- Email: [email protected]
A nanoporous 3D zinc(II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde
Author's Accepted Manuscript
A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde Tahereh Moradpour, Alireza Abbasi, Kristof Van Hecke
www.elsevier.com/locate/jssc
PII: DOI: Reference:
S0022-4596(15)00139-5 http://dx.doi.org/10.1016/j.jssc.2015.04.013 YJSSC18866
To appear in:
Journal of Solid State Chemistry
Received date: 4 January 2015 Revised date: 6 March 2015 Accepted date: 9 April 2015 Cite this article as: Tahereh Moradpour, Alireza Abbasi, Kristof Van Hecke, A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde, Journal of Solid State Chemistry, http://dx.doi. org/10.1016/j.jssc.2015.04.013 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde
Tahereh Moradpour a, Alireza Abbasia*, Kristof Van Heckeb a
School of Chemistry , College of Science, University of Tehran, Tehran, Iran
b
XStruct, Department of inorganic and Physical Chemistry , Ghent University, krigslaan 281-S3,B9000 Ghent,
Corresponding author: Alireza Abbasi Address: school of Chemistry, College of Science, University of Tehran, Tehran, Iran E-mail address: E-mail: [email protected] Fax: +98-21-66495291
Abstract A new 3D nanoporous metal-organic framework (MOF), [[Zn4O(C24H15N6O6)2(H2O)2].6H2O.DMF]n (1) based on 4,4΄,4΄΄-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB) ligand was solvothermally synthesized and characterized by single–crystal X-ray diffraction, Powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and Brunauer–Emmett–Teller (BET) analyses. X-ray single crystal diffraction analysis reveals that 1 exhibits a 3D network with new kvh1 topology. Semi-empirical (AM1) calculations were carried out to obtain stable conformers for TATAB ligand. In addition, the absorption of two typical aldehydes (benzaldehyde and formaldehyde) in the presence of 1 was investigated and the effect of the aldehyde concentration, exposure time and temperature was studied. It was found that compound 1 has a potential for the absorption of aldehydes under mild conditions.
Keywords: Metal–organic framework; Nanoporous MOF; Absorption; Aldehyde; AM1 calculation
1
1. Introduction Metal-Organic Frameworks (MOFs) are new categories of crystalline porous materials fabricated from the self-assembly of inorganic metal ions or metal clusters and organic ligands. Recently, MOFs have been receiving considerable attention as absorbents and separators due to their huge porosity and variety of pore shape and size from micro to nano scales [1-9]. Large surface area, controllable pore geometry, as well as facile tunability of ligands of these materials make them highly suitable for absorptive removal of hazardous compounds. Using functionalized linkers as active sites in MOF materials have successfully induced additional interactions among the absorbates and MOFs. Synthesis of MOFs with nano-sized inner cavity is highly desirable in order to achieve high absorption capacity and absorption of large molecules. However, obtaining nanoporous MOFs poses a great challenge on the structure design because of interpenetration effects [10-21], and only a few 3-D mesoporous MOFs with inner nano-sized cavities have been reported [20-22]. MOFs have been applied for the removal of hazardous materials [23]. Some pollutants such as benzaldehyde and formaldehyde have been shown to be carcinogens. Absorption of ultraviolet sunlight by aldehyde components causes them to decay into free radicals. Solutions, containing about 40% of formaldehyde have been reported to induce severe diseases or death in humans [23-28]. Several methods have been reported and applied to remove these compounds from the environment or convert them into non-toxic compounds [29-32]. Amine-containing molecules as scavenging systems can effectively remove aldehyde compounds during a condensation reaction at ambient conditions [33]. The incorporation of TATAB as linker in the MOF structures with high surface area have been reported [20-21]. In this work, we report the synthesis of a new 3-D nanoporous MOF, 1, based on zinc ions and TATAB ligand. The prepared MOF has been utilized for the absorptive removal of two aldehyde compounds. Also the effect of the aldehydes concentration, exposure time and temperature on the absorptive removal of these two compounds has been investigated.
2
2. Experimental section 2.1. Materials and measurements All the chemicals used in this study were analytical grade and used without further purification. The infrared (IR) spectroscopy of the samples was measured on a Bruker Enquinox 55 spectrometer, equipped with a single reflection diamond ATR system. H-NMR spectra were recorded on a Bruker Avance 500 MHz spectrometer. Thermogravimetric analysis was performed with a TA instruments SDT Q600 thermal analyzer under nitrogen. Identification and quantification of the organic stuff in the samples were carried out on a Chrompack CP 9000 system equipped with ECD detector. Powder X-ray diffraction patterns (PXRD) were obtained on a Philips PW1800. The simulated PXRD pattern was extracted using the Mercury program from the corresponding single-crystal data. N2 adsorption at 77 K was acquired on a Belsorp-mini II (BEL Japan, Inc.). Single crystal X-ray intensity data were collected on an Agilent Supernova Dual Source (Cu at zero) diffractometer equipped with an Atlas CCD detector using CuKα radiation (λ = 1.54178 Å) and ω scans. The images were interpreted and integrated with the program CrysAlisPro (Agilent Technologies) [34]. Using Olex2 [35], the structure was solved by direct methods using the SHELXS structure solution program [36] and refined by full-matrix leastsquares on F2 using the SHELXL program package [36]. Non-hydrogen atoms were anisotropically refined and the hydrogen atoms in the riding mode and isotropic temperature factors fixed at 1.2 times U (eq) of the parent atoms (1.5 times for methyl groups). Prior to publication, the data have been deposited in Cambridge crystallographic data center, with deposition number CCDC-946760. All geometries were optimized by the AM1 semi-empirical calculations by the Gaussian 98 software [37]. 2.2. Synthesis of compound 1 TATAB was synthesized according to the previously reported method [21]. To prepare compound 1, Zn (NO3)2 .6H2O (23.8 mg 0.08 mmol) and TATAB (10.0 mg, 0.02 mmol) were added to a mixture of N, N-dimethylformamide (DMF) and water with a molar ratio of 4:1. The obtained solution was placed into a Teflon-lined autoclave, sealed and located in a preheated electric oven at 140 ºC for 72 hours. The colorless powder containing plate crystals of 1 was collected and washed with the mixture of DMF and H2O for three times. Elem. Anal. Calc. for C,42.3; H, 2.6; N, 12.6. Found: C, 42.9; H, 2.2; N, 12.1%.
