nanomaterials

Article
Ultrafast Synthesis of Ni-MOF in One Minute by
Ball Milling
Ren Zhang 1,2,† , Cheng-An Tao 2, *,† , Rui Chen 2 , Lifang Wu 1,2 , Xiaoxuan Zou 1, *
and Jianfang Wang 2, *
1 College of Chemistry, Key Laboratory of Environmental Friendly Chemistry and Application in Ministry of
Education, Xiangtan University, Xiangtan 411105, China; 13574092586@163.com (R.Z.);
wulifangyou@163.com (L.W.)
2 College of Liberal Arts and Science, National University of Defense Technology, Changsha 410073, China;
Chenrui13@nudt.edu.cn
* Correspondence: tca02@mails.thu.edu.cn (C.-A.T.); zouxiaoxuanxtu@163.com (X.Z.);
wangjianfang@nudt.edu.cn (J.W.); Tel.: +86-731-8700-1822 (C.-A.T.); +86-731-8700-1801 (J.W.)
† These authors contributed equally to this work.




Received: 28 November 2018; Accepted: 16 December 2018; Published: 18 December 2018


Abstract: A mechanical ball milling method for ultrafast synthesis of a nickel-based metal organic
framework (Ni-MOF) has been proposed. The Ni-MOF was successfully synthesized in merely
one minute without any solvent, additives, or preliminary preparation. The effect of milling time,
mechano-frequency, type of assistant liquid, and amount of assistant water were systematically
explored. It was found that the product can be obtained even only at a mechano-frequency of 10 Hz
within one minute without any external solvent-assist, which indicated that the crystal water present
in the nickel precursor was sufficient to promote MOF formation. Increasing the milling time, raising
the mechano-frequency, and the addition of assistant solvent could promote the reaction and increase
the yield. The method is rapid, highly efficient, eco-friendly, and has great scalability. The product
generated within merely one minute even exhibited high capacitance.

Keywords: metal-organic frameworks; ball milling; solvent-free; mechanochemistry; liquid

assisted grinding

1. Introduction
Metal-organic frameworks (MOFs) [1,2] have attracted intense attention during the past two
decades due to their intriguing structural properties, which led to many potential applications,
including gas storage [3], separations [4], catalysis [5], and sensing [6–8], etc. Recently, MOFs have
been proven to be useful for electrochemical energy storage and considered as potential electrode
material for supercapacitors because of their very large surface area, adjustable pore size, controllable
microporous structure, and special structures with potential pseudo-capacitive redox centers [9–12].
Among them, nickel-based MOFs have get more interest not only because they have been
demonstrated to have great application prospects for supercapacitors, but also because they could be
the template/precursor for unique metal oxide and carbon materials with specific structure, especially
the Ni3 (BTC)2 ·12H2 O (BTC = 1,3,5-benzenrtricarboxylic acid). Kong’s group [13] demonstrated
that the hydrothermally-synthesized Ni3 (BTC)2 ·12H2 O had high specific capacitance of 726 F/g.
Wang et al. [14] took the Ni-MOF as a precursor to prepare mesoporous metal oxide by calcining
the precursor in the air, and the prepared nickel oxide (NiO) had high-capacitance retention at high
scan rate and exhibited excellent cycle-life stability due to its special mesoporous character with
bimodal size distribution. Chen et al. [15] synthesized large-scale of multiwalled carbon nanotubes

Nanomaterials 2018, 8, 1067; doi:10.3390/nano8121067 www.mdpi.com/journal/nanomaterials

Nanomaterials
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carbon nanotubes using Ni3(BTC)2·12H2O as precursor. However, the synthesis processes of

