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Continuous synthesis for zirconium metal-organic frameworks with high

quality and productivity via microdroplet flow reaction

Article  in  Chinese Chemical Letters · October 2017

DOI: 10.1016/j.cclet.2017.09.057

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Accepted Manuscript

Title: Continuous synthesis for zirconium metal-organic

frameworks with high quality and productivity via
microdroplet flow reaction

Authors: Ying Wang, Liangjun Li, Liting Yan, Lei Cao,

Pengcheng Dai, Xin Gu, Xuebo Zhao

PII: S1001-8417(17)30407-2
DOI: https://doi.org/10.1016/j.cclet.2017.09.057
Reference: CCLET 4263

To appear in: Chinese Chemical Letters

Received date: 12-8-2017

Revised date: 20-9-2017
Accepted date: 26-9-2017

Please cite this article as: Ying Wang, Liangjun Li, Liting Yan, Lei Cao, Pengcheng Dai,
Xin Gu, Xuebo Zhao, Continuous synthesis for zirconium metal-organic frameworks
with high quality and productivity via microdroplet flow reaction, Chinese Chemical
Letters https://doi.org/10.1016/j.cclet.2017.09.057

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Communication

Continuous synthesis for zirconium metal-organic frameworks with high quality

and productivity via microdroplet flow reaction

Ying Wanga,b,1, Liangjun Lia,1, Liting Yana,b, Lei Caoa, Pengcheng Daia, Xin Gua, Xuebo Zhaoa,

a
Research Center of New Energy Science and Technology, Research Institute of Unconventional Oil & Gas and Renewable Energy, China University of
Petroleum (East China), Qingdao 266580, China
b
College of Science, China University of Petroleum (East China), Qingdao 266580, China

 Corresponding author.
E-mail address: zhaoxuebo@upc.edu.cn (X. Zhao).

1
These authors contributed equally to this work.

Graphical abstract

A series of Zr-based metal-organic frameworks were continuously synthesized with high quality and high productivity through
microdroplet flow reaction.

ARTICLE INFO ABSTRACT

Article history: Zirconium metal-organic frameworks (Zr-MOFs) represent the most promising candidates among
Received MOFs for industrial utilizations owing to their high porosity and excellent stability. However, the
Received in revised form efficient synthesis of Zr-MOFs combining with continuous production, high productivity and good
Accepted product quality still remains a critical issue for practical applications. Herein, we report an efficient
Available online method of synthesizing a series of Zr-MOFs through a microdroplet flow reaction, which is more
accommodate the requirements of industrial production. Four types of Zr-based MOFs with different
Keywords: ligands and topologies (MOF-801, MOF-804, DUT-67 and MOF-808) were produced as a pure phase
Zirconium metal-organic frameworks of high quality crystalline with uniform morphologies. Furthermore, this series of Zr-MOFs were
Microdroplet flow reaction obtained in a continuous way and at a space-time yield (STY) highly up to 367.2 kg·m3·d1. These
Continuous synthesis MOFs exhibit the similar pore structure and thermal stability with that prepared from conventional
Space-time yield solvothermal synthesis. CO2 sorption studies on these MOFs demonstrate that the hydroxyl
CO2 adsorption groups on ligand can render MOFs with high CO2/N2 selectivity.

