Fabrication of MetalâOrganic Framework and Infinite Coordination

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Fabrication of Metal-Organic Framework and Infinite Coordination Polymer Nanosheets by the Spray Technique Yunong Li, Sha Wang, Yuan Zhou, Xiaojue Bai, Guoshuai Song, Xueying Zhao, Tieqiang Wang, Xuan Qi, Xuemin Zhang, and Yu Fu Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b04353 • Publication Date (Web): 09 Jan 2017 Downloaded from http://pubs.acs.org on January 14, 2017

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Fabrication of Metal-Organic Framework and Infinite Coordination Polymer Nanosheets by the Spray Technique Yu-Nong Li,‡* Sha Wang,‡ Yuan Zhou, Xiao-Jue Bai, Guo-Shuai Song, Xue-Ying Zhao, TieQiang Wang, Xuan Qi, Xue-Min Zhang and Yu Fu* College of Sciences, Northeastern University, Shenyang 110819, P. R. China

ABSTRACT: This manuscript has developed a rapid and convenient method to fabricate MOF and ICP nanosheets by spraying the atomized solution of metal ions onto the organic ligands solution. The nanosheets formation could be attributed to the anisotropic diffusion of metal ions in the ligands solution, which may give rise to a lateral interface of metal ions and organic ligands, where the crystals tend to grow laterally as the form of nanosheets. Three kinds of Zn and Cu-based MOF nanosheets and two kinds of Co-based ICP nanosheets have been

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successfully obtained by spray in mild conditions. These two-dimensional structure of nanosheets with nanometer thickness and homogeneous size can be evidenced by the SEM, AFM, XRD, BET and FT-IR measurements. Furthermore, the fabricated ICP nanosheets have shown efficiently catalytic performance for the conversion of CO2 to high value-added chemicals. This spray technique simplifies the nanosheets production process by the industrialized means and enhance its controllability by the fast liquid-liquid interfacial fabrication, thus opening up access to the industrialized fabrication for MOF and ICP nanosheets.

INTRODUCTION Over the past decades, metal-organic frameworks (MOFs) and infinite coordination polymers (ICPs) have attracted much attention due to their porous structures, channel functionalities and structural tailorability, which leads to wide range potential applications.1-3 In particular, making these materials into two-dimensional (2D) nanosheets is highly desirable, on account of the intriguing physical and chemical properties that are rarely present in bulk materials.4-5 In this context, nanosheets are usually considered to be promising candidates for gas separation,6-7 energy storage (e.g. batteries, solar cells),8-9 chemical sensors,10 catalysis11-15 and other application in the field of nanotechnology.16 In the structure of ICPs or MOFs, organic bridging ligands and inorganic connecting points can build an infinite network extending isotropically in three dimensional space.1 Hence, it is difficult to confine them in the 2D direction. With regard to ICP, the fabrication of ICP nanosheets has rarely been reported so far,17-19 and the preparation of spherical ICP particles are mostly focused on.20-22 As for MOF nanosheets, the fabrication approaches have been developed mainly in two ways, which are top-down exfoliation23-24 and bottom-up growth.25-26


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The top-down exfoliation relies on the disintegration of bulk layered materials into single- or multi-layers with large lateral dimensions. However, the morphological damage, re-aggregation and even the introduction of impurities in the exfoliation process are difficult to be avoided.5-6, 27 Therefore, plenty of efforts have been spent on the bottom-up growth strategy, which normally produces nanosheets at their genesis by either enhancing the anisotropic crystal growth or restricting the thermodynamically favored layer stacking.28 Recently, a novel bottom-up growth strategy has been reported to prepare MOF nanosheets by three-layer method. In this system, metal ions and organic ligands were respectively dissolved in the topmost and bottom solutions and separated by the intermediate buffer solvent, forming three vertically arranged liquid layers. The consequent diffusion of metal ions and linker ligands into the buffer segment caused the growth of MOF crystals in the horizontal direction, yielding corresponding nanosheets.7 Inspired by the three-layer mode, we have developed a rapid and convenient method to fabricate MOF and ICP nanosheets by spraying the atomized solution of metal ions onto the organic ligands solution as shown in Scheme 1. The atomization of the metal ion solution could greatly recede the disturbance of the contact between the two reaction solutions. That may give rise to a steady interface where the crystal would tend to grow in the lateral direction with anisotropic diffusion, producing nanosheets without the need of buffer layer. As well known, the spray is an easy-to-handle technique, and valuable for industrial applications, which always works in combination with other manipulation as spray-pyrolysis,29 plasma-spray30 and spraydrying.31-34 Uniquely, the nanoscale MOF with spherical hollow superstructures have been successfully obtained via spray-drying.31 Herein, the spray technique could simplify the nanosheets production process by the industrialized means and enhance its controllability by the