Ni-MOFs
using Ni3 (BTC) 2 ·12H
normally require bulk solvents,
2 O as precursor. However,high temperatures, and longof
the synthesis processes reaction
Ni-MOFs times. For instance,
normally require
Wang et al. [14]
bulk solvents, highsynthesized
temperatures, Ni3(BTC) 2·12Hreaction
and long 2O in a Teflon-lined autoclave
times. For instance, andetheated
Wang al. [14]atsynthesized
200 °C for
◦ C for 24 h,
24
Ni3h, Du et
(BTC) 2 ·12H
al. [16]
2 O insynthesized
a Teflon-lined Ni-BTC MOF and
autoclave in a Teflon-lined
heated at 200autoclave andDuheated to 150
et al. [16] °C for 12
synthesized
h in N,N-dimethyl
Ni-BTC formamideautoclave
MOF in a Teflon-lined (DMF), and andheated
Kong’sto group ◦
150 C [13]for 12prepared Ni-MOF at
h in N,N-dimethyl a lower
formamide
temperature
(DMF), and Kong’s of 105 group °C in [13]
DMF but for Ni-MOF
prepared longer time (up totemperature
at a lower two days). of 105 ◦ C inJin
Although DMFet al.
but[17]
for
described
longer timea (up simpleto two solution-phase
days). Although method Jin et foral.the
[17]synthesis
describedofa simpleNi3(BTC) 2·12H2O under
solution-phase room
method
temperature
for the synthesis in a short
of Ni3time,
(BTC)an 2 · organic
12H 2 O linker
under must
room be deprotonated,
temperature in a and
short an
time,organic
an solvent
organic was
linker
also
mustused. Therefore, a simple,
be deprotonated, and angreen, organic rapid,
solvent and was
energy-efficient route to generate
also used. Therefore, a simple, Ni-based
green, MOFsrapid,
without high temperatures
and energy-efficient route toorgenerate
bulk solvents
Ni-based is still
MOFshighly desirable.
without high temperatures or bulk solvents is
Mechanochemistry,
still highly desirable. i.e., chemical synthesis enabled or sustained by mechanical force [18], has
been Mechanochemistry,
recently introduced as an synthesis
i.e., chemical alternative enabledto or conventional
sustained byMOF mechanical syntheses [19,20].
force [18], has
Mechanochemical
been recently introduced synthesisas anofalternative
MOFs enable avoiding bulk
to conventional MOFsolvents,
syntheseshigh[19,20].temperature,
Mechanochemical and/or
corrosive
synthesis reagents
of MOFsfrequently
enable avoidingemployed bulkin solvents,
solution synthesis. Importantly,
high temperature, it is even
and/or possible
corrosive to be
reagents
more rapidemployed
frequently and efficient than solvent-based
in solution methods. it
synthesis. Importantly, Since
is eventhepossible
synthesis of more
to be the moderately porous
rapid and efficient
copper(II) isonicotinate
than solvent-based MOF in
methods. Sincepioneering work reported
the synthesis by James’ porous
of the moderately group [21], millingisonicotinate
copper(II) procedures
have
MOF been successfully
in pioneering work applied
reported for by
theJames’
synthesis of several
group popular
[21], milling MOF materials,
procedures have been such as zeolitic
successfully
azolate
applied for frameworks
the synthesis [22,23],
of several rare-earth(III)
popular MOF materials, metal−organic frameworks
such as zeolitic [24], isoreticular
azolate frameworks [22,23],
metal-organic
rare-earth(III) metal −organic
frameworks (IRMOFs)
frameworks [25],[24],
iron(III) trimesate
isoreticular MIL-100 (MIL
metal-organic = Materials
frameworks of Institut
(IRMOFs) [25],
Lavoisier) [26], MOF-74
iron(III) trimesate MIL-100 [27],(MIL
Hong=Kong MaterialsUniversity of Science
of Institut and Technology
Lavoisier) [26], MOF-74 （HKUST）-1
[27], Hong Kong [28],
University
Cu of Science and Technology
2I2(triphenylphosphine) 2(L)n (n = 1, (HKUST)-1 [28], Cu2 I2 (triphenylphosphine)
2) [29], copper-based MOF-505 [30], and 2 (L) (n
UiO-66
n = 1, 2)
(UiO [29],
=
copper-based
University MOF-505
of Oslo) and [30],
UiO-67 andderivatives
UiO-66 (UiO = University
[31–33]. Previously,of Oslo) and and
Pichon UiO-67 James derivatives [31–33].
[21] described a
Previously,
survey of thePichon and James
potential [21] described
reactions betweena survey Ni(OAc) of2, the potential
Ni(NO reactions
3)2, NiSO 4 , and between
H3BTC Ni(OAc)
under 2,
Ni(NO3 )2 , NiSO4 , and
mechanochemical H3 BTC under
solvent-free mechanochemical
conditions and, unfortunately, solvent-freeonly conditions
grinding nickel and, unfortunately,
sulfate with
only
H 3BTC grinding nickel reaction.
gave a partial sulfate with H3 BTC gave
Consequently, theaability
partialofreaction. Consequently,
mechanochemistry to accessthe Ni-MOFs
ability of
mechanochemistry
rapidly, has remained to access Ni-MOFs
insufficient rapidly, has remained insufficient explored.
explored.
Herein, we we report the ultrafast synthesis synthesis of Ni-MOF by a mechanical ball milling method
(Figure 1). 1).Notably,
Notably,Ni-MOF Ni-MOF could be obtained
could be obtained in merely one minute
in merely without without
one minute bulk solvent, bulkadditives,
solvent,
or any preliminary
additives, preparation.preparation.
or any preliminary The structure The and the morphology
structure of Ni-MOF were
and the morphology confirmed
of Ni-MOF wereby
powder X-ray
confirmed bydiffraction
powder (PXRD), and scanning
X-ray diffraction electronand
(PXRD), microscopy
scanning (SEM), respectively.
electron microscopy Interestingly,
(SEM),
the Ni-MOF was
respectively. formed bythe
Interestingly, fastNi-MOF
crystallization
was formed withinby onefastminute, after which
crystallization thereone
within wasminute,
no apparentafter
changethere
which in thewasyield noand crystallinity,
apparent change even
in theafter 180 and
yield min.crystallinity,
The effect of even milling time,
after 180mechano-frequency,
min. The effect of
kind of assistant
milling liquid, amount of assistant
time, mechano-frequency, kind of water were systematically
assistant liquid, amount explored. The scalability
of assistant water of the
were
ball milling method
systematically were also
explored. The investigated.
scalability ofThe thegenerated
ball milling Ni-MOFs
method exhibit
werehigh alsocapacitance
investigated. as high
The
as 640 F/gNi-MOFs
generated at the current density
exhibit high of 1 A/g. Toas
capacitance thehigh
bestas of640
ourF/gknowledge, this isdensity
at the current the firstofexample
1 A/g. To of
ultrafast
the best of synthesis of Ni-MOF
our knowledge, thisby is ball milling.
the first example of ultrafast synthesis of Ni-MOF by ball milling.

Figure
Figure 1.
1. Schematic
Schematic representation
representation of
of the
the ball
ball milling
milling method
method for
for the
the rapid
rapid synthesis of Ni
synthesis of Ni--MOF.
MOF.