Metal-organic frameworks (MOFs), an emerging class of multifunctional porous materials, have attracted extensive attentions due to
their unprecedented surface areas, variable structures and tunable functionalities [1-4]. Thanks to these characteristics, they have found
plenty of applications including gas storage [5,6] and separation [7,8], catalysis [9-11], drug delivery [12], photoelectronics [13] and
sensing [14] et al. Furthermore, the derivatives of MOFs also have displayed promising potentials in energy storage and energy
conversion technologies [15-19]. The prerequisite for realizing real-world applications is the ability to produce MOFs at large scale,
and at the same time ensuring high quality and low cost of the product. However, the efficient synthetic technique combining with
continuous production, high productivity and good product quality remains a critical issue for practical applications [20]. In order to
diminish the gaps between laboratory synthesis and industrial production, some synthetic techniques, such as sonchemical [21,22],
microwave [23,24], spray drying [25], electrochemical [26], aerosol [27], mechanochemical [28,29], and flow chemistry synthesis [30-
32], have been explored. Despite of significant advances, few MOFs appear to be commercially available at large quantities (kilogram
scale) [33,34]. Therefore, the development of facial and efficient synthetic methods for MOFs is essential.
Zr-based MOFs, typically contain multi-topic Zr-O clusters connected by organic ligands, exhibit high porosity, excellent
thermal/hydro stability, rich topologies and tunable functionalities [35,36]. Owing to these merits, they have been considered as one of
the most promising candidates among MOFs for practical applications [37]. Although several Zr-based MOFs have been reported in
recent
———years [38-40], the investigation of synthetic methodologies for Zr-based MOFs is still rare. Recently, some groups have
demonstrated that the UiO-66 can be synthesized through flow reaction [41-44]. Nevertheless, such works are still far from adequate
for practical applications, and the general synthetic strategy that is applicable for Zirconium MOFs (Zr-MOFs) comprised of different
structures and topologies is highly desired. In this work, we report a method of continuous production for Zr-based MOFs through a
microdroplet flow reaction strategy. Four types of Zr-MOFs, namely MOF-801 [45], MOF-804 [46], DUT-67 [47] and MOF-808 [48],
which bearing different secondary building units (SBUs) and topologies, were prepared in high yield, high quality and high
productivity (termed as MF-MOF-801, MF-MOF-804, MF-DUT-67, and MF-MOF-808, respectively, where the MF represents
“Microdroplet flow”). Structural studies revealed the nearly same properties of these MOFs compared to that derived from
conventional solvothermal synthesis (termed as ST-MOF-801, ST-MOF-804, ST-DUT-67, and ST-MOF-808, respectively, where the
ST represents “Solvothermal”). Gas-sorption studies of these Zr-based MOFs revealed outstanding CO2 uptake at low pressures and
high CO2/N2 selectivity.
MOF-801 is a Zr-MOF formed by the linkage of fumaric acid and Zr6(μ-O)4(OH)4(COO)12 SBU [45]. The short ligand length of
fumaric acid gives rise to a narrow pore window (0.48 nm), which is the smallest among Zr-series MOFs. MOF-804 is a fcu type MOF
assembled from the Zr6(μ-O)4(OH)4(COO)12 SBU and 2,5-dihydroxyterephthalic acid, which bearing phenolic hydroxyl groups on
ligand [46]. DUT-67 is a Zr-MOF composed of the Zr6(μ-O)4(OH)4(COO)8 SBU and thiophene-2,5-dicarboxylate acid (H2TDC) [47].
The V-shaped ligand leads to a reo network, a rare topology in Zr-MOFs. MOF-808 is a spn type Zr-MOF assembled from H3BTC and
Zr6(μ-O)4(OH)4(COO)6 SBU, in which a meso-scale cage is involved in the framework [48]. Owing to the distinctive steric extension
and functional groups in ligands and different framework topologies of resultant MOFs, these Zr-MOFs were selected as research
objects in this work. They were synthesized through a home-built microdroplet flow system which comprises of three syringe pumps
connected by one micro-mixer, one heating coil and sample collecting unit (Scheme 1). In a typical procedure, both solutions of metal
salt and organic ligand were pumped into the static micro-mixer equipped with a magnetic stirring to form a homogeneous solution.
Organic acid (formic acid, and acetic acid) or inorganic acid (HCl) was added into above solution as the modulator. Then, the solution
of reactants and oil phase was pumped into a micro-pipeline co-currently at a controlled flow rate to form uniform and dispersed
microdroplets. These droplets passed through a heating coil (2 mm i.d. and 3 mm o.d., and the length is 2 m) that were immersed in a
heating bath. White precipitate formed in these microdroplets. Afterwards, these microdroplets were cooled down when passing
through a cooling coil immersed in ice-water bath. The precipitate was separated from mixed phase (including the oil, organic solvent
and samples) by centrifuging at 5000 rpm for 10 min and washed with Soxhlet extraction using petroleum ether and ethanol as the
eluent. These samples were soaked in the ethanol before characterization.
Powder X-ray diffraction (PXRD) patterns confirm that all of these MOFs prepared under MF conditions possess the identical
structure with crystallographic data of MOF-801, MOF-804, DUT-67 and MOF-808, respectively (Fig. 1a-d) [45-48]. No extra peaks
were observed on PXRD patterns, demonstrating high purity of these samples. The high degree of crystallinity is revealed by the sharp
peaks in PXRD patterns. Notably, the crystallinity of these MOFs is even higher than that derived from conventional solvothermal
synthesis, especially for MOF-808, which exhibited a weak crystallinity when prepared under solvothermal condition (see PXRD
patterns in Figs. S1-S4 in Supporting information). These results suggest that the microdroplet flow reaction can produce pure and
highly crystalline Zr-MOFs. The quality of the obtained Zr-MOFs can also be characterized by scanning electron microscopy (SEM).
As shown in Fig. 1a, a pure phase of regular polyhedral crystals is observed for MF-MOF-801. The crystals of MF-MOF-801 exhibit a
uniform dimension of about 300 nm. Different from MF-MOF-801, the MOF-801 derived from conventional solvothermal synthesis
(ST-MOF-801) exhibits an inhomogeneous phase of particles with irregular shapes and non-uniform grain sizes (in the range of 2-5 μm,
Fig. S5 in Supporting information). MF-MOF-804 exhibits a phase of regular polyhedral crystals. The crystal sizes are in the range of
100-500 nm. (Fig. 1b and Fig. S6 in Supporting information). As shown in Fig. 1c, MF-DUT-67 exhibits a phase of crystals with
regular polyhedron crystals (3-5 μm), which is coexisted with some nano-scale crystal grains (200-500 nm). The morphology and
crystal size of MF-DUT-67 is similar to that of ST-DUT-67 (Fig. S7 in Supporting information). MF-MOF-808 exhibits a single phase
of regular hexahedral crystals with a dimension of about 300 nm. The regular shapes and sizes of crystals for MF-MOF-808 show a
clear contrast with that derived from conventional solvothermal synthesis, under which the obtained ST-MOF-808 exhibit irregular
shapes and sizes (Fig. 1d and Fig. S8 in Supporting information).
Although these MOFs were synthesized in a short period (32-80 min) under MF conditions, all of products possess high purity and
crystallinity. In contrast, the solvothermal synthesized MOFs exhibit a much weaker crystallinity and product quality, even though a
long reaction time (e.g., 24 h) is employed under solvothermal conditions. Above observations hints the superiority of MF synthesis to
conventional solvothermal synthesis in terms of product quality. The much smaller sizes combined with uniform morphologies can
render these MOFs with broader application prospects. The high quality of crystals can be attributed to the unique advantages of
microdroplet flow reaction synthesis. The large surface-area-to-volume ratio, the efficient exchange of mass/heat and the rapidly flow
recirculation of reactants in microdroplet flow reaction conditions can accelerate crystal nucleation and advance crystal growth [49-52].
With accelerated nucleation and crystal growth process, high quality Zr-MOFs can be formed in a short reaction time under MF
conditions.
Beside of high quality, the production rate is also an essential aspect for MOF production as it is highly correlated with cost. The
yield calculated from the actual weight of activated MOFs divided by theoretical weight is shown in Fig. 2a. In solvothermal synthesis,
the yield for ST-MOF-801 is 65.7 % (calcd. on the basis of fumaric acid) after 24 h of solvothermal reaction, which is consistent with
the literature results [48]. In comparison, a yield of 85.2% is obtained for MF-MOF-801 after 32 min of reaction under MF conditions,
30% higher than that derived from solvothermal synthesis. The much higher yield is also found on other Zr-MOFs. The higher yield
could be attributed to the functions of MF conditions, under which the more efficient mass/heat transfer lead to the higher efficient
conversion of reactants. With higher conversion rate in a short reaction time, very high STY [41] was observed for these MOFs. As
shown in Fig. 2b, the STY value for MF-MOF-801 was 367.2 kg·m3·d1, which is 29.3 times higher than that of ST-MOF-801 (12.5
kg·m3·d1). The STY values for MF-MOF-804, MF-DUT-67 and MF-MOF-808 were calculated as 247.1, 114.3 and 136.4 kg·m3·d1,
respectively, which were also much higher than STY values of corresponding MOFs derived from solvothermal synthesis (Table S1 in
Supporting information). The remarkable differences highlight the superiority of MF reaction to conventional solvothermal synthesis in
terms of productivity, that MF reaction can produce much higher amount of MOFs at a given time and space. The excellent
productivity renders this method to be very promising for practical application.