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liquid-liquid interfacial fabrication, which would pave a practical way for next-step modifications and applications.

Scheme 1. The fabrication of MOF and ICP nanosheets by spray. Droplets, metal ions, ligands are shown in blue, grey and pink, respectively.

EXPERIMENTAL SECTION Materials.

The

feedstocks

of

(CH3COO)2M.XH2O

(M=

Cu,

Zn,

Co),

1,4-

benzenedicarboxylate acid (BDCA), 1,4-naphthalenedicarboxylate (NDCA), and 1,4diazabicyclo[2.2.2]octane (DABCO) were purchased from Alfa Aesar or Energy Chemical, which were used without any further purification. Preparation. Three kinds of MOF nanosheets including CuBDC (copper 1,4benzenedicarboxylate), Cu(1,4-NDC) (copper 1,4-naphthalenedicarboxylate), ZnBDC (zinc


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1,4-benzenedicarboxylate) and two kinds of ICP nanosheets CoBDC (cobalt 1,4benzenedicarboxylate), Co2(BDC)2(DABCO) (BDC = 1,4-benzenedicarboxylate) can be fabricated by spray in mild conditions. Generally, the fabrication process started with the injection of metal ion solution into the spray nozzle by automatic injection pump, and then underwent the ultrasonic atomization of metal ion solution to microdroplets at a certain rate. Subsequently, the droplets containing the metal ions fell on the surface of the organic ligand solution in the culture dish by spraying as shown in Scheme 1. Taking the CuBDC as an example, 30 mg of (CH3COO)2Cu was dissolved separately in a mixture of 10 mL of N,N-dimethyl formamide (DMF) and 5 mL of acetonitrile (CH3CN), and this (CH3COO)2Cu solution was sprayed to the 1,4-benzenedicarboxylate acid (BDCA) solution (2 mg/mL, DMF:CH3CN = 1:2) in the culture dish with the flow rate of 1 µL/sec for 110 seconds. CH3CN worked as a suitable miscible co-solvent. Then, the instantly appeared precipitates could be distinctly observed at the interface, which were simultaneously assembled to crystalline nanosheets. Subsequently, the precipitates were directly collected by the glass substrate, followed by washing with DMF (1 mL) and dichloromethane (1 mL) to afford the desired product. The optimum structures of CuBDC, Cu(1,4-NDC), ZnBDC, CoBDC and Co2(BDC)2(DABCO) nanosheets with nanometer thickness and homogeneous sizes were obtained in the above method, also with the adjustion of the ions concentrations. Thus, the optimum concentrations of feedstocks were respectively 2 mg/mL (CH3COO)2Cu with 2 mg/mL BDCA for synthesizing CuBDC nanosheets, 0.9 mg/mL (CH3COO)2Cu with 0.75 mg/mL NDCA for synthesizing Cu(1,4-NDC) nanosheets, 2.2 mg/mL (CH3COO)2Zn and 1.1 mg/mL BDCA for synthesizing ZnBDC nanosheets, 52.3 mg/mL (CH3COO)2Co.4H2O with 34.9 mg/mL BDCA for synthesizing CoBDC nanosheets, and 52.3