2. Materials
2. Materials and
and Methods
Methods

2.1. Materials
2.1. Materials
Nickel(II) acetate tetrahydrate [Ni(OAc) ·4H O, AR] was purchased from Tianjin Fenchuan
Nickel(II) acetate tetrahydrate [Ni(OAc)22·4H22O, AR] was purchased from Tianjin Fenchuan
Technology Co. Ltd. (Tianjin, China) and benzene-1,3,5-tricarboxylic acid (H3 BTC, 99%) was purchased
Technology Co. Ltd. (Tianjin, China) and benzene-1,3,5-tricarboxylic acid (H3BTC, 99%) was
from J&K Scientific Ltd. (Beijing, China). DMF(AR) was purchased from Tianjin Hengxing Chemical
purchased from J&K Scientific Ltd. (Beijing, China). DMF(AR) was purchased from Tianjin
Nanomaterials 2018, 8, 1067 3 of 11

Preparation Co. Ltd. (Tianjin, China), methanol (MeOH, AR) was purchased from Sinopharm Chemical
Reagent Co. Ltd. (Beijing, China), and ethanol (EtOH, 99.7%) was purchased from General-Reagent
(Shanghai, China). Pure water was homemade.

2.2. Synthesis of Ni-MOF

Ni-MOFs were synthesized by ball milling of of 2:3 (molar ratio) mixtures of H3 BTC and
Ni(OAc)2 ·4H2 O at varied frequency from 10 Hz to 50 Hz. In a typical reaction, about one gram
of the H3BTC and metal precursor mixture was ball milled for various times (1, 5, 30, 60, and 180 min)
in a agate vial (80 mL) using a QM-QX0.4L mill (Miqi Instrument Equipment Co., Ltd., Changsha,
China) with the addition of specific amount of water (0, 0.5, 1, or 2 mL) or 1 mL of other organic solvent
(MeOH, EtOH, and DMF) and increased the feed rate by three times and five times. The ball-to-powder
mass ratio was consistently kept at about 5:1 for all experiments. The products were scraped off the
jar walls, washed with water and ethanol trice, then the supernatant was removed by centrifugation,
and the solid product was dried at 60 ◦ C in an oven for 12 h. The enlarged scale reaction was performed
with three or five times of the H3 BTC and metal precursor mixture. The yield was calculated according
to the following equation based on the number of moles of Ni(II).
nNi(II) in Ni−btc
Yield = × 100%
nNi(OAc)2

2.3. Characterization
FTIR spectra were recorded in the range of 400–4000 cm−1 on a PerkinElmer Spectra Two
FT-IR spectrophotometer (Waltham, MA, USA) with an attenuated total reflectance (ATR) accessory.
The milled samples were analyzed by powder XRD on a Tri III powder diffractometer (Rigaku, Tokyo,
Japan) using Cu Kα radiation between 8◦ and 60◦ with a scan rate of 5◦ /min. Thermogravimetric
analyses (TGA) were performed on a STA6000 thermal analyzer (PerkinElmer, Waltham, MA, USA)
under N2 with a heating rate of 4 ◦ C/min. Nitrogen adsorption-desorption isotherms, pore size
distributions and surface areas of the samples were measured via N2 adsorption-desorption at 77
K on a BEL SORP-mini II surface area and porosity analyzer (Bel Japan Inc., Osaka, Japan). Before
measurement, the samples were activated at 60 ◦ C for 12 h. The morphology of the sample was
observed by a SEM Model S-4800 (Hitachi, Tokyo, Japan).
All electrochemical measurements were done in a three-electrode experimental setup. A platinum
wire electrode and a saturated Ag/AgCl electrode were used as the counter and reference electrodes,
respectively. All the electrochemical measurements were carried out in 6 mol/L KOH aqueous electrolyte
using a CHI660C (Shanghai Chenhua Apparatus, Shanghai, China) electrochemical workstation.

3. Results and Discussion

3.1. Synthesis of Ni-MOF

3.1.1. Effect of Grinding Time

Firstly, the Ni-MOF Ni3 (BTC)2 ·12H2 O was synthesized by grinding of 2:3 (molar ratio)
mixtures of H3 BTC and Nickel(II) acetate tetrahydrate [Ni(OAc)2 ·4H2 O] with water-assist under
mechano-grinding at 50 Hz for a specific time (1, 5, 30, 60, and 180 min). The products are denoted
as Ni-BTC-1 m, Ni-BTC-5 m, Ni-BTC-30 m, Ni-BTC-60 m, and Ni-BTC-180 m, respectively. There
is no apparent change in the yield, which only varied from 66% to 72% (Table S1). The Fourier
transform infrared (FTIR) spectra of different Ni-MOFs are very similar. These spectra clearly show the
vibrational bands of the waters around 3500 and 3200 cm−1 , which suggests there are crystallization
waters in the product (Figure 2a). Additionally, there is no band at around 1710 cm−1 (which is the
characteristic of protonated carboxylic groups) observed in Ni-MOFs curves, suggesting the absence
of protonated carboxylic groups in the product.
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The XRD pattern shows the characteristic diffraction peaks of Ni 3(BTC)2·12H2O (Figure 2b),
which The XRD pattern
matches well withshows thethe characteristic
result diffraction
of the reported literature of Ni3 (BTC)2 ·and
peaks [14,16,17,34], 12H2theO (Figure 2b),
simulated
which matches well with the result of the reported literature [14,16,17,34],
pattern for [Ni3(BTC)2·12H2O] was based on single-crystal data from the Cambridge and the simulated pattern
for [Ni3 (BTC)2 ·12H
Crystallographic 2 O]Centre
Data was based on single-crystal
(CCDC) data from
[35]. The generated the Cambridge
product in only oneCrystallographic
minute has alreadyData
Centre good
shown (CCDC) [35]. The generated
crystallinity. To evaluateproduct in only
the effect one minute
of grinding timehas
onalready
the sizeshown good crystals,
of Ni-MOF crystallinity.
the
To evaluate the effect of grinding time on the size of Ni-MOF crystals, the full width
full width at half maxima of peaks (FWHM) at 17.7° corresponding to the (220) lattice plane were at half maxima of
peaks in(FWHM) at 17.7 ◦ corresponding to the (220) latticewas
plane were listed in Table S2.
listed Table S2. The average size of Ni-MOF crystals inversely proportional to The average
the FWHM.
size of
The FWHMNi-MOF crystals slightly,
decreases was inversely proportional
at first, and then to the FWHM.
increases, and The FWHM
finally decreases
decreases slightly,
along with
at first, and
grinding thenindicating
time, increases,that
andthe
finally decreases
average along
size of with grinding
Ni-MOF time, indicating
crystals changed slightlythat thewith
along average
the
size of Ni-MOF
grinding time. crystals changed slightly along with the grinding time.