N2 isotherms at 77 K were measured on the activated samples of these Zr-MOFs to evaluate their pore structures. As shown in Fig. 3,
all of these samples exhibited a Type-I isotherm with a steep increase in the low pressure range and a plateau in the middle pressure
range, suggesting an overall microporous nature. The Brunauer-Emmett-Teller (BET) surface areas of MF-MOF-801, MF-MOF-804,
MF-DUT-67 and MF-MOF-808 were calculated as 833.4, 481.8, 679.1 and 1842.2 m2/g, respectively. Pore size distributions (PSD)
calculated from nonlocal density function theory (NLDFT) demonstrated the microporous structure. MF-MOF-801, MF-MOF-804,
MF-DUT-67 and MF-MOF-808 possessed total pore volume values of 0.413, 0.703, 0.314 and 1.263 cm3/g, respectively (Table S2 in
Supporting information). The BET surface areas for these MOFs are comparable to those derived from solvothermal synthesis, except
of MF-MOF-801, which showed a higher BET surface area than ST-MOF-801. This higher BET surface area can be attributed to the
higher quality of obtained MOFs. Thermal gravimetric analysis (TGA) demonstrated that all of these MOFs exhibited excellent
thermal stability in the air. These as-synthesized samples of MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808 show the
thermal stability up to 363 oC, 294 oC, 398 oC and 529 oC respectively, which are almost identical with the MOFs prepared from
conventional solvothermal methods (Fig. S9-S12 in Supporting information).