3
2.3. Aldehyde removal process Prior to absorption, compound 1 was dried for 24 h at 50 °C and was kept in a desiccator. A stock solution of the desired aldehyde (10,000 ppm) was prepared by dissolving it in DMF. Different concentrations of the aldehyde solution (100 to 5000 ppm) were prepared by dilution of the stock solutions. The absorption of the aldehyde on 1 took place in a liquid phase at atmospheric pressure under 120 rpm stirring. In all experiments, 50 mg of 1 as sorbent in 100 g of aldehyde solution in DMF were used. The concentration of the solutions after maximum absorption in the presence of 1 was determined by gas chromatography using the following equation [38]: Qt = (C0 −Ct) V/W
(Eq.1)
Where Qt is the absorption capacity at exposure time t (mg/g), Ct is the concentration of the aldehydes at exposure time t (mg/L), V is the volume of the solution, W is the mass of 1 used in the experiments and t is exposure time. The aldehyde removal (RE (%)) was calculated for each run by Eq.2: RE (%) = (C0 - Ce)/Co x 100
(Eq.2)
3. Results and discussion 3.1. Crystal structure of 1 Table 1 contains the crystallographic details for 1. The structure of TATAB is shown in Fig. 1 and their corresponding H-NMR spectra in Figs. S1 and S2. The asymmetric unit of 1 possesses two TATAB ligands, four zinc ions with a central oxygen atom, two coordinated water molecules, as well as one N, N-dimethylformamide (DMF) and six non-coordinated water molecules. The compound’s framework is constructed from four-nuclear SBUs as six-connected nodes and TATAB ligands as spacers, through coordination bonds (Fig. 2). Each node consists of four ZnII ions that are coordinated to three oxygen atoms belonging to three TATAB ligands and one central bridging µ 4-O oxygen atom for Zn1, Zn2 and Zn4 in a distorted tetrahedral geometry, while Zn3 is coordinated to two more water oxygen atoms in a distorted octahedral configuration. The TATAB ligands act as µ6 bridges, linking six ZnII ions from three different SBUs in µ6-η2:η2:η2 modes. There is one DMF as non-coordinative solvent molecule in each SUB. The 3D framework of 1 is represented in Figs. 3, S3 and S4. The Zn-O (carboxylate) bond lengths are in the range of 1.917(3)-2.081(3)Å and Zn-Owater bond lengths are 2.002(6) and 2.066(4)Å. The Zn···Zn distances differ from 3.1012(7) to 3.0791(7)Å and bond lengths of each Zn and the central oxygen atom (µ4-O) vary from 1.917(3) to 2.30(3)Å (table S1).
4
Table 1. Data collection and structure refinement statistics for 1
Empirical formula Formula weight Crystal system Space group Temperature (K) Wavelength (Å) Unit cell dimensions a (Å) b (Å) c (Å) α (°) β (°) γ (°) Volume (Å3) Z Calculated density (Mg m-3) Absorption coefficient (mm-1) F(000) θ range for data collection (°)
C51 H37 N13 O22 Zn4 1445.50 Monoclinic C2/c 100(2) 1.5418
Independent reflections
26.0338(8) 26.3415(7) 27.5327(7) 90.00 97.836(3) 90.00 18704.8(9) 8 1.027 1.655 5840 3.36-70.07 -31 ≤ h ≤31; 0 ≤ k ≤ 31; 0 ≤ l ≤ 33 17701 (Rint = 0.0450)
Total reflections
41917
Data/restraints/parameters
17701/ 90/ 813
GOF
0.995
Final R indices [I>2σ(I)]
R1 = 0.0625, wR2 = 0.1798
Limiting indices
5
Fig. 1. 4,4’,4’’ 4,4’,4’’-s-triazine-1,3,5-triyltri-p-aminbenzoate (TATAB).
Fig. 2. Secondary building unit.
6
Fig. 3. Representation of the 3D network in the crystal structure of 1 as viewed down the crystallographic c-axis, for clarity H-atoms and solvent are omitted.
Topological studies show a two-fold interpenetrated uninodal 3D Network for 1. The structure can be simplified by considering the triazine-1,3,5-triyl and {Zn4O(CO2)6(H2O)2} cluster group as 3coordinated and 6-coordinated node, respectively, and Benzene-1,4-diyl and amine groups can be replaced by 2-coordinated nodes (fig 4.a and 4.b) . The resulting simplified structure shows that this structure is a bindal 3,6-coordinated underlying net with stoichiometry (3-c)2(6-c) which is not known (fig 5), however it is very close to topological type flu-3,6-I41cd [39] with the same point symbol (611.84)(63)2 and vertex symbol [6.6.6.6.62.62.62.62.62.62.62.8.8.*.*][63.63.63]2. Moreover, almost all other topological indices of this net and flu-3,6-I41cd are the same, in particular, coordination and circuit sequences. The only indices that are tiny different are so called ‘all circuits’ showing the numbers of circuits of different size meeting at each angle of each vertex. This net has a lower symmetry of Aba2 instead of I41cd in flu-3,6-I41cd. It was deposited to the TOPOS TTD collection [40] under the name kvh1.
7
Fig. 4.a. Illustration for trigonal-coordinated node in underlying net merged with initial framework fragment.
Fig. 4.b. Illustration for {Zn4O(H2O)2} clusters and corresponding node coordination in initial framework merged with underlying net.
8
Fig. 5. Illustration for coordination of underlying net in the cluster representation.
3.2. Thermal analysis Thermogravimetric analysis curve for 1 was obtained by heating the sample from 25 °C to 800 °C at the rate of 20 °C min−1 under a stream of nitrogen (Fig. S5). The first weight loss of 3.0% (calculated 2.5%) between 25 and 160 °C corresponds to the loss of two non -coordinated waters and the second weight loss of 10.8% (calculated 10.0%) in the range of 160 – 200 °C is related to the loss of the four non-coordinated water molecules and one DMF molecule. The final decomposition step begins at about 200 °C and the residue is ZnO. Fig. S6 shows the PXRD pattern of the heated 1 at 800°C. We confirmed the existence of ZnO structure by comparison of the diffraction pattern with the values reported in the database of ZnO (JCPDS card no. 0-3-0888).
3.3. Absorption of benzaldehyde and formaldehyde by 1 Absorption of two aldehydes including benzaldehyde and formaldehyde was studied. We examined the absorption of a mixture of benzaldehyde, formaldehyde, n-pentane and propylamine by 1 in DMF as solvent at 50 °C for 2 hours. We have found that 1 has more tendencies for the absorption of two aldehydes compared to that of n-pentane and propylamine (Figs. S7-S9). Benzaldehyde and 9
formaldehyde were selected as two representative absorbate molecules to evaluate the absorption ability of 1 and the effect of some absorption parameters such as exposure time, temperature and the concentration for each aldehyde molecule has been investigated separately. The effect of the temperature on the absorption of the aldehydes on 1 as absorbent was studied. After the absorption process, compound 1 was filtered and washed with DMF and the filtrate was analyzed
Extent of absorption (g S/kg sorbent)
by GC analysis. The effect the exposure time on the aldehyde absorption by 1 is presented in Fig. 6.