Figure 2. Characterizations of the Ni-BTC samples obtained at various reaction times. (a) FTIR spectra,
Figure 2. Characterizations of the Ni-BTC samples obtained at various reaction times. (a) FTIR
(b) XRD patterns, (c) TGA curve of Ni-BTC-1m, and (d) Nitrogen adsorption and desorption.
spectra, (b) XRD patterns, (c) TGA curve of Ni-BTC-1m, and (d) Nitrogen adsorption and desorption.
To further confirm the composition of the Ni-MOF, the thermogravimetric analyses (TGA) were
To further confirm the composition of ◦the Ni-MOF, the thermogravimetric analyses (TGA)
performed under air with a heating rate of 4 C/min. There are two different stages of weight loss
were performed under air with a heating rate of 4 °C/min. There are two different stages of weight
in the TGA curve of Ni-MOF-1m, as shown in Figure 2c. In the first stage, weight loss of 27.35 wt %
loss in the◦ TGA curve of Ni-MOF-1m, as shown in Figure 2c. In the first stage, weight loss of 27.35
from 100 C to 250 ◦ C could be ascribed to the loss of crystallization water molecules. The second
wt % from 100 °C to 250 °C could◦ be ascribed to the loss of crystallization water molecules. The
sharp weight loss started from 250 C and ended at 400 ◦ C, due to the decomposition of the organic
second sharp weight loss started from 250 °C and ended at 400 °C, due to the decomposition of the
frameworks, and the final residue was NiO [17]. These evidences further prove that the coordinated
organic frameworks, and the final residue was NiO [17]. These evidences further prove that the
or adsorbed H2 O molecules existence in the Ni-MOFs. This result is in conformity to the FTIR data.
coordinated or adsorbed H2O molecules existence in the Ni-MOFs. This result is in conformity to
Additionally, the weight loss is in agreement with the chemical formula Ni3 (C6 H3 (COO)3 )2 ·12H2 O.
the FTIR data. Additionally, the weight loss is in agreement with the chemical formula
In addition, nitrogen adsorption-desorption isotherms, the specific surface area and pore
Ni3(C6H3(COO)3)2·12H2O.
structures of Ni-MOFs were studied by surface area and porosity analyzer, and the results are shown
In addition, nitrogen adsorption-desorption isotherms, the specific surface area and pore
in Figure 2d and Table S3. The Brunauer–Emmett–Teller (BET) specific surface area of Ni-MOF-1m is
structures of Ni-MOFs were studied by surface area and porosity analyzer, and the results are
only 4.85 m2 /g, after the longer reaction time, the specific surface area of Ni-MOF-180m reaches the
shown in Figure 2d 2and Table S3. The Brunauer–Emmett–Teller (BET) specific surface area of
maximum of 10.08 m /g. The average pore sizes of Ni-MOFs are about 4.6 nm except Ni-MOF-180m
Ni-MOF-1m is only 4.85 m2/g, after the longer reaction time, the specific surface area of
(4.1 nm). According to the Barrett–Joyner–Halenda (BJH) analysis of the Ni-BTC samples obtained at
Ni-MOF-180m reaches the maximum of 10.08 m2/g. The average pore sizes of Ni-MOFs are about
various reaction times, as shown in Figure S1, the pore sizes in the micropore range are around 1.7 nm
4.6 nm except Ni-MOF-180m (4.1 nm). According to the Barrett–Joyner–Halenda (BJH) analysis of
for all MOF samples. However, the pore sizes in the mesopore range are different, and it is inferred
the Ni-BTC samples obtained at various reaction times, as shown in Figure S1, the pore sizes in the
micropore range are around 1.7 nm for all MOF samples. However, the pore sizes in the mesopore
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that the
range areporosity comes
different, and from the interparticle
it is inferred that the voids, which
porosity is different
comes from thedue to the varied
interparticle morphology
voids, which is
of the MOFs.
different due to the varied morphology of the MOFs.
Morphological investigations
Morphological investigations of of Ni-MOFs
Ni-MOFswerewerecarried
carriedout
outusing a field-emission
using a field-emission SEM, andand
SEM, the
SEM images are shown in Figure 3. Ni-MOF-1 m exhibits rod-like shapes, but the
the SEM images are shown in Figure 3. Ni-MOF-1 m exhibits rod-like shapes, but the dispersion of dispersion of their
sizes is
their veryisbroad.
sizes very The
broad.largerTheones have ones
larger a length andawidth
have lengthof and
10 µm and 500
width of nm,
10 μmrespectively,
and 500while
nm,
the smaller ones have a length and width of about 500 nm and 100 nm (Figure
respectively, while the smaller ones have a length and width of about 500 nm and 100 nm (Figure 3a,b). The surface of
microcrystals of Ni-MOF-1 m looks very smooth. For the products with longer reaction
3a,b). The surface of microcrystals of Ni-MOF-1 m looks very smooth. For the products with longer time, there are
no apparent
reaction change
time, there inare
theno morphology (Figuresin
apparent change 3c–f
theand S2), suggesting
morphology the success
(Figure 3c–f and of synthesis of
Figure S2),
Ni-MOF in merely one minute.
suggesting the success of synthesis of Ni-MOF in merely one minute.

