VIETNAM NATIONAL UNIVERSITY – HOCHIMINH CITY
UNIVERSITY OF TECHNOLOGY
TRAN VAN THUAN
COPPER – BASED METAL – ORGANIC FRAMEWORKS
AS EFFICIENT AND RECYCLABLE CATALYSTS FOR
THE OXIDATIVE AMINATION REACTIONS
Major: Chemical technology
Major code: 60 52 03 01
M. ENG. THESIS
HO CHI MINH CITY, JANUARY 2015
The thesis was completed at Ho Chi Minh City University of Technology - Vietnam National
University – Ho Chi Minh City.
Supervisor:
……………………………………
Dr. Truong Vu Thanh
Independent opponent 1: Dr. Nguyen Quoc Thiet
……………………………………
Independent opponent 2: Dr. Phan Thi Hoang Anh
……………………………………
Master thesis was defended at Ho Chi Minh City University of Technology – Vietnam
National University – Ho Chi Minh City on January 14th, 2015
Member of the committee included:
1. Assoc. Prof. Nguyen Ngoc Hanh
2. Dr. Phan Thi Hoang Anh
3. Dr. Nguyen Quoc Thiet
4. Dr. Bui Tan Nghia
5. Dr. Ha Cam Anh
Identification of the President’s committee and Dean of the faculty for several adjustments
(if any)……………………………………………………………………………………….
President’s committee
Dean of the faculty of chemical engineering
Assoc. Prof. Dr. Nguyen Ngoc Hanh
Prof. Dr. Phan Thanh Son Nam
VIETNAM NATIONAL UNIVERSITY HCMC
SOCIALIST REPUBLIC OF VIETNAM
Independence – Freedom – Happiness
UNIVERSITY OF TECHNOLOGY
Ho Chi Minh City, January 28th, 2015
I.
Personal information
Full name:
TRAN VAN THUAN
Birthday:
20/12/1990
Major:
Chemical technology
Student code:
II.
Gender:
Male
Major code: 60 52 03 01
12144423
Thesis title
COPPER – BASED METAL – ORGANIC FRAMEWORKS AS EFFICIENT AND
RECYCLABLE CATALYSTS FOR THE OXIDATIVE AMINATION
REACTIONS
III. Aim and objectives
1. Characteristics of the Cu2(BDC)2(BPY) and Cu3(BTC)2 by various techniques
including XRD, FT-IR, SEM, TEM, TGA, ICP and nitrogen physisorption
measurement.
2. Catalytic investigation of the Cu2(BDC)2(BPY) and Cu3(BTC)2 for the oxidative
amination reactions.
IV. Started date:
January 20th, 2014
V.
November 21st, 2014
Finished date:
VI. Supervisor:
Dr. Truong Vu Thanh
The project was approved by the Department of Organic Chemical Engineering.
Faculty of Chemical
Engineering
Organic Chem. Eng. Department
Supervisor
Prof. Dr.
Assoc. Prof. Dr.
Dr. Truong Vu Thanh
Phan Thanh Son Nam
Le Thi Hong Nhan
ACKNOWLEDGEMENTS
I would like to express sincere gratitude to my supervisor, Dr. Truong Vu Thanh for his
constant advice, guidance, insight, and for sharing his extensive knowledge of chemistry.
I am also grateful to all teaching staffs of the Organic Chemical Engineering Department
for their valuable help. I would like to give my special thanks to Ms. Nguyen Thi Ngoc
Hạnh, Mr. Nguyen Kim Chung, Ms. Dang Huynh Giao, Mr. Nguyen Thai Anh, Mr.
Nguyen Dang Khoa, Mr. Nguyen Thanh Tung, Mr. Nguyen Tran Vu, Mr. Tran Hai Quan
and Mr. Phan Vu Duc Ha and for their meaningful encouragement and help.
I wish to thank all of my friends and all students for their support during course of my
study.
Especially, I would like to express my sincere thankfulness to my family who are always
standing by my side through the hardest times. Their unconditional love and support
have always accompanied with every achievement in my life.