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(CH3COO)2Co.4H2O, 34.9 mg/mL BDCA with 23.4 mg/mL DABCO for synthesizing Co2(BDC)2(DABCO) nanosheets. Characterization. Nanosheets with nanometer thickness and homogeneous size have been evidenced by the Scanning Electron Microscopy (SEM), Atomic-force Microscopy (AFM), Xray diffraction (XRD), Brunauer Emmett Teller (BET) and Fourier Transform Infrared Spectroscopy (FT-IR) measurements. The SEM images were taken with a JEOLJSM-6700F field emission scanning electron microscope (15 kV). The AFM images were collected using a Bruker Dimension Icon equipped with Scanasyst-Air peak force tapping mode AFM tips from Bruker. The XRD patterns were recorded using a diffractometer (model D/max-IIB, Rigaku Co., Tokyo, Japan) in the 2θ range 20–60° using CuKα1 (λ= 1.5405 Å) radiation. The surface area was calculated using a multipoint BET model. The total pore volume was estimated at a relative pressure of 0.99, assuming full surface saturation with nitrogen. The IR spectra were recorded on a Bruker Tensor 27 FT-IR spectropho-tometer with KBr pellets.

RESULTS AND DISCUSSION Using the spray technique described above, CuBDC nanosheets have been synthesized smoothly, which are well-dispersed and homogeneously distributed in small square shapes, demonstrated in SEM image (Fig. 1a). In the AFM image, the square lamellae of CuBDC exhibits lateral dimensions in the range of 220-440 nm with the thickness of 5 nm approximately (Fig. 1c and 1d). The CuBDC can be proven to be formed via the coordinated synthesis from FT-IR spectroscopy (Fig. 1e). Characteristic peaks at 3051 and 1507 cm-1 refer to C-H stretching vibration absorption and ring vibration in beneze, respectively. The absorptions of 1629 and 1387 cm-1 indicate the COO- group.35-36 The XRD pattern of CuBDC gives only two reflections,


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the 2θ at 16.8o and 34.1o (Fig. 1b), being indexed as the (-201) and (-402) crystallographic planes of the CuBDC structure, which can be detected from the peaks of CuBDC-MOF crytals.7 Besides, no additional Bragg diffractions of the bulk counterpart are observed, showing agreements with standards of 2D MOF structures. Through the cryogenic nitrogen physisorption/desorption and BET analysis, CuBDC feature a specific surface area (SBET) of 130.1 m2 g-1 and an average micropore size of 6.5-7 Å (Fig. 1f). The rapid N2 uptake observed at low relative pressure also indicates the CuBDC to be the microporous MOF material. There is a H1-type hysteresis loop at the high relative pressure (P/P0>0.8), probably owing to the interlaminar porosity between the nanosheets, which is usually absent in the bulk solid.7


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Figure 1. Characterizations of CuBDC-MOF nanosheets fabricated by spray. (a) SEM image; (b) XRD pattern; (c) AFM image; (d) The height profiles in colour-coded red and blue tracks in AFM image; (e) FT-IR spectrum; (f) N2 sorption isotherms and BET analysis.


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The ligand and metal center have also been varied to synthesize MOF nanosheets of Cu(1,4NDC) and ZnBDC. The ligand in the MOF may have great influence on the surface profile and nanosheet distribution. When the ligand is changed to 1,4-naphthalenedicarboxylate acid, Cu(1,4-NDC) nanosheets become thick with round and swell edges (Fig. 2a). The appearances of 2θ at 10.14o, 12.26o in XRD measurement can confirm the product to be isostructural to the 2D structure of Cu(1,4-NDC) (Fig. 2c).7 The FT-IR spectrum shows the characteristic peaks of COO- group in Cu(1,4-NDC) at 1616 and 1370 cm−1. Absorption peaks of naphthalene ring37 can be observed at 3070, 1489 and 1414 cm-1 (Fig. 2e). Compared with others, Zn(BDC) displays the thinnest nanosheets and the largest pieces from 2 µm×4.7 µm to 3.6 µm×5.3 µm (Fig. 2b). Interestingly, bulk ZnBDC named MOF-5 has limited stability, which can be reversible transformed into MOF-5W and MOF-5H when exposed to water for different exposure time.38 In our XRD measurement of ZnBDC (Fig. 2d), the intensity of 2θ at 8.71o corresponds to the special structure of MOF-5W, and the three reflections 2θ at 8.71o, 17.42o and 26.36o support its 2D framework. In the FT-IR spectrum, signals at 1562 and 1390 cm-1 can be assigned to C=O bands in BDC- group in ZnBDC. The peaks at 2989 and 1507 cm-1 correspond to C-H stretching vibration absorption and ring vibration in beneze, respectively (Fig. 2f). These characterizations all suggest the successful synthesis of Cu- and Zn-based MOF nanosheets.