Figure
Figure 3.
3. SEM
SEM images
images ofof the
the Ni-BTC
Ni-BTC samples
samples obtained
obtained at
at various
various reaction
reaction times.
times. (a,b)
(a,b) Ni-BTC-1
Ni-BTC-1m,m,
(c)
(c) Ni-BTC-5 m, (d) Ni-BTC-30m, (e) Ni-BTC-60 m, and (f) Ni-BTC-180 m. The bar in (a) represents 55
Ni-BTC-5 m, (d) Ni-BTC-30m, (e) Ni-BTC-60 m, and (f) Ni-BTC-180 m. The bar in (a) represents
μm,
µm, and
and the
the bars
bars in
in (b–f)
(b–f) to
to represent
represent 500
500 nm.
nm.

3.1.2. Effect
3.1.2. Effect of
of Mechano-Frequency
Mechano-Frequency of Grinding
In addition
In addition totothe
thegrinding
grindingtime,
time,thethemechano-frequency
mechano-frequency ofof grinding
grinding is is also
also oneone
keykey factor
factor of
of ball-milling conditions. With the assist of water, the products were obtained
ball-milling conditions. With the assist of water, the products were obtained under different under different
frequencies from
frequencies from10 10HzHztoto
5050
HzHzby keeping
by keepingthe reaction time of
the reaction only
time offor onefor
only minute, and theyand
one minute, denoted
they
as Ni-BTC-10 Hz, Ni-BTC-20 Hz, Ni-BTC-30 Hz, Ni-BTC-40 Hz, and Ni-BTC-50
denoted as Ni-BTC-10 Hz, Ni-BTC-20 Hz, Ni-BTC-30 Hz, Ni-BTC-40 Hz, and Ni-BTC-50 Hz, Hz, respectively. Their
XRD patterns were
respectively. TheirshownXRD in Figure 4a.
patterns All these
were shown patterns show the
in Figure 4a. characteristic diffraction
All these patterns peaksthe
show of
Ni3 (BTC)2 ·12Hdiffraction
characteristic 2 O, even the product
peaks of 3Ni-BTC-10Hz.
of Ni (BTC)2·12H2O, The crystallinity
even the product of the
of products obtained
Ni-BTC-10Hz. at
The
10 Hz and 20 Hz are also significantly lower than that obtained at higher frequencies.
crystallinity of the products obtained at 10 Hz and 20 Hz are also significantly lower than that The yield of
Ni-BTC-10Hz
obtained is only
at higher about 39% (Table
frequencies. S4). of
The yield When the mechano-frequency
Ni-BTC-10Hz is only aboutincreases
39% (Tableto 20 Hz,When
S4). the yield
the
increases to about 60%.
mechano-frequency To further
increases increase
to 20 Hz, the theyield
milling frequency,
increases the yield
to about maintains
60%. at about
To further 60–70%.
increase the
milling frequency, the yield maintains at about 60–70%.
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Figure 4. XRD patterns of the Ni-BTC samples obtained at various grinding frequencies (a), with
Figure 4. XRD patterns of the Ni-BTC samples obtained at various grinding frequencies (a), with
addition of different solvents (b), with addition of varied amount of water (c), and at enlarged scales (d).
addition of different solvents (b), with addition of varied amount of water (c), and at enlarged scales
3.1.3.(d).
Effect of Auxiliary Liquid