Ho Chi Minh City, January 2015
Tran Van Thuan
i
ABSTRACT
The utilization of both ligand 1,4-dicarboxylic acid and 4,4-bipyridine preparing for the
Cu2(BDC)2(BPY) were implemented by solvothermal method. The Cu3(BTC)2 also was
synthesized according to previous works. The structure of this materials were
characterized using several various techniques, including X-ray powder diffraction
(XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM),
thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR),
inductively coupled plasma (ICP) analysis, and nitrogen physisorption measurements.
The Cu2(BDC)2(BPY) and Cu3(BTC)2 were used as heterogeneous catalysts for the
oxidative amination reactions. Several essential factors including solvent, temperature,
molar ratio, catalyst concentration and oxidant component were rigorously investigated
in order to establish optimal circumstances of reaction. In leaching test, the catalyst was
facilely separated from the reaction by centrifugation. The catalyst recyclability was also
specifically investigated and the reaction could be reused several times without a
significant degradation in catalytic activity. Under optimal reaction, reactions scope with
respect to coupling partners were also determined. The products were confirmed by GCMS, 1H NMR and 13C NMR.
ii
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ..................................................................................................i
ABSTRACT ....................................................................................................................... ii
LIST OF ABBREVIATIONS .............................................................................................. v
LIST OF FIGURES ............................................................................................................vi
LIST OF TABLES ..............................................................................................................ix
LIST OF SCHEMES ............................................................................................................ x
CHAPTER 1: LITERATURE REVIEW. ............................................................................ 1
1.1 METAL – ORGANIC FRAMEWORKS ....................................................................... 1
1.1.1 General background............................................................................................... 1
1.1.2 Structural characteristics ....................................................................................... 2
1.1.3 Properties ............................................................................................................... 4
1.1.4 Synthetic methods ................................................................................................. 6
1.1.5 General applications .............................................................................................. 7
1.2 MOFs AS CATALYST FOR ORGANIC REACTION .............................................. 11
1.2.1 MOFs with catalytically active metal nodes in the framework ........................... 11
1.2.2 Catalytic functionalization of organic framework linkers ................................... 14
1.2.3 Homochiral MOFs ............................................................................................... 15
1.2.4 MOF-encapsulated catalytically active guests .................................................... 16
1.3 C – N OXIDATIVE COUPLING REACTION .......................................................... 17
1.3.1 Copper-catalyzed oxidative amidation of terminal alkynes ................................ 17
1.3.2 Copper-catalyzed C-N oxidative amination of C-H/N-H ................................... 19
iii
CHAPTER 2: EXPERIMENTAL SECTION .................................................................... 22
2.1 MATERIALS AND INSTRUMENTATION .............................................................. 22
2.2 SYNTHESIS OF THE METAL-ORGANIC FRAMEWORKS ................................. 23
2.2.1 Chemical catalogue ............................................................................................. 23
2.2.2 Preparation of Cu2(BDC)2(BPY)......................................................................... 24
2.2.3 Preparation of Cu3(BTC)2.................................................................................... 24
2.3 Catalytic Studies .......................................................................................................... 25
2.3.1 Oxidative amindation of terminal alkynes between phenylacetylene and 2 –
oxazolidone ................................................................................................................... 25
2.3.2 The oxidative α-amination between propiophenone and morpholine ................. 25