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Figure 2. Characterizations of Cu(1,4-NDC)-MOF and ZnBDC-MOF nanosheets. Cu(1,4-NDC): SEM image (a), XRD pattern (c), FT-IR spectrum (e); ZnBDC: SEM image (b), XRD pattern (d), FT-IR spectrum (f). Employing the spray technique, we have also obtained Co-based ICP nanosheets. Remarkably, CoBDC nanosheets can be verified from the regular lamellaes and their thinner transverse sections (Fig 3a). Adding DABCO into the metal ion solution before the spray step can also fabricate Co2(BDC)2(DABCO) nanosheets, which closely weave andvertically and insert into each other (Fig. 3b). Through the XRD analysis, we have found XRD patterns of CoBDC and Co2(BDC)2(DABCO) nanosheets are totally different from the standards of bulk MOFs. Nevertheless, both of CoBDC and Co2(BDC)2(DABCO) nanosheets have been proven to be synthesized via coordination between the Co center and ligands according to the existing


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characteristic absorptions of COO-, beneze and DABCO groups in the FT-IR spectra, which supports their ICP structures.

Figure 3. SEM images of ICP nanosheets fabricated by spray. (a) CoBDC; (b) Co2(BDC)2(DABCO). In order to investigate the role of the spray technique, the direct mixing of the salt (CH3COO)2Zn or (CH3COO)2Co solution with the ligand BDCA solution without the spraying process has been carried out as the control experiments. However, the irregular bulks have been obtained instead of MOFs or ICPs nanosheets, which conforms with the situation and the result of the omission of the intermediate buffer layer in three-layer mode7, and further validates the indispensable role of the spray technique in creating the nanosheet morphology in this work. Basing on the experimental results and the related references,7, 31, 39-40 the possible mechanism of nanosheets formation through spraying was illustrated in Scheme 1. When metal ions solution was sprayed on the surface of the organic ligands solution, the droplets containing metal ions were supposed to diffuse in the lateral direction rather than in the vertical one. Consequently, metal ions would diffuse along with the lateral expansion of droplets and distribute evenly at the interface. This procedure benefited the rapid interfacial contaction and reaction between metal ions and organic ligands, thereby tending to generate the MOF or ICP nanometric crystals quickly as the form of nanosheets in lateral directions. The rapid nanosheets fabrication could largely rely on the fast reaction by employing the acetate salt (CH3COO)2M as the metal ion


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precursor, which would give high kinetic reaction rate due to the intrinsically protophilic weak acid anion of CH3COO-. Instead, using M(NO3)2 could not achieve the formation of corresponding nanosheets. That is probably because NO3- may result in a hysteretic reaction, whose occurrence would miss the opportunity of the lateral diffusion at the interface, yet be carried out tardily with the follow-up vertical diffusion, failing to afford the 2D structure. Hence, this nanosheets fabrication process arises from the anisotropic diffusion, which is strategically similar to the reported three-layer diffusion method. However, the spray approach needs no buffer layer and has more advantages in combining with the industrialization technology for nanosheets production depending on the fast interfacial synthesis. With the nanosheets in hand, we also tried to develop their application in catalysis. The coordination nanosheets with multiple Lewis acid centers, zeolite-like properties and 2D structural features represent promising heterogeneous catalysts for some organic reactions. Particularly, the cycloaddition of CO2 with epoxides to produce five-membered cyclic carbonates41-42 is of great significance for the utilization of waste gas CO2.43-44 In the cycloaddition, the homogeneous catalysts usually have the limitation of hard separation and high reaction temperatures (>100 oC).41 Fortunately, using CoBDC nanosheets as the catalyst, the phenyl epoxide 1 can be successfully converted 95% to selectively produce phenyl cyclic carbonates 2 in the high yield of 85%, also affording little of byproducts phenylglycol 3 (Scheme 2). It is worth mentioning that the reaction conditions are extremely mild with the atmospheric pressure of CO2 and the temperature of 70 oC, without any organic solvent, which is difficult to implement in the previous cycloaddition (details see SI).


