Elsevier Editorial System(tm) for Materials

Letters
Manuscript Draft

Manuscript Number: MLBLUE-D-16-00783

Title: Rapid synthesis of Titanium based Metal Organic framework (MIL-

125) via Microwave route and its performance evaluation in photocatalysis

Article Type: Short Communication

Keywords: Porous materials; Solar energy materials; MIL-125;

Photocatalysis

Corresponding Author: Dr. pradip chowdhury, Ph.D.

Corresponding Author's Institution: National Institute of Technology

Rourkela

First Author: Prince George, M.Tech

Order of Authors: Prince George, M.Tech; Nikhil R Dhabarde, B.Tech;

pradip chowdhury, Ph.D.

Abstract: In this work, we report rapid synthesis procedure of MIL-125

(or, Ti-BDC) Metal Organic Framework (MOF) via microwave route. The
synthesized product was characterized using SEM, powder XRD, FT-IR
analysis, TGA and UV-Vis diffused reflectance spectroscopy. The aim of
this work was to establish a faster synthesis methodology for bulk
synthesis of a potential MOF. The optimum synthesis temperature and time
were found to be 120oC and 40 minutes respectively. The variation of both
microwave power and development of pressure during the synthesis
conditions were closely monitored and it was observed that at optimum
synthesis conditions, during the initial heating rate period, the
pressure was linearly developed and reached a maximum value of ca. 14
bar, however, during the holding time both the pressure and power
remained fairly constant at around 6 bar and 10 watts respectively. The
product was found be photocatalytically active with a band gap energy of
3.14eV and successfully degraded methylene blue dye to ca. 96.77% in 360
minutes.

Suggested Reviewers: Sasidhar Gumma Ph.D

Professor, Chemical Engineering, Indian Institute of Technology Guwahati
s.gumma@iitg.ernet.in
An Expert

Randall Q Snurr Ph.D

John G. Searle Professor of Chemical and Biological Engineering, Chemical
and Biological Engineering, Northwestern University
snurr@northwestern.edu
An Expert

Giridhar Madras Ph.D

Professor, Chemical Engineering, Indian Institute of Science Bangalore
giridhar@chemeng.iisc.ernet.in
An Expert
Highlights (for review)

Highlights

(1) Rapid synthesis of MIL-125 using microwave technique

(2) Optimum temperature and time was 120oC and 40 minutes respectively

(3) The band gap energy of MIL-125 was measured to be ca. 3.14 eV

(4) Photocatalytic degradation of methylene blue was ca. 96.77% in 360 min
*Manuscript
Click here to view linked References

