Science and Technology of China,No. 96, JinZhai Road, Baohe District, Hefei, Anhui 230026, P. R. China. * Corresponding author. E-mail address: [email protected], [email protected] ABSTRACT: Nowadays, preparation of nanosized metal-organic frameworks (NMOFs) has attracted great attention for diverse applications, such as drug delivery, biological imaging, catalysis, functional membranes. In this report, highly uniform nanosized HKUST-1 crystals with sizes from about 30 to 140 nm were obtained by the liquid-solid-solution (LSS) method, which is mainly based on a general phase transfer and separation mechanism occurring at the interfaces of the liquid, solid and solution phases. The SEM, TEM, PXRD, FTIR, TGA and gas adsorption-desorption analysis results demonstrated the successful preparation of nanosized HKUST-1 crystals. This work further proves its feasibility of the LSS method to synthesize NMOFs, which may open up a facile and universal method to facilitate the fundamental research on preparing NMOFs.

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Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Controllable Synthesis of Highly Uniform Nanosized HKUST-1 Crystals by LSS method

Xuechao Cai,a,b Zhongxi Xie,a,c Maolin Pang a,* and Jun Lin,a,*

b.

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China.

b. University of the Chinese Academy of Sciences, Beijing 100049, PR China. c. University of Science and Technology of China,No. 96, JinZhai Road, Baohe District, Hefei, Anhui 230026, P. R. China

* Corresponding author. E-mail address: [email protected], [email protected]

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Metal-organic frameworks (MOFs),1 porous crystalline materials made up of metal clusters linked by organic ligands, have attracted extensive research interests for their potential applications in gas storage and separation,2,3 heterogeneous catalysis,4,5 biomedicine,6-9 etc. To date, nanosized metal-organic frameworks (NMOFs) have received great attention due to their unique characteristics. For example, MOFs with nanometer dimension have important applications in biomedicine;6-11 NMOFs even have advantages in traditional separation and catalytic applications.12 Until now, the methods for preparing NMOFs mainly include the conventional

solvothermal,9,13-19

room

temperature

precipitation,20-23

reverse

microemulsion,11,24,25 microwave assisted synthesis,26,27 coordination modulation method,28-30 etc. In fact, due to the complexity during the growth of MOF crystals, the methods for preparing NMOFs are confined. Therefore, exploring new method to controllably synthesize NMOFs is vitally important. Li and coworkers have proved that liquid-solid-solution (LSS) strategy could effectively prepare versatile nanomaterials.31 Inspired by the special interface activity, our group recently reported the successful preparation of nanosized Fe-soc-MOF via the LSS method.32,33 We are convinced that this method has clear prospects for preparing NMOFs and we have been trying to produce other kinds of NMOFs by this method. HKUST-1, also denoted as Cu3(BTC)2, is a well-known MOF material constructed from copper dimer units linked by benzene-1,3,5-tricarboxylic acid (BTC), which is first reported by Williams et al.34 So far, there have been several reports about the preparation of nanosized HKUST-1 crystals.35-38 For instance, Baiker et al. developed a general functional organic polymer-based methodology for the synthesis of nanoscale HKUST-1.35 Kitagawa and coworkers employed the microwave-assisted coordination modulation method to efficiently control the size of [Cu3(btc)2] crystals, ranging from few tenths of nanometers to micrometers.36

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The above two reports used traditional solvothermal methods to controll the size of MOF crystals by introducing additional structure-directing agents (SDAs). The SDAs usually occupy the skeleton of the MOF materials, which may affect the inherent properties of the products. However, their removal/exchange after the synthesis is difficult, because strong host-guest interactions will lead to structural collapse upon removal of the guest molecules.39 In addition, the traditional solvothermal method is usually cost consuming and inefficient, and more importantly, it cannot effectively control the nucleation and growth of MOF nanoparticles, thus hindering the uniformity and monodispersity of the NMOF particles. Martens et al. obtained 100 nm sized Cu3(BTC)2 crystals by freezing the reaction mixture in liquid nitrogen immediately after mixing and freeze drying.37 This method is a little bit complicated during the operation process, and the nucleation and growth process of the nanoparticles are also not well controlled. Thus the MOF nanocrystals are non-uniform and less monodispersed. Very recently, Zhang’ group reported the preparation of nanosized HKUST-1 and other nanoMOFs by using syringe pump to separately deliver metal and ligand stock solutions at a controlled feed rate into the reaction system.38 In this general and wonderful approach, the preciseness of size control is ensured by the separated and controlled nucleation and growth. Therefore, highly uniform and monodispersed NMOF particles can be obtained. But a little regret, the organic solvent N,NDimethylformamide (DMF) used in the preparation of nano HKUST-1 may occupy the pores of the nano MOFs and influence the performance of the products.39 In addition, organic solvent DMF is expensive and may also cause potential pollution to the environment.40 In this study, we report for the first time, the LSS approach to precisely control the size of HKUST-1 nanocrystals. During this experiment, water and ethanol are the main solvents, which are inexpensive and less infectant to nature. Moreover, this method is facile and the nucleation