2.4 Formulate for reaction calculation ............................................................................... 26
2.4.1 Formulate for calculating conversion of reaction ............................................... 26
2.4.2 Formulate for calculating selectivity of reaction ................................................. 26
CHAPTER 3: RESULTS AND DISCUSSION ................................................................. 28
3.1 CATALYST CHARACTERIZATION ....................................................................... 28
3.1.1 Cu2(BCD)2(BPY) ...................................................................................................... 28
3.1.2 Cu3(BTC)2 ................................................................................................................. 33
3.2. CATALYTIC INVESTIGATION OF THE Cu2(BCD)2(BPY) FOR THE
OXIDATIVE AMINDATION OF TERMINAL ALKYNES ........................................... 37
3.3 CATALYTIC INVESTIGATION OF THE Cu3(BTC)2 FOR THE C-N OXIDATIVE
AMINATION OF C-H/N-H .............................................................................................. 50
CONCLUSION ............................................................................................................................. 63
REFERENCES ............................................................................................................................. 64
APPENDIXIES ............................................................................................................................. 76
iv
LIST OF ABBREVIATIONS
DMF:
N,N-Dimethylformamide
DCM:
Dichloromethane
FT-IR:
Fourier transform infrared
GC:
Gas chromatography
GC-MS:
Gas chromatography-mass spectrometry
ICP-AES: Inductively coupled plasma atomic emission spectroscopy
BDC:
1,4 – benzenedicarboxylic acid
BTC:
1,3,5 – benzenetricarboxylic acid
DABCO: 1,4-diazabicyclo[2.2.2]octane
IRMOF:
Iso-reticular metal-organic framework
MIL:
Materials of Institut Lavoisier
MOF:
Metal-organic framework
SEM:
Scanning electron microscopy
TBHP:
Tert-butyl hydroperoxide
TEM:
Transmission electron microscopy
TGA:
Thermogravimetric analysis
TON:
Turnover number
TOF:
Turnover frequency
BPY:
4,4’ – bipyridine
DBU:
1,8-Diazabicycloundec-7-ene
H2BTEC: 1,4-benzenedicarboxylic acid
4-BTAPA: 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide
v
LIST OF FIGURES
Page
Content
2
Figure 1.1 (a) The Re6Se8(CN)6 unit and (b) the same abstracted as an octahedral
SBU
2
Figure 1.2 (a) The basic SBU OZn4(CO2)6. (b) The basic SBU OCr3(CO2)X3.
3
Figure 1.3 SBUs with (from top) eight, eight, and 12 points of extension
3
Figure 1.4 Examples of tetratopic linkers: (a and b) tetrahedral and (c) square.
4
Figure 1.5 Different modes of interpenetration for 1D nets: (a) 1D → 1D parallel
(b) 1D → 2D parallel and (c) 1D → 3D inclined interpenetration
4
Figure 1.6 (a) Heterochiral and (b) homochiral interpenetration of two 3D nets.
5
Figure 1.7 Crystal structure of MOF-210, DOI: 10.1126/science.1192160
5
Figure 1.8 Structural representations of the different forms of [Zn2(2,5-BMEBDC)2(DABCO)] n along the crystal ographic c-axis.
8
Figure 1.9 Schematic view of the formation of a Bio-MOF (Bio-MIL-1) built up
from bioactive linker and its delivery. Here the bioactive linker is nicotinic acid.
Iron, oxygen, nitrogen, and carbon atoms are in orange, red, gray, and black,
respectively.
9
Figure 1.10 (Left): Kinetics of delivery of ibuprofen from several porous MOFs
carriers; (Top right): Pore openings of the MIL-53 solid: water (left), ibuprofen
(center) and open form (right); (Bottom right): Schematic view of the larger cage
(left) and the smaller cage (right) of MIL – 100. Metal octahedra, oxygen and
carbon atoms are in orange, red, and black, respectively.
10
Figure 1.11 Schematic representation of the synthesis of POST – 1.
11
Figure 1.12 The diamond – like 3D network of Cd(QA)2; selective sorption in favor
of S-alcohol.
12
Figure 1.13 Fluctuation of reagent and product concentration of the Cu3(BTC)2catalyzed cyanosilylation of benzaldehyde (in pentane, 40 oC).
vi
15
Figure 1.14. Ligand employed in POST-1 synthesis (left) and transesterification of
2,4-dinitrophenylacetate with alcohol in CCl4 at 27 oC in the presence of POST-1
(right)
16
Figure 1.15 Cyclohexane catalytic oxidation catalyzed by Mn-metalated porphyrin
encapsulated in rho-ZMOF.
17
Figure 1.17 Farnesyl tethered ynamide based on C-N coupling reaction.
18
Figure 1.18 A model of C-N coupling reaction between phenylacetylene and 2oxazolidinone using copper catalyst
19
Figure 1.19 Common pharmacophore in medicinal agents toward α-amino
carbonyls.
28
Figure 3.1 X-ray powder diffractograms of the Cu2(BDC)2(BPY)
29
Figure 3.2 FT-IR spectra of the Cu2(BDC)2(PBY) (a); 1,4 – benzenedicarboxylic
acid (b) and 4,4’-bipyridine (c).
30
Figure 3.3 Nitrogen adsorption/desorption isotherm of the Cu2(BDC)2(BPY).