The different porous structures for these Zr-based MOFs encourage us to investigate their CO2 adsorption properties which are
relevant with CO2 capture from flue gas. As shown in Fig. 4a, CO2 adsorption isotherms were measured at 298 K on the activated
samples of these Zr-based MOFs in the pressure range of 0-1 bar. CO2 uptake at 298 K and 1 bar on MF-MOF-801, MF-MOF-804,
MF-DUT-67 and MF-MOF-808 are 1.37, 1.00, 1.98 and 2.00 mmol/g, respectively. Comparatively, rather small amount of N2 was
adsorbed on these MOFs, which can be ascribed to the zero quadrupole moments for N2 molecules. The higher adsorption affinity for
CO2 compared with the limited uptake of N2 indicated the significant improvement in the CO2/N2 adsorptive selectivity of these Zr-
based MOFs. To predict CO2/N2 binary mixture selectivity, the ideal adsorption solution theory (IAST) calculation, whose reliability
has been verified on several MOFs and other adsorbents [53-55], was used to evaluate the gas adsorption selectivity of CO 2/N2. CO2/N2
Selectivities of MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808 for equal fractions of gas mixtures (CO2/N2 = 50/50,
v/v) in the pressure range of 0-1 bar were revealed in Fig. 4b. The CO2/N2 selectivity on these Zr-MOFs are 31.1, 57.2, 26.9 and 9.14 at
298 K and 1 bar, respectively. The MF-MOF-804 exhibits the highest CO2/N2 selectivity among those MOFs and the superior CO2/N2
selectivity can be ascribed to the function of decorated phenolic hydroxyl groups [56]. The polar phenolic hydroxyl groups on MOF-
804 can increase the hydrophilic of frameworks, thus increasing the interaction strength of CO2 with the frameworks, which also have
been suggested by the high Qst (~ 33 kJ/mol, Fig. S13-S16 in Supporting information). Such observations are consistent with the recent
report in CO2 adsorption [57,58]. The outstanding CO2/N2 selectivity combined with excellent stability allows MOF-804 to be a
promising candidate for CO2 capture.