Rapid synthesis of Titanium based Metal Organic framework (MIL-125) via Microwave
1 route and its performance evaluation in photocatalysis
2
3 Prince George, Nikhil R Dhabarde, Pradip Chowdhury*
4
5 Department of Chemical Engineering, National Institute of Technology Rourkela, Rourkela, Orissa, India.
6
7 * Corresponding author Tel: 0661-2462269, Email: chowdhuryp@nitrkl.ac.in
8
9
10
11 Abstract
12
13 In this work, we report rapid synthesis procedure of MIL-125 (or, Ti-BDC) Metal Organic Framework (MOF)
14
15 via microwave route. The synthesized product was characterized using SEM, powder XRD, FT-IR analysis,
16
17 TGA and UV-Vis diffused reflectance spectroscopy. The aim of this work was to establish a faster synthesis
18
19 methodology for bulk synthesis of a potential MOF. The optimum synthesis temperature and time were found to
20
21 be 120oC and 40 minutes respectively. The variation of both microwave power and development of pressure
22
23 during the synthesis conditions were closely monitored and it was observed that at optimum synthesis
24
25 conditions, during the initial heating rate period, the pressure was linearly developed and reached a maximum
26
27 value of ca. 14 bar, however, during the holding time both the pressure and power remained fairly constant at
28
29 around 6 bar and 10 watts respectively. The product was found be photocatalytically active with a band gap
30
31 energy of 3.14eV and successfully degraded methylene blue dye to ca. 96.77% in 360 minutes.
32
33
34 Key words: MOFs, Microwave synthesis, MIL-125, Photocatalysis
35
36
37 1. Introduction
38
39 Metal Organic Frameworks (MOFs) are a class of novel materials and are primarily synthesized by
40
41 hydrothermal/solvothermal, sol-gel, microwave, electrochemical, ultrasound and mechanical methods [1-2]. For
42
43 bulk synthesis of potential MOFs, it is imperative upon to maintain rapidity in synthesis and consistency in
44
45 reaction conditions without compromising the product quality. Synthesis of MOFs is generally prone to get
46
47 affected on subtle variations in reaction conditions e.g. temperature and time. It has been observed that both the
48
49
product yield as well as the quality of materials synthesized varies considerably from batch to batch once there
50
51
is slight variation in reaction conditions [3]. This often results into products with widely different surface
52
53
characteristics, affecting their overall performance in gas storage, separation and catalytic applications. More
54
55
benign reaction conditions in terms of low temperature and short reaction time is preferable to yield products
56
57
58 with less imperfections, higher purity with less or no by-products and uniformity in surface morphologies.
59
60 Microwave assisted synthesis of MOFs has often been carried out at temperatures above 100 C with synthesis
61
62 1
63
64
65
 times rarely exceeding 1hr.MOFs are generally formed via self-assembly, hence slight variation in
1
2 composition(molar ratio of reactants)and process parameters such as reaction time, temperature and heating rate
3
4 might influence the final product in case of Ti based MIL-125[4].
5
6 Synthesis of Ti based MIL-125 was first reported by Férey et.al. [5] using a solvothermal technique and ever
7
8 since all the recipes involving synthesis of Ti-BDC and other Ti based oxo clusters reported synthesis time
9
10 ranging from 15 hours to 6 days whereas average reaction temperature was approximately 150oC[5-7].
11
12 In this article, a novel microwave route was proposed to rapidly synthesize Ti based MIL-125 and process
13
14 parameters such as reaction time and temperature were optimized. The development of pressure and microwave
15
16 heating rate was closely monitored for the overall consistency in reaction conditions and the synthesized product
17
18 was evaluated for its performance as a potential photocatalyst.
19
20 2. Experimental
21
22
23 Optimization of synthesis conditions w.r.t reaction time and temperature was carried out by keeping