Time(h) Fig. 6. Effect of exposure time on the absorption of benzaldehye, formaldehyde (DMF as solvent, absorption temperature and initial concentration of 25 °C and 100 ppm, respectively).
As seen the absorption of each aldehyde improves by increasing the exposure time. The results of the aldehyde absorption at different temperatures (Fig. 7) indicate that at higher temperature the absorption increases. After the absorption process compound 1 was filtered and washed with DMF.
10
Extent of absorpton (g S/kg sorbent) Extent of absorption (g S/kg sorbent)
Concentration (ppm) of formaldehyde
Concentration (ppm) of benzaldehyde Fig. 7. Absorption isotherms of formaldehyde (top) and benzaldehyde (bottom), on 1 at different temperatures.
The PXRD patterns of 1 before and after the absorption are shown in Fig Fig. 8.. The similarity of the PXRD patterns of the simulated and fresh 1 shows phase purity of the prepared MOF. Moreover the PXRD patterns of 1 before and after the absorption process are almost the same indicating that the structure of the MOF is retained after aldehyde loading.
11
Intensity (a.u.)
2-theta (°) Fig. 8. PXRD of 1 (a) simulated pattern, (b) before, (c) after the formaldehyde and (d) after the benzaldehyde absorption.
After the absorption of the aldehydes, the stretching bands appeared in the IR spectra of 1 at 1649 cm−1 (Fig. 9) were assigned to (-C=N) iminium salt due to the reaction of free -NH of TATAB in 1 and COH groups of aldhydes [41-42]. The interaction was verified by using a blank experiment without
Transmittance (%)
aldehyde (Fig 9).
Wavenumbers (cm-1) Fig. 9. IR spectra of the 1 and benzaldehyde, formaldehyde and blank.
12
In order to study the changes in textural properties upon absorption of the aldehydes, multi point nitrogen adsorption measurements at 77 K were carried out. Before the measurements, compound 1 was immersed in chloroform and evacuated at ambient temperature for 3 h to obtain the activated sample. Specific surface area, average pore size and total pore volume were taken by multi point Brunauer–Emmet–Teller (BET) method at P/P0 = 0.99 (Table 2). Table 2. Textural properties of 1 before and after absorption
Absorbent
Surface area(m2/g−1)
Average pore size (n.m)
Pore volume (cm 3 /g – 1 )
1
278.7
1.8
0.784
1, after benzaldhyde absorption
86.3
0.8
0.345
1, after formaldhyde absorption
105
1.1
0.478
After aldehyde absorption, BET of compound 1 showed a decrease in the amount of N2 absorbption that is apparently resulting from an increased density of the framework, moreover, the pore sizes of 1 decreased suggesting that benzaldehyde and formaldhyde have been captured in the pores of framework. H-NMR Spectroscopy has been used to characterize chemical structure of 1 before (blank) and after aldehydes absorption. (Figs. S10- S12).
3.4. Computational In order to understand the flexibility of the TATAB structure, AM1 and DFT methods with B3LYP/631G** functions for conformational analysis were used. Two torsion angles D5 and D30 have clearly shown the significant impact on the energy of TATAB structure (Fig. 1). We obtained the energy levels of the structure by simultaneous scanning of both of the angles from 0 to 180°. Although the most popular method for the optimization of organic compounds is Density Functional Theory (DFT), the DFT method is not appropriate for the conformational analysis of TATAB because in this method the energy of different conformers based on D5 and D30 torsion angles is the same. Conformational analysis of the TATAB ligand by AM1 shows 324 conformers (Fig. 10a). According to these results, the energy of the conformers depends on the torsion angle D5. The vibrational analysis shows that only 70 conformers are thermodynamically possible that the D5 angle of them is around 40° (Fig. 10b). As 13
shown in Fig. 10b, these conformers are highly flexible and can be converted to each other with low energy barrier suggesting that the synthesis of MOF structures using TATAB as ligand is quite challenging [20-21]. The conformer of TATAB in 1 has torsion angle of 155° and 24° for D5 and D30 respectively. This conformer is one of the 70 stable conformers which are computationally analyzed.
Fig. 10a. 3D- relative energy plot for different conformations of TATAB versus its two torsions, D5 and D30.
Fig. 10b. Stable conformers Of TATAB versus its two torsion angles D5 and D30.
14
4. Conclusions The 3D nanoporous MOF, 1, based on TATAB ligand and Zn (NO3)2 .6H2O with new topology has been successfully synthesized under solvothermal conditions. Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by 1 was studied. The results indicated that compound 1 has a potential for absorption removal of the aldehydes in DMF. Also Semi-empirical AM1 calculations were used to perform conformational analysis of TATAB.
Supporting Information Available: Table S1. Selected bond lengths (Å) and angles (°) for {[Zn4O (C24H15N6O6)2(H2O)2].6H2O.DMF]}n , 1. Figure S1.NMR spectrum of TATAB. Figure S2.Expanded NMR spectrum of TATAB. Figure S3 .Representation of the 3D network in the crystal structure of compound 1 as viewed down the crystallographic a-axis. Figure S4. Representation of the 3D network in the crystal structure of compound 1 as viewed down the crystallographic b-axis. Fig S5. TGA analysis of the 1. Fig S6. The XRD pattern for the ZnO. Figure S7. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), n-pentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T0 (time step). Figure S8. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), n-pentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T1 ( after 1 hour ). Fig S9. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), npentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T2 ( after 2hour ). Figure S10. H- NMR spectrum of 1 before aldehydes absorption (blank). Figure S11, H- NMR spectrum of 1 after benzaldehyde absorption. Figure S12. H- NMR spectrum of 1 after formaldehyde absorption.
15
CCDC-946760 contains the supplementary crystallographic data for this paper and can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44-1223-336033; or [email protected]).
Acknowledgements We thank the University of Tehran for financial support. K.V.H. thanks the Hercules Foundation (project AUGE/11/029 "3D-SPACE: 3D Structural Platform Aiming for Chemical Excellence") for funding.