3.1.3.The effect
Effect of the type
of Auxiliary of auxiliary liquid on the ball milling reaction was studied. In addition
Liquid
to water, the polar solvents MeOH, EtOH, and DMF, commonly used in MOF synthesis, were
also The effect of
explored. ThetheXRD
typepatterns
of auxiliary liquid onwere
of products the ball
shownmilling reaction
in Figure 4b.was Allstudied.
of themInhaveaddition to
similar
water, the polar solvents MeOH, EtOH, and DMF, commonly used in
patterns which match well with the simulated pattern for Ni3 (BTC)2 ·12H2 O, suggesting the success of MOF synthesis, were also
explored.
preparation Theof XRD
productpatterns
in oneofminute
products were shown
whatever the kind in of
Figure 4b. All
auxiliary of them
liquid. The have
yieldssimilar patterns
of the products
which match well with the simulated pattern for Ni (BTC) ·12H
are between 60% to 70% (Table S5). Water is the best choice among them, considering its environment
3 2 2 O, suggesting the success of
preparation
friendliness. of product the
Moreover, in one
effectminute whateverofthe
of the quantity kind
water was ofalso
auxiliary liquid. Unexpectedly,
investigated. The yields of it the
is
products are between 60% to 70% (Table S5). Water is the best choice
found that the product can be obtained without water, as shown in Figure 4c, and the yield can among them, considering its
environment
achieve aboutfriendliness.
56% (Table S6). Moreover,
Under the thewater-assist
effect of the quantity
condition, theofyields
waterincrease
was also investigated.
a little to around
Unexpectedly,
65%. This result it is foundthe
implies thataddition
the product can is
of water benot
obtained without
necessary. Based water, as shown
on this result, in
theFigure
effects4c,
of
and the yield can achieve about 56% (Table S6). Under the water-assist
mechano-frequency were explored again under no liquid-assist condition. In the absence of additives, condition, the yields
increase
even at aa minimum
little to aroundof 10 65%.
Hz, we Thiscan
result
stillimplies
obtain a the addition
product of water
with good is not necessary.
crystallization Based S3).
(Figure on
this result,the
However, theyield
effects of mechano-frequency
drops to only about 29% (Table were S7).explored
As theagain underincreases,
frequency no liquid-assist
the yieldcondition.
increases
In the absence of additives, even at a minimum of 10 Hz, we can still
slightly. Even if the frequency rises to 40 Hz, the yield is only about 40%. When the frequency obtain a product with good
is raised
crystallization (Figure S3).
to 50 Hz (the maximum limitHowever,
frequency the
of yield drops to only
the instrument), the about 29% to
yield rises (Table
56%. S7). As the frequency
In contrast to the case
increases, the yield increases slightly. Even if the frequency rises to 40 Hz, the
with liquid assist (Figure 5), it can be seen that the yield of product with liquid assistance is significantly yield is only about
40%. When the frequency is raised to 50 Hz (the maximum limit frequency
higher than that without liquid assistance. Under the liquid assist condition, the maximum yield can of the instrument), the
yield rises toat56%.
be achieved when In the
contrast to theiscase
frequency overwith
30 Hz,liquid
whileassist (Figure
without 5), itassistance
liquid can be seen thatisthe
there stillyield of
a large
product with liquid
increase in yield at 50 Hz. assistance is significantly higher than that without liquid assistance. Under the
liquid assist condition, the maximum yield can be achieved at when the frequency is over 30 Hz,
while without liquid assistance there is still a large increase in yield at 50 Hz.
Nanomaterials 2018, 8, 1067 7 of 11
Nanomaterials 2018, 8, x FOR PEER REVIEW 7 of 10

Figure5.5.Comparison
Figure Comparisonofof
yields of Ni-BTC
yields samples
of Ni-BTC obtained
samples withwith
obtained and without addition
and without of water
addition (1 mL).(1
of water
mL).
3.1.4. Scalability
3.1.4.InScalability
addition, we investigated the scalability and expandability of the method. We increased the
feed rate by three times
In addition, and five times,
we investigated and foundand
the scalability thatexpandability
the crystallinity of the
of the product
method. Wewas basically
increased the
the
feedsame
rate(Figure
by three4d), andand
times thefive
yield was and
times, slightly
found improved
that the (Table S8). This
crystallinity method
of the canwas
product be used for
basically
bulk preparation
the same (Figureof4d), MOFs andeasily
the yieldat the
wasgram scaleimproved
slightly (2.77 g in (Table
a run). S8).
In general,
This methodthe method
can beisusedrapid,for
high-efficiency, eco-friendly, low cost, and has great scalability.
bulk preparation of MOFs easily at the gram scale (2.77 g in a run). In general, the method is rapid,
Recently, a few
high-efficiency, reports [17,36,37]
eco-friendly, low cost, have
andalso
hasdemonstrated
great scalability. the rapid synthesis of MOFs (Table S9).
Duan Recently,
et al. [36] demonstrated the synthesis of hierarchical
a few reports [17,36,37] have also demonstrated the porous ZIF-8
rapidmaterials
synthesis within
of MOFsone min at
(Table
room temperature
S9). Duan et al. [36]by using organic amines
demonstrated as a supramolecular
the synthesis of hierarchicaltemplate (organic
porous ZIF-8 amine-template),
materials within one
but the bulk organic solvent (methanol) and additives
min at room temperature by using organic amines as a supramolecular template(organic amines) were still required. Jin et(organic
al. [17]
synthesized
amine-template),Ni 3 (BTC) · 12H
but2 the bulk2 O byorganic solvent (methanol) and additives (organic amines) were but
a solution-phase method under room temperature in short time, still
the organic Jin
required. linkeret must
al. [17] to be deprotonated,
synthesized and the
Ni3(BTC) organic solvent were also used. Huang et al. [37]
2·12H2O by a solution-phase method under room
reported
temperaturethe synthesis
in short of F4 -UiO-66
time, but the in 100 s using
organic linkerwater-assisted grinding, however,
must to be deprotonated, and thethe metal source
organic solvent
must be the pre-prepared zirconium clusters. Despite these developments,
were also used. Huang et al. [37] reported the synthesis of F4-UiO-66 in 100 s using water-assisted it should be noted that
the work described
grinding, however,here therepresents
metal source the first
mustexample
be the of ultrafast synthesis
pre-prepared of Ni-MOF
zirconium clusters.byDespite
ball milling
these
without solvent or any preliminary preparation.
developments, it should be noted that the work described here represents the first example of
This fast
ultrafast reaction
synthesis speed is due
of Ni-MOF by ballto the sufficient
milling without energy provided
solvent or anyby the mechanical
preliminary force during
preparation.
ball milling.
This fast reaction speed is due to the sufficient energy provided by the mechanicalsubstance
From a thermodynamic point of view, generally, the chemical potential of a force during in
the solid state is higher than that of the same one in the liquid state [30,38–40].
ball milling. From a thermodynamic point of view, generally, the chemical potential of a substance Thus, the driving force
ofinthe
theformation
solid stateofisNi-MOF
higher than is higher
that ofthan
the that
sameofone solution-based
in the liquidsynthesis methodThus,
state [30,38–40]. [30]. theTherefore,
driving
the
force of the formation of Ni-MOF is higher than that of solution-based synthesis methodhand,
mechanochemical construction of Ni-MOF can be reacted within a short time. On the other [30].
the additional solvents (water, MeOH, EtOH, or DMF) had a good
Therefore, the mechanochemical construction of Ni-MOF can be reacted within a short time. On thedissolution of the raw materials
and,
other thus,
hand,they thecan boost molecular
additional solventsmobility
(water, of the reactants
MeOH, EtOH, or during
DMF)reaction.
had a good Evendissolution
if no addition of
of the
solvent,
raw materials and, thus, they can boost molecular mobility of the reactants during reaction. Evenofif
a small amount of crystal water contained in nickel acetate separates out under the action
ball
no milling,
additionthereby
of solvent,acting a as an auxiliary
small amount solvent.
of crystal Moreover, the acetate
water contained in ion actsacetate
nickel as a base to catalyze
separates out
the deprotonation of the H 3 BTC, thereby increasing the reaction rate.
under the action of ball milling, thereby acting as an auxiliary solvent. Moreover, the acetateIn the experiment, nickel chloride ion
and nickel nitrate were used as the metal source to carry out the reaction,
acts as a base to catalyze the deprotonation of the H3BTC, thereby increasing the reaction rate. In theand no detectable product
was found, which
experiment, nickel proved the inference.
chloride and nickel nitrate were used as the metal source to carry out the
reaction, and no detectable product was found, which proved the inference.
3.2. Electrochemical Performance of Ni-MOF