24
25 reactants/solvent molar ratio constant. A stoichiometric mixture of anhydrous Titanium isopropoxide (0.6 ml), 1,
26
27 4-benzenedicarboxylic acid (0.3323 gm) and 20 ml of DMF/Methanol mixture (1:1) were taken in a glass vial.
28
29 Microwave irradiation time was set for 20, 40 and 60 minutes whereas temperature was maintained at 100 oC,
30
31 120 oC and 150 oC respectively. Resulting gel like precipitate was re-suspended in DMF and was centrifuged at
32
33 3000 rpm. The supernatant was discarded and the crystals obtained were dried in hot air oven at 175 oC to
34
35 remove excess solvent.
36
37 The morphologies of synthesized product were observed via scanning electron microscope (SEM, JEOL JSM-
38
39 6480 LV) equipped with an energy dispersive X-ray spectrometer (EDX). Prior to imaging, each sample was
40
41 gold coated in high vacuum. The synthesized samples were subjected to X-ray diffraction by a diffractometer
42
43 (XRD, Philips Analytical, PW-3040) equipped with monochromatized CuKα radiation (λ=1.5406Å) in 2θ
44
45 angles ranging from 5o to 50oto collect the crystallographic information. Diffused UV reflectance study was
46
47 performed in a spectrophotometer (JASCO V-750). FT-IR was performed in ThermoFischer Nicolate I S 10
48
49 analyzer and thermal stability of the samples was carried out in a TGA apparatus (Shimadzu DTG 60 H).
50
51 In photocatalytic experimentation, a high pressure mercury vapor lamp was employed as the artificial light
52
53 source of 100W rating. The light was directed to a sealed conical flask (100 ml volume) made of Pyrex glass.
54
55 The conical flask was filled with known concentration of methylene blue dye solution. To this, a known quantity
56
57 of synthesized material (MIL-125) was added. The mixing was carried out using a magnetic stirrer to ensure
58
59
60
61
62 2
63
64
65
 uniform distribution of catalyst throughout the dye solution. Photocatalytic degradation was studied by
1
2 observing the change in absorbance of dye solution.
3
4 3. Results and Discussion
5
6
7 Fig 1.A shows the PXRD patterns of synthesised Ti based MIL-125 at various synthesis time and temperature.
8
9 The optimum synthesis time and temperature was determined from the powder XRD pattern of Fig 1.A (e) to be
10
11 120ºC and 40 min. For this particular condition, corresponding PXRD peaks were indexed with space group I
12
13 4/mmm and unit cell parameters of a=9.832 Å, b=9.832 Å, c=15.345 Å, α=90º, β=90º and γ=90º.The indexed
14
15 peaks were extended to samples with other synthesis time and temperature and was found to be a close to
16
17 perfect match as observed in Fig 1.A.The % crystallinity of MIL-125 was found to the highest at 120oC for 40
18
19 min synthesis duration. Similar inference on % crystallinity could also be drawn from Fig 1.C based on peak
20
21 intensities in the FTIR spectra.
22
23
From Fig 1.B, SEM images show the samples consist of well crystalline block-like particles with various
24
25
26 shapes. The SEM image of Fig 1.B (e), (h) and (i) matches with the images of MIL-125 published in literature
27
28 [8]. The elemental composition analysis (using EDX) indicates the presence of Ti, C, and O (see supporting
29
30 information). Fig 1.C, shows the FTIR spectra of Ti based MOF synthesized at different temperatures (100, 120
31
32 and 150 oC) for 40 min duration having the fingerprint region (i.e.  <1500 cm-1) similar to published literature
33
34 on MIL-125[8,9].The peaks in FTIR spectra shows marked increase in intensity, indicating the repetition of
35
36 same functional groups. The peaks at 1677 cm-1 and 1281 cm-1 is associated with the presence of dicarboxylate
37
38 linker in the synthesised material. The region from 1680 - 1400 cm-1 relates to O-C-O asymmetric and
39
40 symmetric stretching of carboxylic acids. The difference between asymmetric and symmetric stretching falls
41
42 within 104,169 and 273 cm-1.The corresponding coordination network formed is related to the difference
43