References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17]
H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi, A. Ö. Yazaydin, R. Q. Snurr, M. O’Keeffe, J. Kim, Science 329 (2010) 424-428. S. Shimomura, M. Higuchi, R. Matsuda, K. Yoneda, Y. Hijikata, Y. Kubota, Y. Mita, J. Kim, M. Takata, S. Kitagawa, Nature chemistry 2 (2010) 633-637. A. J. Blake, N. R. Champness, T. L. Easun, D. R. Allan, H. Nowell, M. W. George, J. Jia, X.-Z. Sun, Nature chemistry 2 (2010) 688-694. D.-S. Li, Y.-P. Wu, J. Zhao, J. Zhang, J. Y. Lu, Coordination Chemistry Reviews 261(2014) 127. J. J. Perry Iv, J. A. Perman, M. J. Zaworotko, Chemical Society Reviews 38 (2009) 1400-1417. P. SeeáLee, Chemical Science 5 (2014) 3404-3408. Y. Zhou, W. Chen, J. Zhu, W. Pei, C. Wang, L. Huang, C. Yao, Q. Yan, W. Huang, J. S. C. Loo, Small 10 (2014) 4802-4802. D.-S. Li, Y.-P. Wu, P. Zhang, M. Du, J. Zhao, C.-P. Li, Y.-Y. Wang, Crystal Growth & Design 10 (2010) 2037-2040. D.-S. Li, J. Zhao, Y.-P. Wu, B. Liu, L. Bai, K. Zou, M. Du, Inorganic chemistry 52 (2013) 8091-8098. S. L. James, Chemical Society Reviews 32 (2003) 276-288. C. Janiak, Dalton Transactions 14 (2003) 2781-2804. M. Rosseinsky, Microporous and Mesoporous Materials 73 (2004) 15-30. J. S. Seo, D. Whang, H. Lee, S. Im Jun, J. Oh, Y. J. Jeon, K. Kim, Nature 404 (2000) 982-986. M. Eddaoudi, J. Kim, J. Wachter, H. Chae, M. O'keeffe, O. Yaghi, Journal of the American Chemical Society 123 (2001) 4368-4369. Q.-R. Fang, G.-S. Zhu, Z. Jin, M. Xue, X. Wei, D.-J. Wang, S.-L. Qiu, Crystal growth & design 7 (2007) 1035-1037. L. Pan, B. Parker, X. Huang, D. H. Olson, J. Lee, J. Li, Journal of the American Chemical Society 128 (2006) 4180-4181. S. Ma, H.-C. Zhou, Journal of the American Chemical Society 128 (2006) 11734-11735.
16
[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]
J. Zhang, S. Chen, T. Wu, P. Feng, X. Bu, Journal of the American Chemical Society 130 (2008) 12882-12883. L. J. Murray, M. Dincă, J. R. Long, Chemical Society Reviews 38 (2009) 1294-1314. N. Tian, Z.-Y. Zhou, N.-F. Yu, L.-Y. Wang, S.-G. Sun, Journal of the American Chemical Society 132 (2010) 7580-7581. A. G. Wong-Foy, A. J. Matzger, O. M. Yaghi, Journal of the American Chemical Society 128 (2006) 3494-3495. J. H. Liao, C. Y. Lai, C. L. Yang, Journal of the Chinese Chemical Society 61(2014) 11151120. N. A. Khan, Z. Hasan, S. H. Jhung, Journal of hazardous materials 244 (2013) 444-456. X.-S. Wang, S. Ma, D. Sun, S. Parkin, H.-C. Zhou, Journal of the American Chemical Society 128 (2006) 16474-16475. Q. R. Fang, G. S. Zhu, Z. Jin, Y. Y. Ji, J. W. Ye, M. Xue, H. Yang, Y. Wang, S. L. Qiu, Angewandte Chemie (International ed. in English) 46 (2007) 6638-6642. B. Wang, A. P. Côté, H. Furukawa, M. O’Keeffe, O. M. Yaghi, Nature 453 (2008) 207-211. K. Koh, A. G. Wong-Foy, A. J. Matzger, Angewandte Chemie International Edition 47 (2008) 677-680. Y. K. Park, S. B. Choi, H. Kim, K. Kim, B.-H. Won, K. Choi, J.-S. Choi, W.-S. Ahn, N. Won, S. Kim, D. H. Jung, S.-H. Choi, G.-H. Kim, S.-S. Cha, Y. H. Jhon, J. K. Yang, J. Kim, Angewandte Chemie International Edition 46 (2007) 8230-8233. S. Nuasaen, P. Opaprakasit, P. Tangboriboonrat, Carbohydrate polymers 101( 2014) 179-187. K. Yamashita, M. Noguchi, A. Mizukoshi, Y. Yanagisawa, International journal of environmental research and public health 7 (2010) 3489-3498. Y. Sekine, Atmospheric Environment 36 (2002) 5543-5547. A. Nomura, C. W. Jones, ACS applied materials & interfaces 5 (2013) 5569-5577. a; bR. Deitrich, V. Erwin, Annual review of pharmacology and toxicology 20 (1980) 55-80. A. T. CrysAlisPro, Version 1.171.36.28. Agilent Technologies: Santa Clara, CA, 2013. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. Howard, H. Puschmann, Journal of Applied Crystallography 42 (2009) 339-341. G. Sheldrick, Acta Crystallographica Section A 2008, 64, 112-122. M. Frisch, G. Trucks, H. Schlegel, G. Scuseria, M. Robb, J. Cheeseman, V. Zakrzewski, J. Montgomery Jr, R. Stratmann, J. Burant, Inc.. Revision A 1998, 6. C.-F. Chang, C.-Y. Chang, K.-H. Chen, W.-T. Tsai, J.-L. Shie, Y.-H. Chen, Journal of colloid and interface science 277 (2004) 29-34. V. A. Blatov, D. M. Proserpio, Acta Crystallographica Section A: Foundations of Crystallography 65 (2009) 202-212. V. A. Blatov, D. M. Proserpio, Acta Crystallographica Section A: Foundations of Crystallography 65(2009) 202-212. H. Matsushita, Y. Tsujino, M. Noguchi, S. Yoshikawa, Bulletin of the Chemical Society of Japan 50 (1977) 1513-1516. C. B. McArdle, L. Zhao, US Patents No. 8022251 20 sep 2011.
17
Graphical abstract Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by solvothermally synthesized of a 3D nano-porous MOF based on TATAB tricarboxylate ligand and Zn (NO3)2 .6H2O.
Highlights • • • •
We present a 3D Zn(II)-MOF with TATAB linker by solvothermal method. The framework possesses a new kvh1 topology. The framework displays formaldehyde and benzaldehyde absorption property. Conformational analysis was performed to determine the stable linker geometry.