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and growth process can be well controlled by the designed oil-water interface. Herein, highly uniform nanosized HKUST-1 crystals with sizes from about 30 to 140 nm were obtained, we will describe the preparation of 70-nm HKUST-1 crystals as a typical example. As confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) (Figure 1), when 0.30 mL of oleic acid (OA) was used in the experiment (see experimental details in SI), highly uniform spherical HKUST-1 nanoparticles with an average size about 70 nm were obtained by the LSS method. The powder X-ray diffraction (PXRD) pattern result (Figure 2a) demonstrated the formation of pure phase of HKUST-1 nanocrystals. The formation mechanism of OA-capped nano HKUST-1 crystals was proposed as follows (Figure 3): First, a thermostable

Figure 1. SEM (a, b) and TEM (c, d) images of 70-nm HKUST-1 crystals with different magnifications.

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Figure 2. (a) The PXRD patterns of nano HKUST-1. (b) The FTIR spectra of Cu-oleate, nano HKUST-1 and bulk HKUST-1. (c) TGA curves of nano HKUST-1 and bulk HKUST-1. (d) N2 adsorption-desorption isotherms and BJH size distribution (inset). microemulsion system was prepared by mixing NaOH aqueous solution with ethanol, OA and nhexane under stirring.41 After the addition of Cu2+ cations, Cu(II) oleate clusters formed immediately due to the strong coordination ability between copper(II) and oleate ligands, and then moved to the upper mixed solution of OA and n-hexane (Figure S1a, SI). Next, when BTC ligands were added, HKUST-1 nanocrystals generated gradually at the emulsion phase interface and were “protected” by OA molecules with the alkyl chains on the outside, thus, the nanoparticles transferred from the O/W interface into the inner oil core, which gave the nanocrystals hydrophobic surfaces (Figure S1b-c, SI). In a nutshell, the coordination reaction of

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Figure 3. Formation mechanism of OA-capped nanosized HKUST-1 prepared by the LSS method. copper(II) oleate (solid) and BTC ligand were mainly conducted at the interfaces between ethanol-n-hexane-OA liquid phase (liquid) and water-ethanol solutions (solution). It is worth mentioning that different from conventional solvothermal method, owing to the generation of copper(II) oleate clusters first and the protection of OA, the nucleation speed significantly slowed down, eventually resulting in the formation of highly uniform nanosized HKUST-1 crystals.32,33 For comparison, HKUST-1 particles synthesized in aqueous phase (denoted as bulk HKUST-1) were prepared according the previous literature.34 The fourier transform infrared (FTIR) spectrum was used to characterize functional groups in HKUST-1 samples. As shown in Figure 2b, FTIR spectrum of the nanosized HKUST-1 crystals is in good agreement with the bulk HKUST-1 samples and other previous reports of HKUST-142-44 in the range of 2500-400 cm-1.

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The peaks in the range of 1560-1440 cm-1 and 1374 cm-1 corresponded to asymmetric and symmetric vibration of coordinated carboxyl groups, respectively. Besides, the band at 1447 cm-1 is ascribed to the C-C vibration in the aromatic ring.42,43 The 492 cm-1 peak is the typical vibration mode directly involving Cu(II) species. The additional two strong peaks at 2854 and 2924 cm-1 are the CH2 symmetric and asymmetric stretching vibrations in oleate ligands respectively,44 which is the same as the FTIR spectrum of copper oleate samples. However, there is no such phenomenon in bulk HKUST-1 samples. In addition, as shown in Figure S1b, the obtained nanosized HKUST-1 products floated on the upper layer of OA and n-hexane at the end of the reaction. Moreover, the HKUST-1 nanoparticles can be easily dispersed in nonpolar solvent (such as cyclohexane) to form a homogenous colloidal solution (Figure S1c). The above results proved the presence of coordinated oleate ligands on the surface of nanosized HKUST-1 crystals. The thermal gravimetric analysis (TGA) of both the nano and bulk HKUST-1 samples was performed under a nitrogen atmosphere. As revealed in Figure 2c, the TGA curve of nano HKUST-1 is similar to that of the bulk crystals,42 except for about 10 percent increase in weight loss, further indicating the presence of coordinated oleate ligands in the final products. As shown in Figure 2d, the fully reversible type-I nitrogen adsorption isotherms conducted at 77 K confirmed permanent microporosity of the activated nano HKUST-1 compounds. The apparent BET surface area was estimated to be of 1472 m2/g. Pore size distribution was calculated to be 0.78 nm by using DFT models, which is usually employed for analyzing micropores with pore diameter less than 2 nm.45 The above results are consistent with the data reported in the previous literatures,34,46-49 which further proves the successful preparation of nano HKUST-1 crystals. In addition, we also examined the effect of the amount of OA on the size of nano HKUST-1. As shown in Figure 4a-e and Figure S2-S6 (SI), when the dosage of OA was changed from 0.20