Adsorption data is shown as closed circles and desorption data as vertical bars.
30
Figure 3.4 Pore size distribution of the Cu2(BDC)2(BPY)
31
Figure 3.5 TGA analysis of the Cu2(BDC)2(BPY)
32
Figure 3.6 SEM micrograph of the Cu2(BDC)2(BPY)
32
Figure 3.7 TEM micrograph of the Cu2(BDC)2(BPY)
33
Figure 3.8 XRD diffraction of Cu3(BTC)2 after 24 h heating (a) and after activating
under vacuum pressure (b)
34
Figure 3.9 FT-IR spectra of the Cu3(BTC)2 (a) 1,3,5-benzenetricarboxylic acid (b)
34
Figure 3.10 Nitrogen adsorption/ desorption isotherm of the Cu3(BTC)2. Adsorption
data is shown as closed circles and desorption data as vertical bars.
35
Figure 3.11 Pore size distribution of the Cu3(BTC)2.
vii
35
Figure 3.12 TGA analysis of the Cu3(BTC)2
35
Figure 3.13 SEM micrograph of the Cu3(BTC)2.
40
Figure 3.14 TEM micrograph of the Cu3(BTC)2.
40
Figure 3.15 Effect of catalyst loading on reaction conversion (a) and selectivity (b)
41
Figure 3.16 Effect of reagent ratio on reaction conversion (a) and selectivity (b)
44
Figure 3.17 Leaching test with catalyst removal after first 40 minutes
45
Figure 3.18 Catalyst recycling studies.
46
Figure 3.19 FT-IR spectra of the fresh (a) and reused (b) Cu2(BDC)2(BPY) catalyst.
47
Figure 3.20 X-ray powder diffractograms of the fresh (a) and reused (b)
Cu2(BDC)2(BPY)
51
Figure 3.21 Impact of the content of salt KBr on conversion
52
Figure 3.22 Impact of reagent molar ratio on conversion
53
Figure 3.23 Impact of the catalyst concentration on conversion
56
Figure 3.24 Leaching test with catalyst removal after 2 hours
57
Figure 3.25 Catalyst recycling studies
58
Figure 3.26 FT-IR spectra of the fresh Cu3(BTC)2 (a) and first reused (b)
58
Figure 3.27 PXRD spectra of the fresh Cu3(BTC)2 (a) and first reused (b)
viii
LIST OF TABLES
Page
Content
14
Table 1.1 Knoevenagel condensation reaction of benzlaldehyde with substrates,
catalyzed by [Cd(4-BTAPA)2(NO3)2].6H2O.2DMF] n
23
Table 2.1 List of common chemicals for experience
37
Table 3.1 Optimization of reaction conditions with respect to solvent and base
39
Table 3.2 Effect of oxidant
40
Table 3.3 Effect of other components in air to reaction efficiency
43
Table 3.4 Reactivity of other catalysts
47
Table 3.5 Comparative summary: Role of Bipyridine ligand
48
Table 3.6 Reactions scope with respect to coupling partners
54
Table 3.7 Optimization of reaction conditions with respect to solvent
59
Table 3.8 Reactivity of other catalysts
60
Table 3.9 Reactions scope with respect to coupling partners
ix
LIST OF SCHEMES
Page
Content
12
Scheme 1.1 Cyanosilylation of benzaldehyde.