3.2. Finally, to provePerformance

Electrochemical that the Ni-MOF produced within one minute has considerable electrochemical
of Ni-MOF
performance, cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) were performed
Finally, to prove that the Ni-MOF produced within one minute has considerable
using a three electrode system in 6 mol/L KOH electrolyte and the results were presented in Figure 6.
electrochemical performance, cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD)
The CV was carried out with a potential range from 0 to 0.5 V at varied scan rates (5, 10, 25, 50, 75,
were performed using a three electrode system in 6 mol/L KOH electrolyte and the results were
and 100 mV/s). There are a couple of distinct redox peaks could be observed, which are correspond to
presented in Figure 6. The CV was carried out with a potential range from 0 to 0.5 V at varied scan
the reversible redox of the reversible intercalation and deintercalation of OH- ions [13]. These surface
rates (5, 10, 25, 50, 75, and 100 mV/s). There are a couple of distinct redox peaks could be observed,
which are correspond to the reversible redox of the reversible intercalation and deintercalation of
OH- ions [13]. These surface faradic redox reactions lead to the typical pseudocapacitive behavior of
Nanomaterials 2018, 8, 1067 8 of 11

Nanomaterials 2018, 8, x FOR PEER REVIEW 8 of 10

faradic redox reactions lead to the typical pseudocapacitive behavior of Ni-MOFs. The GCD curves
Ni-MOFs.
under The GCD
different curves
current under
densities in different current
a potential range densities
of 0–0.45 in a potential
V are shown in range of 4b.
Figure 0–0.45 V are
It can be
shown in Figure 4b. It can be found that there is a plateau in the potential from 0.2 to
found that there is a plateau in the potential from 0.2 to 0.25 V at different current densities from 1 to 0.25 V at
different
10 A/g. Suchcurrent densities
a plateau from 1to to
is ascribed the10 A/g.reaction,
redox Such a indicating
plateau istheascribed to the
significant redox reaction,
contribution of the
indicating the significant
pseudo-capacitance, contribution
which agrees well withofthe
thephenomena
pseudo-capacitance,
of CV curves. which agrees capacitance
The specific well with C the
m
phenomena of CV curves. The specific capacitance C (F/g) is calculated from
(F/g) is calculated from the GCD measurement (Figure 4b) according to the following equation [13]:
m the GCD
measurement (Figure 4b) according to the following equation [13]:
Cm = I∆t/∆E = i∆t/(m∆E)
𝐶m = 𝐼∆t/∆𝐸 = 𝑖∆𝑡/(𝑚∆𝐸)
where II is
where is the
the discharge
discharge current
current density
density calculated using II== i/m,
calculated using i/m, i is the current and m is is the
the active
active
mass
mass ofof the electrode, ∆t
the electrode, Δt is
is the
the during
during time
time ofof the
the discharge
discharge curve, and ∆E
curve, and ΔE is
is the
the potential
potential window
window
of
of the
the discharge
discharge curve,
curve, respectively.
respectively. The calculated C
The calculated Cmm values of Ni-MOF-1 are present in Figure S4.

The
The specific capacitance can achieve 640 F/g at the current density
specific capacitance can achieve 640 F/g at the current density ofof11A/g,
A/g, which is comparable
comparable to to
the
the performance
performance of of the
the hydrothermally-synthesized
hydrothermally-synthesized one one[13].
[13].