18
A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde Tahereh Moradpour, Alireza Abbasi, Kristof Van Hecke
www.elsevier.com/locate/jssc
PII: DOI: Reference:
S0022-4596(15)00139-5 http://dx.doi.org/10.1016/j.jssc.2015.04.013 YJSSC18866
To appear in:
Journal of Solid State Chemistry
Received date: 4 January 2015 Revised date: 6 March 2015 Accepted date: 9 April 2015 Cite this article as: Tahereh Moradpour, Alireza Abbasi, Kristof Van Hecke, A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde, Journal of Solid State Chemistry, http://dx.doi. org/10.1016/j.jssc.2015.04.013 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
A nanoporous 3D zinc (II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde
Tahereh Moradpour a, Alireza Abbasia*, Kristof Van Heckeb a
School of Chemistry , College of Science, University of Tehran, Tehran, Iran
b
XStruct, Department of inorganic and Physical Chemistry , Ghent University, krigslaan 281-S3,B9000 Ghent,
Corresponding author: Alireza Abbasi Address: school of Chemistry, College of Science, University of Tehran, Tehran, Iran E-mail address: E-mail: [email protected] Fax: +98-21-66495291
Abstract A new 3D nanoporous metal-organic framework (MOF), [[Zn4O(C24H15N6O6)2(H2O)2].6H2O.DMF]n (1) based on 4,4΄,4΄΄-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB) ligand was solvothermally synthesized and characterized by single–crystal X-ray diffraction, Powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and Brunauer–Emmett–Teller (BET) analyses. X-ray single crystal diffraction analysis reveals that 1 exhibits a 3D network with new kvh1 topology. Semi-empirical (AM1) calculations were carried out to obtain stable conformers for TATAB ligand. In addition, the absorption of two typical aldehydes (benzaldehyde and formaldehyde) in the presence of 1 was investigated and the effect of the aldehyde concentration, exposure time and temperature was studied. It was found that compound 1 has a potential for the absorption of aldehydes under mild conditions.
Keywords: Metal–organic framework; Nanoporous MOF; Absorption; Aldehyde; AM1 calculation
1
1. Introduction Metal-Organic Frameworks (MOFs) are new categories of crystalline porous materials fabricated from the self-assembly of inorganic metal ions or metal clusters and organic ligands. Recently, MOFs have been receiving considerable attention as absorbents and separators due to their huge porosity and variety of pore shape and size from micro to nano scales [1-9]. Large surface area, controllable pore geometry, as well as facile tunability of ligands of these materials make them highly suitable for absorptive removal of hazardous compounds. Using functionalized linkers as active sites in MOF materials have successfully induced additional interactions among the absorbates and MOFs. Synthesis of MOFs with nano-sized inner cavity is highly desirable in order to achieve high absorption capacity and absorption of large molecules. However, obtaining nanoporous MOFs poses a great challenge on the structure design because of interpenetration effects [10-21], and only a few 3-D mesoporous MOFs with inner nano-sized cavities have been reported [20-22]. MOFs have been applied for the removal of hazardous materials [23]. Some pollutants such as benzaldehyde and formaldehyde have been shown to be carcinogens. Absorption of ultraviolet sunlight by aldehyde components causes them to decay into free radicals. Solutions, containing about 40% of formaldehyde have been reported to induce severe diseases or death in humans [23-28]. Several methods have been reported and applied to remove these compounds from the environment or convert them into non-toxic compounds [29-32]. Amine-containing molecules as scavenging systems can effectively remove aldehyde compounds during a condensation reaction at ambient conditions [33]. The incorporation of TATAB as linker in the MOF structures with high surface area have been reported [20-21]. In this work, we report the synthesis of a new 3-D nanoporous MOF, 1, based on zinc ions and TATAB ligand. The prepared MOF has been utilized for the absorptive removal of two aldehyde compounds. Also the effect of the aldehydes concentration, exposure time and temperature on the absorptive removal of these two compounds has been investigated.
2
2. Experimental section 2.1. Materials and measurements All the chemicals used in this study were analytical grade and used without further purification. The infrared (IR) spectroscopy of the samples was measured on a Bruker Enquinox 55 spectrometer, equipped with a single reflection diamond ATR system. H-NMR spectra were recorded on a Bruker Avance 500 MHz spectrometer. Thermogravimetric analysis was performed with a TA instruments SDT Q600 thermal analyzer under nitrogen. Identification and quantification of the organic stuff in the samples were carried out on a Chrompack CP 9000 system equipped with ECD detector. Powder X-ray diffraction patterns (PXRD) were obtained on a Philips PW1800. The simulated PXRD pattern was extracted using the Mercury program from the corresponding single-crystal data. N2 adsorption at 77 K was acquired on a Belsorp-mini II (BEL Japan, Inc.). Single crystal X-ray intensity data were collected on an Agilent Supernova Dual Source (Cu at zero) diffractometer equipped with an Atlas CCD detector using CuKα radiation (λ = 1.54178 Å) and ω scans. The images were interpreted and integrated with the program CrysAlisPro (Agilent Technologies) [34]. Using Olex2 [35], the structure was solved by direct methods using the SHELXS structure solution program [36] and refined by full-matrix leastsquares on F2 using the SHELXL program package [36]. Non-hydrogen atoms were anisotropically refined and the hydrogen atoms in the riding mode and isotropic temperature factors fixed at 1.2 times U (eq) of the parent atoms (1.5 times for methyl groups). Prior to publication, the data have been deposited in Cambridge crystallographic data center, with deposition number CCDC-946760. All geometries were optimized by the AM1 semi-empirical calculations by the Gaussian 98 software [37]. 2.2. Synthesis of compound 1 TATAB was synthesized according to the previously reported method [21]. To prepare compound 1, Zn (NO3)2 .6H2O (23.8 mg 0.08 mmol) and TATAB (10.0 mg, 0.02 mmol) were added to a mixture of N, N-dimethylformamide (DMF) and water with a molar ratio of 4:1. The obtained solution was placed into a Teflon-lined autoclave, sealed and located in a preheated electric oven at 140 ºC for 72 hours. The colorless powder containing plate crystals of 1 was collected and washed with the mixture of DMF and H2O for three times. Elem. Anal. Calc. for C,42.3; H, 2.6; N, 12.6. Found: C, 42.9; H, 2.2; N, 12.1%.