44 between asymmetric and symmetric stretching vibration. The bidentate bridging for 169 cm -1,273 cm-1 and
45
46 bidentate chelating for 104 cm-1 is observed. The degree of bidentate bridging formed is twice more than the
47
48 bidentate chelating, indicating the occurrence in the same cluster [10, 11]. The peaks around 850 cm-1 is
49
50 assigned to Ti-O stretching for non-bound oxygen atom. Peaks at 780,680 and 500 cm-1 is associated with Ti-O-
51
52 Ti stretching vibration [9-12]. Moreover, the optimum reaction temperature and time for best MIL-125 synthesis
53
54 can be drawn from the bond intensities in the FTIR spectra.
55
56
57 Fig 2.A&B shows the pressure – power profile in the reaction vessel during optimum synthesis time and
58
59 temperature. In regular solvothermal synthesis, the pressure in the autoclave is the autogenous pressure. Fig 2.A
60
61
62 3
63
64
65
 shows the pressure –power profile during initial heating rate period and Fig 2.B shows the profile during
1
2 reaction holding time. It is observed that at optimum synthesis conditions (120 oC for 40 min), during the initial
3
4 heating rate period, the pressure is linearly developed and reaches a maximum value of ca. 14 bar, however,
5
6 during the holding time both the pressure and power remains fairly constant at around 6 bar and 10 watts
7
8 respectively. The above pressure and power interpretations were obtained by averaging 8 sets of experimental
9
10 data sets within same time domain.
11
12
13 The TGA-DSC profile in (see supporting information) of synthesised Ti based MOF (MIL-125) shows little
14
15 weight loss in 100 ºC -125 ºC region, indicating presence of very less moisture in the sample. The material
16
17 remains thermally stable upto 325 ºC beyond which the structure collapses [5, 13]. The DSC data as well
18
19 corroborates the degradation temperature. The room temperature diffused reflectance absorption spectra of Ti
20
21 based MOF (MIL-125) (see supporting information) was used to determine the optical band gap using Kubelka
22
23 –Munk method with TiO2 as the benchmark photo catalyst (see supporting information). The optical band gap
24
25 was found to be ca. 3.14 eV for MIL-125 in comparison with 3.22 eV for TiO2. With a band gap of 3.14 eV, the
26
27 synthesised material might have the potential to be photo catalytically active as its band gap energy lies within
28
29 the UV and upper end of visible electromagnetic spectrum [9, 13-14].
30
31
32 The photocatalytic activity of MIL-125 samples was evaluated for its potential in degradation of an organic dye
33
34 viz. methylene blue under visible-light irradiation. Initially the experiments were carried out in dark to estimate
35
36 the adsorption efficiency of the sample and it was found to be 90.4% in 360 min (details can be found in
37
38 supporting information). Photocatalytic degradation of methylene blue dye using MIL-125 was found to be
39
40 96.77% in 360 min (details can be found in supporting information).Based on the initial findings it may be
41
42 inferred that Ti based MIL-125 is a promising material as an adsorbent and photocatalyst and many research
43
44 works are going on to unravel its potential in various applications [4-6,8-9,13,14].
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 4
63
64
65
 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
61
62 5
63
64
65
 4. Conclusion
1
2
Ti based MOF (MIL-125) was successfully synthesised using microwave route. The optimum synthesis time
3
4
5 and temperature were found to be 120 oC and 40 minutes respectively. The variation of both microwave power
6
7 and development of pressure during the synthesis conditions were closely monitored for their consistency during
8
9 various batch studies. The product was found be photocatalytically active with a band gap energy of 3.14eV and
10
11 successfully degraded methylene blue dye to ca. 96.77% in 360 minutes. It also showed adsorptive removal
12
13 efficiency for the same dye (90.4% in 360 min) when the reactions were carried out in dark. Further research has