Figure 6. (a)
Figure 6. (a) Evolution
Evolution of
of CVs
CVs of
of Ni-BTC-1
Ni-BTC-1 at
atvarious
variousscan
scanrates:
rates: 5,
5,10,
10,25,
25,50,
50,75,
75,and
and100
100mV/s;
mV/s; and
and
(b)
(b) charge-discharge diagrams of Ni-BTC-1 at different current densities: 1, 2, 3, 5, 7, and 10A/g.
charge-discharge diagrams of Ni-BTC-1 at different current densities: 1, 2, 3, 5, 7, and 10 A/g.

4. Conclusions
4. Conclusions
We have proposed a mechanical ball milling method for ultrafast synthesis of Ni-based metal
We have proposed a mechanical ball milling method for ultrafast synthesis of Ni-based metal
organic frameworks. The results of XRD show that there is no significant difference in the crystallinity
organic frameworks. The results of XRD show that there is no significant difference in the
of the products obtained at different reaction times (1–180 min), and the stable product can be obtained
crystallinity of the products obtained at different reaction times (1–180 min), and the stable product
even only at macheno-frequency of 10 Hz within one minute without any solvent-assist. Generally,
can be obtained even only at macheno-frequency of 10 Hz within one minute without any
increasing the milling time, raising the mechanical frequency, and the addition of assistant solvent will
solvent-assist. Generally, increasing the milling time, raising the mechanical frequency, and the
increase the yield, while the kind of assistant solvent has no evident effect on the yield. The water is
addition of assistant solvent will increase the yield, while the kind of assistant solvent has no
the best choice among the solvents, considering the environment friendliness. The method is rapid,
evident effect on the yield. The water is the best choice among the solvents, considering the
highly efficiency, eco-friendly, and has great scalability (at the gram scale in a run).
environment friendliness. The method is rapid, highly efficiency, eco-friendly, and has great
scalability (at the
Supplementary gram scale
Materials: in a run).are available online at http://www.mdpi.com/2079-4991/8/12/1067/
The following
s1; Table S1. Yields of Ni-BTC samples obtained at various reaction times; Table S2. FWHM of Ni-BTC samples
obtained at various
Supplementary reaction The
Materials: times; Table S3.are
following Surface area online
available and poreat structures of Ni-BTC samples
www.mdpi.com/link; Table S1.obtained
Yields atof
various
Ni-BTC reaction
samplestimes; Figure
obtained S1. Thereaction
at various BJH analysis
times;ofTable
the Ni-BTC
S2. FWHMsamples obtained
of Ni-BTC at various
samples reaction
obtained times;
at various
Figure S2. SEM images of the Ni-BTC samples obtained at various reaction times. (a) Ni-BTC-5 m, (b) Ni-BTC-30
reaction times; Table S3. Surface area and pore structures of Ni-BTC samples obtained at various reaction times;
m, (c) Ni-BTC-60 m, and (d) Ni-BTC-180 m; Table S4. Yields of Ni-BTC samples obtained at various grinding
Figure S1. The
frequencies withBJH analysis
addition of 1ofmL
thewater;
Ni-BTC samples
Table obtained
S5. Yields at various
of Ni-BTC reaction
samples times;
obtained withFigure S2. SEM
addition images
of different
of the Ni-BTC
solvents; Table samples
S6. Yieldsobtained
of Ni-BTC at various
samplesreaction
obtainedtimes. (a) Ni-BTC-5
with addition m, (b)amount
of varied Ni-BTC-30 m, (c)
of water; Ni-BTC-60
Figure S3. XRDm,
patterns
and (d) of the Ni-BTC
Ni-BTC-180 m;samples
Table S4.obtained
Yieldsatofvarious
Ni-BTCgrinding
samplesfrequencies
obtained at without
variousthe water addition;
grinding Table
frequencies S7.
with
Yields of Ni-BTC
addition of 1 mLsamples obtained
water; Table at various
S5. Yields grinding
of Ni-BTC frequencies
samples without
obtained withthe addition
addition of of water; Table
different S8. Yields
solvents; Table
of Ni-BTC samples obtained at enlarged scales; Table S9. Comparison of the synthesis of MOF in previously
S6. Yields of Ni-BTC samples obtained with addition of varied amount of water; Figure S3. XRD patterns of the
published reports; Figure S4. Diagram of the specific capacitance of materials at different current densities.
Ni-BTC samples obtained at various grinding frequencies without the water addition; Table S7. Yields of
Ni-BTC samples obtained at various grinding frequencies without the addition of water; Table S8. Yields of
Ni-BTC samples obtained at enlarged scales; Table S9. Comparison of the synthesis of MOF in previously
published reports; Figure S4. Diagram of the specific capacitance of materials at different current densities.

Author Contributions: Conceptualization: C.-A.T.; data curation: R.Z. and L.W.; formal analysis: R.Z. and R.C.;
funding acquisition: C.-A.T.; investigation: R.Z. and R.C.; methodology: C.-A.T. and J.W.; project
Nanomaterials 2018, 8, 1067 9 of 11

Author Contributions: Conceptualization: C.-A.T.; data curation: R.Z. and L.W.; formal analysis: R.Z. and R.C.;
funding acquisition: C.-A.T.; investigation: R.Z. and R.C.; methodology: C.-A.T. and J.W.; project administration:
J.W.; supervision: C.-A.T. and X.Z.; visualization: L.W.; writing—original draft: C.-A.T.; writing—review and
editing: X.Z. and J.W.
Funding: The National Natural Science Foundation of China (21573285), the Natural Science Foundation of
Hunan Province (2018JJ3597), and a research project of National University of Defense Technology (ZK16-03-51).
Conflicts of Interest: The authors declare no conflict of interest.

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