3
2.3. Aldehyde removal process Prior to absorption, compound 1 was dried for 24 h at 50 °C and was kept in a desiccator. A stock solution of the desired aldehyde (10,000 ppm) was prepared by dissolving it in DMF. Different concentrations of the aldehyde solution (100 to 5000 ppm) were prepared by dilution of the stock solutions. The absorption of the aldehyde on 1 took place in a liquid phase at atmospheric pressure under 120 rpm stirring. In all experiments, 50 mg of 1 as sorbent in 100 g of aldehyde solution in DMF were used. The concentration of the solutions after maximum absorption in the presence of 1 was determined by gas chromatography using the following equation [38]: Qt = (C0 −Ct) V/W
(Eq.1)
Where Qt is the absorption capacity at exposure time t (mg/g), Ct is the concentration of the aldehydes at exposure time t (mg/L), V is the volume of the solution, W is the mass of 1 used in the experiments and t is exposure time. The aldehyde removal (RE (%)) was calculated for each run by Eq.2: RE (%) = (C0 - Ce)/Co x 100
(Eq.2)
3. Results and discussion 3.1. Crystal structure of 1 Table 1 contains the crystallographic details for 1. The structure of TATAB is shown in Fig. 1 and their corresponding H-NMR spectra in Figs. S1 and S2. The asymmetric unit of 1 possesses two TATAB ligands, four zinc ions with a central oxygen atom, two coordinated water molecules, as well as one N, N-dimethylformamide (DMF) and six non-coordinated water molecules. The compound’s framework is constructed from four-nuclear SBUs as six-connected nodes and TATAB ligands as spacers, through coordination bonds (Fig. 2). Each node consists of four ZnII ions that are coordinated to three oxygen atoms belonging to three TATAB ligands and one central bridging µ 4-O oxygen atom for Zn1, Zn2 and Zn4 in a distorted tetrahedral geometry, while Zn3 is coordinated to two more water oxygen atoms in a distorted octahedral configuration. The TATAB ligands act as µ6 bridges, linking six ZnII ions from three different SBUs in µ6-η2:η2:η2 modes. There is one DMF as non-coordinative solvent molecule in each SUB. The 3D framework of 1 is represented in Figs. 3, S3 and S4. The Zn-O (carboxylate) bond lengths are in the range of 1.917(3)-2.081(3)Å and Zn-Owater bond lengths are 2.002(6) and 2.066(4)Å. The Zn···Zn distances differ from 3.1012(7) to 3.0791(7)Å and bond lengths of each Zn and the central oxygen atom (µ4-O) vary from 1.917(3) to 2.30(3)Å (table S1).
4
Table 1. Data collection and structure refinement statistics for 1
Empirical formula Formula weight Crystal system Space group Temperature (K) Wavelength (Å) Unit cell dimensions a (Å) b (Å) c (Å) α (°) β (°) γ (°) Volume (Å3) Z Calculated density (Mg m-3) Absorption coefficient (mm-1) F(000) θ range for data collection (°)
C51 H37 N13 O22 Zn4 1445.50 Monoclinic C2/c 100(2) 1.5418
Independent reflections
26.0338(8) 26.3415(7) 27.5327(7) 90.00 97.836(3) 90.00 18704.8(9) 8 1.027 1.655 5840 3.36-70.07 -31 ≤ h ≤31; 0 ≤ k ≤ 31; 0 ≤ l ≤ 33 17701 (Rint = 0.0450)
Total reflections
41917
Data/restraints/parameters
17701/ 90/ 813
GOF
0.995
Final R indices [I>2σ(I)]
R1 = 0.0625, wR2 = 0.1798
Limiting indices
5
Fig. 1. 4,4’,4’’ 4,4’,4’’-s-triazine-1,3,5-triyltri-p-aminbenzoate (TATAB).
Fig. 2. Secondary building unit.
6
Fig. 3. Representation of the 3D network in the crystal structure of 1 as viewed down the crystallographic c-axis, for clarity H-atoms and solvent are omitted.
Topological studies show a two-fold interpenetrated uninodal 3D Network for 1. The structure can be simplified by considering the triazine-1,3,5-triyl and {Zn4O(CO2)6(H2O)2} cluster group as 3coordinated and 6-coordinated node, respectively, and Benzene-1,4-diyl and amine groups can be replaced by 2-coordinated nodes (fig 4.a and 4.b) . The resulting simplified structure shows that this structure is a bindal 3,6-coordinated underlying net with stoichiometry (3-c)2(6-c) which is not known (fig 5), however it is very close to topological type flu-3,6-I41cd [39] with the same point symbol (611.84)(63)2 and vertex symbol [6.6.6.6.62.62.62.62.62.62.62.8.8.*.*][63.63.63]2. Moreover, almost all other topological indices of this net and flu-3,6-I41cd are the same, in particular, coordination and circuit sequences. The only indices that are tiny different are so called ‘all circuits’ showing the numbers of circuits of different size meeting at each angle of each vertex. This net has a lower symmetry of Aba2 instead of I41cd in flu-3,6-I41cd. It was deposited to the TOPOS TTD collection [40] under the name kvh1.
7
Fig. 4.a. Illustration for trigonal-coordinated node in underlying net merged with initial framework fragment.
Fig. 4.b. Illustration for {Zn4O(H2O)2} clusters and corresponding node coordination in initial framework merged with underlying net.
8
Fig. 5. Illustration for coordination of underlying net in the cluster representation.
3.2. Thermal analysis Thermogravimetric analysis curve for 1 was obtained by heating the sample from 25 °C to 800 °C at the rate of 20 °C min−1 under a stream of nitrogen (Fig. S5). The first weight loss of 3.0% (calculated 2.5%) between 25 and 160 °C corresponds to the loss of two non -coordinated waters and the second weight loss of 10.8% (calculated 10.0%) in the range of 160 – 200 °C is related to the loss of the four non-coordinated water molecules and one DMF molecule. The final decomposition step begins at about 200 °C and the residue is ZnO. Fig. S6 shows the PXRD pattern of the heated 1 at 800°C. We confirmed the existence of ZnO structure by comparison of the diffraction pattern with the values reported in the database of ZnO (JCPDS card no. 0-3-0888).
3.3. Absorption of benzaldehyde and formaldehyde by 1 Absorption of two aldehydes including benzaldehyde and formaldehyde was studied. We examined the absorption of a mixture of benzaldehyde, formaldehyde, n-pentane and propylamine by 1 in DMF as solvent at 50 °C for 2 hours. We have found that 1 has more tendencies for the absorption of two aldehydes compared to that of n-pentane and propylamine (Figs. S7-S9). Benzaldehyde and 9
formaldehyde were selected as two representative absorbate molecules to evaluate the absorption ability of 1 and the effect of some absorption parameters such as exposure time, temperature and the concentration for each aldehyde molecule has been investigated separately. The effect of the temperature on the absorption of the aldehydes on 1 as absorbent was studied. After the absorption process, compound 1 was filtered and washed with DMF and the filtrate was analyzed
Extent of absorption (g S/kg sorbent)
by GC analysis. The effect the exposure time on the aldehyde absorption by 1 is presented in Fig. 6.