13
Scheme 1.2 Isomerization of a-pineneoxide to campholenic aldehyde
14
Scheme 1.3 Proposed mechanism for the formation of the epoxide using
[Cu(H2BTEC)(BPY)] as heterogeneous catalyst
17
Scheme 1.4 Copper-catalyzed pathways for ynamine synthesis
18
Scheme 1.5 Procedures and issues summary forming C-N bond in comparison
19
Scheme 1.6 Proposed mechanism for copper-catalyzed oxidative coupling terminal
alkyne and nitrogen nucleophiles
20
Scheme 1.7 Traditional strategy via many protocols between nucleophilic enolate and
electrophilic amine
20
Scheme 1.8 Procedures and issues summary forming C-N bond in comparison
21
Scheme 1.9 Proposed mechanism for Cu(II)-Catalyzed Carbonyl−Amine Coupling
x
Chapter 1
Literature Review
CHAPTER 1: LITERATURE REVIEW
1.1 METAL – ORGANIC FRAMEWORKS
1.1.1 General background
Over the several decades, the study of porous solid materials has been arousing great
attention from researches of various fields, including chemistry, physics and material
science.1 From the first ideal about coordination network having a chemical formula of
Ni(CN)2(NH3).C6H6 discovered by Hofmann and Küspert in 1897,2 the porous structures
have illustrated with a vast number of applications in various fields such as adsorption,
separation and purification as well as catalysis.3 Because of numerous features concerning
about high stability and porosity, the exploration of advanced porous materials for such
applications is therefore an interesting subject of scientific research. Metal – Organic
Frameworks (MOFs) emerged as a new class of porous solid materials, as well as, have
unprecedentedly evolved into a potential research field.4,5
Although the first reports on MOFs began from the late 1950s,6 Robson and co-workers,7
followed by Kitagawa et al.8 also discovered many innovative structures, there was no
evidence that both official definitions and considerable characteristics were indicated. At
the beginning 1990s, Yaghi and co-workers 9, and then Ferey et al.10 much contributed
toward boost in applicable extent. Thus, new terms of Materials Institute Lavoisier (MILs),
Secondary Building Units (SBUs), Meso–Porous Metal–Organic Framework (meso –
MOF) and Pore size were integrally described. 11 Moreover, several MOFs are nowadays
industrially prepared and marked by BASF, such as ZIF-9 (Zeolite Imidazolate
Frameworks, BASOLITETM Z2100) and Cu3(BTC)2 (HKUST-1, MOF-199, BASOLITETM
C300). Some also commercially available through Aldrich.12 In addition, reticular
chemistry forms and predetermines thousands of structure in proportion to topology in
which unit is repeated and held together by strong bonds.13 This is also one of the most
highlighting and advanced features in comparison with traditional materials.
M. ENG. THESIS
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Chapter 1
Literature Review
1.1.2 Structural characteristics
MOFs are classified the family of porous coordination polymers built up from the
combination of an inorganic subunit (metal cluster) and organic linker (ligand) by
coordination bonds
3,14
. Different from other organic polymers, this material generates
orderly organization in three – dimensional framework whose skeleton based on strong
connection between organic components and central metal ions (often called as SBUs,
secondary building units).15
Figure 1.1 (a) The Re6Se8(CN)6 unit and
Figure 1.2 (a) The basic SBU OZn4(CO2)6. (b)
(b) The same abstracted as an octahedral The basic SBU OCr3(CO2)X3.
SBU.
According to their definition, SBUs are categorized into two major kinds. The first kind is
organic linkers that may be ditopic or polytopic. The second kind of SBU may be a metal
atom or (most commonly) a finite polyatomic cluster containing two or more metal atoms
or an infinite unit such as a one-periodic rod of atoms. Both shapes are treated slightly
differently in a way that reflects their different roles in the design and synthesis process.16
Metal-containing SBUs are formed at the time of synthesis using conditions (e.g.,
temperature, pH) designed to produce just that SBU. Their shape is defined by points of
extension where they connect to organic linking components.17
In particular, the latter may have the same topology but a different metric, producing, one
anticipates, an iso-reticular series of structures with the same underlying net.
M. ENG. THESIS
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Chapter 1
Literature Review
Figure 1.3 SBUs with (from top) eight, eight, Figure 1.4 Examples of tetratopic linkers: (a
and 12 points of extension.
and b) tetrahedral and (c) square.
The crystal science reaching out porous networks becomes a complicated task because of
the topology of interpenetration which can even be beneficial to porous networks,
stabilizing structures that would otherwise likely collapse upon removal of solvent.18
Furthermore, a flexible structure can fill available space a sit forms by whether through
intercalation (ranging from ordered guests pieces to completely disordered, essentially
liquid solvent), interdigitation (for 1D or 2D networks), or interpenetration.19
Interpenetration occurs when two or more polymeric networks are not chemically bonded
to each other but cannot be separated without the breaking of bonds.20 There are two
important topological properties of interpenetrating 1D and 2D networks. Firstly, the nets
can interpenetrate such that they are all parallel or inclined in two or more directions.