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Figure 4. SEM images of HKUST-1 nanocrystal samples prepared with different amounts of OA. (a) 30-nm sample, 0.20 mL of OA, (b) 50-nm sample, 0.25 mL of OA, (c) 70-nm sample, 0.30 mL of OA, (d) 100-nm sample, 0.35 mL of OA, (e) 140-nm sample, 0.40 mL of OA and (f) PXRD patterns. Scale bar is 200 nm. Insets are particle size distributions obtained by counting about 100 particles according to corresponding SEM images. to 0.40 mL, while keeping the remaining reaction conditions identical, the diameter of the HKUST-1 nanoparticles increased from about 30 to 140 nm. The PXRD data (Figure 4f), FTIR spectra (Figure S7, SI) and TGA curves (Figure S8, SI) revealed that changes in the amount of OA did not affect the crystal structure and ingredient of the nano HKUST-1. According to the previous published literatures,50-53 increasing amounts of OA are known to increase the early time ripening (ETR). As a result, OA molecules can inhibit nucleation and promote growth of the nanocrystals. On the basis of these related reports, we conclude that excess OA could accelerate the surface reaction rate of nano HKUST-1 crystals in this work, resulting in a reduction in the maximum number of nanoparticles. Therefore, the OA molecules can not only be used to coordinate with copper ions to form copper(II) oleate, but also acted as a surfactant to

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control the growth of nano HKUST-1. As a result, when the amount of OA increases, the size of the HKUST-1 nanoparticles increases gradually. In conclusion, highly uniform nanoscale HKUST-1 crystals were obtained by LSS method. By changing the amount of OA, we could accurately regulate the size of HKUST-1 nanocrystals from about 30 to 140 nm. More importantly, this work extends its feasibility of the LSS method to synthesize NMOFs. The present and our previous works32,33 may open up a facile and universal method to manufacture nano MOF crystals which is very important in the fields of drug delivery, bioimaging, membranes, optics, building blocks for nano-device assembly, etc.

ASSOCIATED CONTENT Supporting Information: This material is available free of charge via the Internet at http://pubs.acs.org. Experimental section, photographs, additional SEM images, FTIR spectra and TGA curves for nano HKUST-1. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected], [email protected] ORCID ID: Xuechao Cai: 0000-0002-6388-6078

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Maolin Pang: 0000-0001-5125-4615 Jun Lin: 0000-0001-9572-2134 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This project is financially supported by the National Natural Science Foundation of China (NSFC 21471145, 51720105015), Science and Technology Development Planning Project of Jilin Province (20170101179JC) and the ‘‘Hundred Talents Program’’ of the Chinese Academy of Science.

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For Table of Contents Use Only Controllable Synthesis of Highly Uniform Nanosized HKUST-1 Crystals by LSS method Xuechao Cai,a,b Zhongxi Xie,a,c Maolin Pang a,* and Jun Lina,* a. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China. b. University of the Chinese Academy of Sciences, Beijing 100049, PR China. c. University of Science and Technology of China, No. 96, JinZhai Road, Baohe District, Hefei, Anhui 230026, P. R. China.

SYNOPSIS: Highly uniform nanosized HKUST-1 crystals with sizes from about 30 to 140 nm were obtained by the LSS method. This work may open up a facile and universal method to manufacture nano MOF crystals which is very important in the fields of drug delivery, biological imaging, membranes, optics, building blocks for nano-device assembly, etc.

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Controllable Synthesis of Highly Uniform Nanosized HKUST-1

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