14
15 been going on to unravel its potential on various other organic-inorganic substrates.
16
17
Acknowledgement
18
19
20 We gratefully acknowledge the financial support provided by Science and Engineering Research Board
21
22 (Department of Science and Technology, Govt. Of India) (Letter No. SB/FTP/ETA-419/2012) in funding the
23 project.
24
25
5. References
26
27
28 [1]Norbert Stock and Shyam Biswas, Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF
29
30 Topologies, Morphologies, and Composites,Chem. Rev., 112 (2) (2012), 933–969.
31
32
33 [2] Yu-Ri Lee, Jun Kim, and Wha-Seung Ahn, Synthesis of metal-organic frameworks: A mini review,Korean J.
34
35 Chem. Eng., 30(9) (2013), 1667-1680.
36
37
38 [3]Colin McKinstry, Russell J. Cathcart, Edmund J. Cussen, Ashleigh J. Fletcher, Siddharth V. Patwardhan, Jan
39
40 Sefcik, Scalable continuous solvothermal synthesis of metal organic framework (MOF-5) crystals, Chemical
41
42 Engineering Journal ,285 (2016) 718–725.
43
44
[4] Lanfang Zou, Dawei Feng, Tian-Fu Liu, Ying-Pin Chen, Shuai Yuan, Kecheng Wang, Xuan Wang, Stephen
45
46
47 Fordhama and Hong-Cai Zhou,A versatile synthetic route for the preparation of titanium metal–organic
48
49 frameworks,Chem. Sci., 7(2016), 1063.
50
51 [5] Meenakshi Dan-Hardi, Christian Serre, Theo Frot, Laurence Rozes, Guillaume Maurin, Clement Sanchez,
52
53 and Gerard Férey,A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate, J. Am. Chem.
54
55 Soc., 131(2009),10857–10859.
56
57
58 [6] Keunil Hong and Hyungphil Chun, Nonporous Titanium−Oxo Molecular Clusters That Reversibly and
59
60 Selectively Adsorb Carbon Dioxide, Inorg. Chem., 52(2013), 9705−9707.
61
62 6
63
64
65
 [7]Yin-Yin Wu, Wen Luo, Yu-Hong Wang, Ya-Yang Pu, Xiang Zhang, Li-Sheng You, Qin-Yu Zhu, and Jie
1
2 Dai, Titanium−oxo−Clusters with Dicarboxylates: Single-Crystal Structure and Photochromic Effect, Inorg.
3
4 Chem., 51(2012), 8982−8988.
5
6
7 [8]Hongxu Guo, Fan Lin, Jianhua Chen, Feiming Li and Wen Weng, Metal–organic framework MIL-125(Ti)
8
9 for efficient adsorptive removal of Rhodamine B from aqueous solution, Appl. Organometal. Chem, 29 (2015),
10
11 12–19.
12
13 [9]Irina D. Ivanchikova, Ji Sun Lee, Nataliya V. Maksimchuk, Alexander N. Shmakov, Yurii A. Chesalov,
14
15
Artem B. Ayupov, Young Kyu Hwang, Chul-Ho Jun, Jong-San Chang,andOxana A. Kholdeeva, Highly
16
17
Selective H2O2-Based Oxidation of Alkylphenols to p-Benzoquinones Over MIL-125 Metal–Organic
18
19
Frameworks, Eur. J. Inorg. Chem. (2014), 132–139.
20
21
22 [10]Daniela Cordeiro, Leite Vasconcelos, Vilma Conceição Costa1, Eduardo Henrique Martins Nunes, Antônio
23
24 Claret Soares Sabioni, Massimo Gasparon, Wander Luiz Vasconcelos, Infrared Spectroscopy of Titania Sol-Gel
25
26 Coatings on 316L Stainless Steel,Materials Sciences and Applications, 2 (2011) , 1375-1382.
27
28
29 [11]Del Castillo, P.C.H., Manuel, S.R. and Ruiz F, An Easy and Efficient Method to Functionalize Titanium
30
31 Dioxide Nanoparticles with Maleic Anhydride, Soft Nanoscience Letters, 4 (2014), 53-62.
32
33
34 [12] Balram Prasad Baranwal, Alok Kumar Singh, Nano-sized, quaternary titanium (IV) metal-organic
35
36 frameworks with multidentate ligands, Spectrochimica Acta Part A, 77 (2010) 938–941.
37
38
39 [13]Se-Na Kim, Jun Kim, Hee-Young Kim, Hye-Young Cho, Wha-Seung Ahn, Adsorption/catalytic properties
40
41 of MIL-125 and NH2-MIL-125,Catalysis Today 204 (2013) 85–93.
42
43 [14] Christopher H. Hendon, Davide Tiana, Marc Fontecave, Clement Sanchez, Loïc D’arras, Capucine
44
45 Sassoye, Laurence Rozes, Caroline Mellot-Draznieks, and Aron Walsh, Engineering the Optical Response of the
46
47 Titanium-MIL-125 Metal−Organic Framework through Ligand Functionalization, J. Am. Chem. Soc., 135
48
49 (2013), 10942−10945.
50
51
52
53
54
55
56
57
58
59
60
61
62 7
63
64
65
Electronic Supplementary Material (online publication only)
Click here to download Electronic Supplementary Material (online publication only): Manuscript_Materials Letters_Supporting In