Secondly, the interpenetration can produce entanglements that are either of the same
dimensionality of the nets or higher. Both these considerations lead to different topologies
of interpenetration.
M. ENG. THESIS
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Chapter 1
Literature Review
Figure 1.5 Different modes of interpenetration for 1D nets: (a) 1D → 1D parallel (b) 1D →
2D parallel and (c) 1D → 3D inclined interpenetration.
There are numerous examples of interpenetrating 3D networks, the most common of which
are the diamond and α-Po nets.21 Therefore, self-penetration and heterogeneous
interpenetration are also mentioned.22
Figure 1.6 (a) Heterochiral and (b) homochiral interpenetration of two 3D nets.
1.1.3 Property
While traditional materials such as zeolite or silica normally obtain specific surface area
no more than 500 m2/g by BET method, MOFs are with ultrahigh porosity up to 90% free
volume and surface areas, for example, MOF-200 and MOF-210 extending with 8,000
m2/g.23
M. ENG. THESIS
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Chapter 1
Literature Review
Figure 1.7 Crystal structure of MOF-210, DOI: 10.1126/science.1192160
Several MOFs have open metal sites (coordinative unsaturated) that are built into the pore
“walls” in a repeating, regular fashion. Indeed, the presence of open metal sites is of key
importance for adsorption and catalysis, since it strongly favors the direct interaction
between metal and substrate.24 Consequently, materials originally designed for adsorption
may as well show good performance for the latter and vice versa, as has been
demonstrated.25 For example, Yousung Jung and co-workers have implemented
chemospecific affinity toward CO2 using M-MOF-74 (M = Mg, Ca, and the first transition
metal elements). Report showed that Ti- and V-MOF-74 can have an enhanced affinity
compared to Mg-MOF-74 by 6−9 kJ/mol. Otherwise, the origin of the major affinity trend
is the local electric field effect of the open metal site that stabilizes CO2, but forward
donation from the lone-pair electrons of CO2 to the empty d-levels of transition metals as
in a weak coordination bond makes Ti and V have an even higher binding strength than
Mg, Ca, and Sc.26
Figure 1.8 Structural representations of the different forms of [Zn2(2,5-BME-BDC)2(DABCO)] n
(1) along the crystal ographic c-axis. (where, lp = large pore, np = narrow pore).
M. ENG. THESIS
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Chapter 1
Literature Review
In 2007, G. Férey’s group has detected the reversible “breathing” motion of MILs
concerning about behaviors of structural flexibility in which reversible transitions are
dependent on both quantity of adsorbed guest molecules and role of solvent – host
interactions.27 Although mechanism of transformation and the interactions between the
guests and the skeleton are sophisticated based on combination between control the nature
of the inorganic building block and computer simulation, in situ techniques show that these
flexible solids are highly selective absorbents.28 For example, Fisher et al. have presented
a powerful approach for the targeted manipulation of responsiveness and framework
flexibility of an important family of pillared-layered MOFs based on the parent structure
[Zn2(BDC)2(DABCO)]n. The parent MOF is only weakly flexible; however, the
substituted frameworks of [Zn2(BDC)2(DABCO)]n contract drastically upon guest
removal and expand again upon adsorption of DMF, EtOH, or CO2, etc., while N2 is hardly
adsorbed and does not open the narrow-pored form. These “breathing” dynamics are
attributed to the dangling side chains that act as immobilized “guests”, which interact with
mobile guest molecules as well as with themselves and with the framework backbone.29
1.1.4 Synthetic methods
The synthesis of crystalline porous materials has immensely attracted attention over the
past several decades. Up to now, some typical synthetic routes have already known, such
as microwave-assisted,30 electrochemical,31 mechanochemical
32
and sonochemical
synthesis.33 Generally, although these methods have some specific advantages as well as
disadvantages, in fact solvothermal method is mostly used as an essential method because
of low-cost, high porous crystal and fluctuating temperature of reaction only from 80 oC
to 200 oC.34 Thus, the metal source combines with organic linkers under suitable
conditions of solvent, temperature, structure-directing agents and mineralizers to form
crystalline material. 35
The solvent is one of the most important parameters in the synthesis of MOFs. Although
most often no direct interaction with the framework is observed, solvents are almost
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