Time(h) Fig. 6. Effect of exposure time on the absorption of benzaldehye, formaldehyde (DMF as solvent, absorption temperature and initial concentration of 25 °C and 100 ppm, respectively).
As seen the absorption of each aldehyde improves by increasing the exposure time. The results of the aldehyde absorption at different temperatures (Fig. 7) indicate that at higher temperature the absorption increases. After the absorption process compound 1 was filtered and washed with DMF.
10
Extent of absorpton (g S/kg sorbent) Extent of absorption (g S/kg sorbent)
Concentration (ppm) of formaldehyde
Concentration (ppm) of benzaldehyde Fig. 7. Absorption isotherms of formaldehyde (top) and benzaldehyde (bottom), on 1 at different temperatures.
The PXRD patterns of 1 before and after the absorption are shown in Fig Fig. 8.. The similarity of the PXRD patterns of the simulated and fresh 1 shows phase purity of the prepared MOF. Moreover the PXRD patterns of 1 before and after the absorption process are almost the same indicating that the structure of the MOF is retained after aldehyde loading.
11
Intensity (a.u.)
2-theta (°) Fig. 8. PXRD of 1 (a) simulated pattern, (b) before, (c) after the formaldehyde and (d) after the benzaldehyde absorption.
After the absorption of the aldehydes, the stretching bands appeared in the IR spectra of 1 at 1649 cm−1 (Fig. 9) were assigned to (-C=N) iminium salt due to the reaction of free -NH of TATAB in 1 and COH groups of aldhydes [41-42]. The interaction was verified by using a blank experiment without
Transmittance (%)
aldehyde (Fig 9).
Wavenumbers (cm-1) Fig. 9. IR spectra of the 1 and benzaldehyde, formaldehyde and blank.
12
In order to study the changes in textural properties upon absorption of the aldehydes, multi point nitrogen adsorption measurements at 77 K were carried out. Before the measurements, compound 1 was immersed in chloroform and evacuated at ambient temperature for 3 h to obtain the activated sample. Specific surface area, average pore size and total pore volume were taken by multi point Brunauer–Emmet–Teller (BET) method at P/P0 = 0.99 (Table 2). Table 2. Textural properties of 1 before and after absorption
Absorbent
Surface area(m2/g−1)
Average pore size (n.m)
Pore volume (cm 3 /g – 1 )
1
278.7
1.8
0.784
1, after benzaldhyde absorption
86.3
0.8
0.345
1, after formaldhyde absorption
105
1.1
0.478
After aldehyde absorption, BET of compound 1 showed a decrease in the amount of N2 absorbption that is apparently resulting from an increased density of the framework, moreover, the pore sizes of 1 decreased suggesting that benzaldehyde and formaldhyde have been captured in the pores of framework. H-NMR Spectroscopy has been used to characterize chemical structure of 1 before (blank) and after aldehydes absorption. (Figs. S10- S12).
3.4. Computational In order to understand the flexibility of the TATAB structure, AM1 and DFT methods with B3LYP/631G** functions for conformational analysis were used. Two torsion angles D5 and D30 have clearly shown the significant impact on the energy of TATAB structure (Fig. 1). We obtained the energy levels of the structure by simultaneous scanning of both of the angles from 0 to 180°. Although the most popular method for the optimization of organic compounds is Density Functional Theory (DFT), the DFT method is not appropriate for the conformational analysis of TATAB because in this method the energy of different conformers based on D5 and D30 torsion angles is the same. Conformational analysis of the TATAB ligand by AM1 shows 324 conformers (Fig. 10a). According to these results, the energy of the conformers depends on the torsion angle D5. The vibrational analysis shows that only 70 conformers are thermodynamically possible that the D5 angle of them is around 40° (Fig. 10b). As 13
shown in Fig. 10b, these conformers are highly flexible and can be converted to each other with low energy barrier suggesting that the synthesis of MOF structures using TATAB as ligand is quite challenging [20-21]. The conformer of TATAB in 1 has torsion angle of 155° and 24° for D5 and D30 respectively. This conformer is one of the 70 stable conformers which are computationally analyzed.
Fig. 10a. 3D- relative energy plot for different conformations of TATAB versus its two torsions, D5 and D30.
Fig. 10b. Stable conformers Of TATAB versus its two torsion angles D5 and D30.
14
4. Conclusions The 3D nanoporous MOF, 1, based on TATAB ligand and Zn (NO3)2 .6H2O with new topology has been successfully synthesized under solvothermal conditions. Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by 1 was studied. The results indicated that compound 1 has a potential for absorption removal of the aldehydes in DMF. Also Semi-empirical AM1 calculations were used to perform conformational analysis of TATAB.
Supporting Information Available: Table S1. Selected bond lengths (Å) and angles (°) for {[Zn4O (C24H15N6O6)2(H2O)2].6H2O.DMF]}n , 1. Figure S1.NMR spectrum of TATAB. Figure S2.Expanded NMR spectrum of TATAB. Figure S3 .Representation of the 3D network in the crystal structure of compound 1 as viewed down the crystallographic a-axis. Figure S4. Representation of the 3D network in the crystal structure of compound 1 as viewed down the crystallographic b-axis. Fig S5. TGA analysis of the 1. Fig S6. The XRD pattern for the ZnO. Figure S7. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), n-pentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T0 (time step). Figure S8. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), n-pentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T1 ( after 1 hour ). Fig S9. Selective Absorption condition:DMF (5ml), benzaldhade ( 10 mmol), formaldhyde( 10 mmol), npentane( 10 mmol), propylamine( 10 mmol), adsorbent ( 80 mg) at T2 ( after 2hour ). Figure S10. H- NMR spectrum of 1 before aldehydes absorption (blank). Figure S11, H- NMR spectrum of 1 after benzaldehyde absorption. Figure S12. H- NMR spectrum of 1 after formaldehyde absorption.
15
CCDC-946760 contains the supplementary crystallographic data for this paper and can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44-1223-336033; or [email protected]).
Acknowledgements We thank the University of Tehran for financial support. K.V.H. thanks the Hercules Foundation (project AUGE/11/029 "3D-SPACE: 3D Structural Platform Aiming for Chemical Excellence") for funding.