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Scheme 2. CoBDC nanosheets-catalyzed cycloaddition of CO2 with epoxides. CONCLUSION In summary, we have developed a fast, economical and versatile spray method for the fabrication of MOF and ICP nanosheets, which is applicable to the fabrication of a series of Cu, Zn-based MOF nanosheets and Co-based IPC nanosheets with different organic ligands. On the basis of the anisotropic diffusion in the bottom-up strategy, the liquid-liquid interfacial synthesis and the simultaneous lateral assembly of nanosheets have been readily achieved, dispensed with the need of the buffer layer or the solid substrate during the nanosheets formation. Furthermore, the fabricated ICP nanosheets also have efficiently catalytic performance for the conversion of CO2 to high value-added chemicals under mild conditions. This spray approach opens up an effective way for the MOF and ICP nanosheets fabrication by industralized means, potentially beneficial for the further manipulations and applications. The researches on deeper insight of synthetic mechanism as well as further utilization are ongoing. ASSOCIATED CONTENT Supporting Information Instruments for catalytic conversion of CO2 and the characterization data of products. AUTHOR INFORMATION Corresponding Author


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*E-mail: [email protected]; [email protected]. Notes The authors declare no competing financial interest. ‡

These two authors contributed equally.

ACKNOWLEDGMENTS The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (Grant no. 21404021, 21503037, 51601032), the Doctoral Scientific Research Foundation of Liaoning Province (20141013, 201501149), Fundamental Research Funds for the Central Universities (N130205001, N150504004, N150504005, N140502001, N142004001, N140503001) and the Open Project of the State Key Laboratory of Supra molecular Structure and Materials (SKLSSM201609). REFERENCES (1) Ma, L.; Abney, C.; Lin, W. Enantioselective catalysis with homochiral metal-organic frameworks. Chem. Soc. Rev. 2009, 38 (5), 1248-1256. (2) Spokoyny, A. M.; Kim, D.; Sumrein, A.; Mirkin, C. A. Infinite coordination polymer nanoand microparticle structures. Chem. Soc. Rev. 2009, 38 (5), 1218-1227. (3) Wang, S.; Morris, W.; Liu, Y.; McGuirk, C. M.; Zhou, Y.; Hupp, J. T.; Farha, O. K.; Mirkin, C. A. Surface-specific functionalization of nanoscale metal-organic frameworks. Angew. Chem. 2015, 127 (49), 14951-14955. (4) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306 (5696), 666-669. (5) Li, P.-Z.; Maeda, Y.; Xu, Q. Top-down fabrication of crystalline metal-organic framework nanosheets. Chem. Commun. 2011, 47 (29), 8436-8438. (6) Peng, Y.; Li, Y.; Ban, Y.; Jin, H.; Jiao, W.; Liu, X.; Yang, W. Metal-organic framework nanosheets as building blocks for molecular sieving membranes. Science 2014, 346 (6215),


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Fabrication of Metal-Organic Framework and Infinite Coordination Polymer Nanosheets by the Spray Technique Yu-Nong Li,‡* Sha Wang,‡ Yuan Zhou, Xiao-Jue Bai, Guo-Shuai Song, Xue-Ying Zhao, TieQiang Wang, Xuan Qi, Xue-Min Zhang and Yu Fu* College of Sciences, Northeastern University, Shenyang 110819, P. R. China A rapid and convenient spray method has been developed to fabricate metal-organic framework and infinite coordination polymer nanosheets by the fast liquid-liquid interfacial fabrication on the basis of anisotropic diffusion.


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Fabrication of MetalâOrganic Framework and Infinite Coordination

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Fabrication of MetalâOrganic Framework and Infinite Coordination