References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17]
H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi, A. Ö. Yazaydin, R. Q. Snurr, M. O’Keeffe, J. Kim, Science 329 (2010) 424-428. S. Shimomura, M. Higuchi, R. Matsuda, K. Yoneda, Y. Hijikata, Y. Kubota, Y. Mita, J. Kim, M. Takata, S. Kitagawa, Nature chemistry 2 (2010) 633-637. A. J. Blake, N. R. Champness, T. L. Easun, D. R. Allan, H. Nowell, M. W. George, J. Jia, X.-Z. Sun, Nature chemistry 2 (2010) 688-694. D.-S. Li, Y.-P. Wu, J. Zhao, J. Zhang, J. Y. Lu, Coordination Chemistry Reviews 261(2014) 127. J. J. Perry Iv, J. A. Perman, M. J. Zaworotko, Chemical Society Reviews 38 (2009) 1400-1417. P. SeeáLee, Chemical Science 5 (2014) 3404-3408. Y. Zhou, W. Chen, J. Zhu, W. Pei, C. Wang, L. Huang, C. Yao, Q. Yan, W. Huang, J. S. C. Loo, Small 10 (2014) 4802-4802. D.-S. Li, Y.-P. Wu, P. Zhang, M. Du, J. Zhao, C.-P. Li, Y.-Y. Wang, Crystal Growth & Design 10 (2010) 2037-2040. D.-S. Li, J. Zhao, Y.-P. Wu, B. Liu, L. Bai, K. Zou, M. Du, Inorganic chemistry 52 (2013) 8091-8098. S. L. James, Chemical Society Reviews 32 (2003) 276-288. C. Janiak, Dalton Transactions 14 (2003) 2781-2804. M. Rosseinsky, Microporous and Mesoporous Materials 73 (2004) 15-30. J. S. Seo, D. Whang, H. Lee, S. Im Jun, J. Oh, Y. J. Jeon, K. Kim, Nature 404 (2000) 982-986. M. Eddaoudi, J. Kim, J. Wachter, H. Chae, M. O'keeffe, O. Yaghi, Journal of the American Chemical Society 123 (2001) 4368-4369. Q.-R. Fang, G.-S. Zhu, Z. Jin, M. Xue, X. Wei, D.-J. Wang, S.-L. Qiu, Crystal growth & design 7 (2007) 1035-1037. L. Pan, B. Parker, X. Huang, D. H. Olson, J. Lee, J. Li, Journal of the American Chemical Society 128 (2006) 4180-4181. S. Ma, H.-C. Zhou, Journal of the American Chemical Society 128 (2006) 11734-11735.
16
[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]
J. Zhang, S. Chen, T. Wu, P. Feng, X. Bu, Journal of the American Chemical Society 130 (2008) 12882-12883. L. J. Murray, M. Dincă, J. R. Long, Chemical Society Reviews 38 (2009) 1294-1314. N. Tian, Z.-Y. Zhou, N.-F. Yu, L.-Y. Wang, S.-G. Sun, Journal of the American Chemical Society 132 (2010) 7580-7581. A. G. Wong-Foy, A. J. Matzger, O. M. Yaghi, Journal of the American Chemical Society 128 (2006) 3494-3495. J. H. Liao, C. Y. Lai, C. L. Yang, Journal of the Chinese Chemical Society 61(2014) 11151120. N. A. Khan, Z. Hasan, S. H. Jhung, Journal of hazardous materials 244 (2013) 444-456. X.-S. Wang, S. Ma, D. Sun, S. Parkin, H.-C. Zhou, Journal of the American Chemical Society 128 (2006) 16474-16475. Q. R. Fang, G. S. Zhu, Z. Jin, Y. Y. Ji, J. W. Ye, M. Xue, H. Yang, Y. Wang, S. L. Qiu, Angewandte Chemie (International ed. in English) 46 (2007) 6638-6642. B. Wang, A. P. Côté, H. Furukawa, M. O’Keeffe, O. M. Yaghi, Nature 453 (2008) 207-211. K. Koh, A. G. Wong-Foy, A. J. Matzger, Angewandte Chemie International Edition 47 (2008) 677-680. Y. K. Park, S. B. Choi, H. Kim, K. Kim, B.-H. Won, K. Choi, J.-S. Choi, W.-S. Ahn, N. Won, S. Kim, D. H. Jung, S.-H. Choi, G.-H. Kim, S.-S. Cha, Y. H. Jhon, J. K. Yang, J. Kim, Angewandte Chemie International Edition 46 (2007) 8230-8233. S. Nuasaen, P. Opaprakasit, P. Tangboriboonrat, Carbohydrate polymers 101( 2014) 179-187. K. Yamashita, M. Noguchi, A. Mizukoshi, Y. Yanagisawa, International journal of environmental research and public health 7 (2010) 3489-3498. Y. Sekine, Atmospheric Environment 36 (2002) 5543-5547. A. Nomura, C. W. Jones, ACS applied materials & interfaces 5 (2013) 5569-5577. a; bR. Deitrich, V. Erwin, Annual review of pharmacology and toxicology 20 (1980) 55-80. A. T. CrysAlisPro, Version 1.171.36.28. Agilent Technologies: Santa Clara, CA, 2013. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. Howard, H. Puschmann, Journal of Applied Crystallography 42 (2009) 339-341. G. Sheldrick, Acta Crystallographica Section A 2008, 64, 112-122. M. Frisch, G. Trucks, H. Schlegel, G. Scuseria, M. Robb, J. Cheeseman, V. Zakrzewski, J. Montgomery Jr, R. Stratmann, J. Burant, Inc.. Revision A 1998, 6. C.-F. Chang, C.-Y. Chang, K.-H. Chen, W.-T. Tsai, J.-L. Shie, Y.-H. Chen, Journal of colloid and interface science 277 (2004) 29-34. V. A. Blatov, D. M. Proserpio, Acta Crystallographica Section A: Foundations of Crystallography 65 (2009) 202-212. V. A. Blatov, D. M. Proserpio, Acta Crystallographica Section A: Foundations of Crystallography 65(2009) 202-212. H. Matsushita, Y. Tsujino, M. Noguchi, S. Yoshikawa, Bulletin of the Chemical Society of Japan 50 (1977) 1513-1516. C. B. McArdle, L. Zhao, US Patents No. 8022251 20 sep 2011.
17
Graphical abstract Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by solvothermally synthesized of a 3D nano-porous MOF based on TATAB tricarboxylate ligand and Zn (NO3)2 .6H2O.
Highlights • • • •
We present a 3D Zn(II)-MOF with TATAB linker by solvothermal method. The framework possesses a new kvh1 topology. The framework displays formaldehyde and benzaldehyde absorption property. Conformational analysis was performed to determine the stable linker geometry.
18