In summary, a series of Zr-based MOFs: MOF-801, MOF-804, DUT-67 and MOF-808, which comprise of different ligands and
topologies, were continuously synthesized via a microdroplet flow reaction. Compared to MOFs derived from conventional
solvothermal synthesis, the MOFs obtained from microdroplet flow reaction possess a higher degree of crystallinity and more uniform
morphologies. Besides, these Zr-MOFs exhibit higher yields and much superior space-time yields compared to that prepared from
solvothermal synthesis, even though microdroplet flow reaction proceeds with a short reaction time. The space-time yield values for
MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808 are highly up to 367.2, 247.1, 114.3, and 136.4 kg·m3·d1, respectively,
which outperforms current synthetic technologies. N2 isotherms and TGA plots of these Zr-MOFs that prepared from microdroplet
flow reaction demonstrate the similar pore structure and thermal stability with that derived from solvothermal synthesis. Gas sorption
studies reveal that the MOF-804, which is decorated with phenolic hydroxyl groups on ligand, exhibits the higher CO2/N2 selectivity
over other Zr-MOFs. The continuous synthesis, good product quality and high productivity of microdroplet flow reaction are expected
to realize large-scale production for Zr-MOFs in practical applications.
Acknowledgments
This work was supported by grants from the National Natural Science Foundation of China (Nos. 21401215, 21473254) and the
Special Project Fund of “Taishan Scholars” of Shandong Province (No. ts201511017).
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(a) Simulated pattern for MOF-801 (b) Simulated pattern for MOF-804
MF-MOF-801 MF-MOF-804
Intensity (a.u.)

Intensity (a.u.)
Fumaric acid DOBDC

10 20 30 40 50 60 10 20 30 40 50 60
2-Theta (degree) 2-Theta (degree)
(c) Simulated pattern for DUT-67
(d) Simulated pattern for MOF-808
MF-DUT-67
MF-MOF-808
Intensity (a.u.)

Intensity (a.u.)
H2TDC
H3BTC

10 20 30 40 50 60 10 20 30 40 50 60
2-Theta (degree) 2-Theta (degree)

Fig. 1. PXRD patterns and SEM images of the crystal obtained by microdroplet flow synthesis: (a) MF-MOF-801, (b) MF-MOF-804, (c) MF-DUT-67 and (d)
MF-MOF-808 crystals.
(a) 120 Microdroplets flow synthesized MOFs (b) 500
Microdroplets flow synthesized MOFs
100 Solvothermally synthesized MOFs Solvothermally synthesized MOFs
400

STY (kg m d )
80

-1
Yield (%)

300

-3
60
200
40

20 100

0 0
MOF-801 MOF-804 DUT-67 MOF-808 MOF-801 MOF-804 DUT-67 MOF-808

Fig. 2. (a) High conversion and (b) space-time yield (STY) of these crystals obtained by microdroplet flow synthesis and conventional solvothermal synthesis of
MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808.
(a) 300 (b) (c) (d) 800
500 1.0 200 MF-MOF-808-ads

dv/(d) (cm g nm )
-1

Amount adsorbed (cm STP/g)

700
Amount adsorbed (cm STP/g)

MF-MOF-808-des

Amount adsorbed (cm STP/g)

Amount adsorbed (cm STP/g)

ST-MOF-808-ads

-1
400 0.5 600 ST-MOF-808-des

3
200 150

3
3

0.8

3
500

dv/(d) (cm g nm )
1.0 MF-DUT-67-ads

-1
dv/(d) (cm g nm )

300
-1

0.8 MF-MOF-801-ads 0.0 0.6 MF-DUT-67-des

400 1.0

dv/(d) (cm g nm )
-1
100

-1
MF-MOF-801-des
-1

0.6 0 10 20 30 40 ST-DUT-67-ads
100 0.4

3
200
3

ST-MOF-801-ads Pore (nm) ST-DUT-67-des 300

-1
0.4 ST-MOF-801-des 0.5
0.2

3
0.2
MF-MOF-804-ads
50 200
100 0.0
0 0.0 MF-MOF-804-des 0.0
0 5 10 15 20 0 5 10 15 20 100
ST-MOF-804-ads Pore (nm) 0 5 10 15 20 25 30
Pore (nm) 0 0
ST-MOF-804-des 0 Pore (nm)

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0) Relative pressure (P/P0) Relative pressure (P/P0) Relative pressure (P/P0)

Fig. 3. N2 sorption isotherms at 77 K and pore size distribution obtained from Nonlocal density function theory (NLDFT) on (a) MF- and ST-MOF-801; (b) MF-
and ST-MOF-804; (c) MF- and ST-DUT-67; (d) MF- and ST-MOF-808.
(a) (b) 60
2.0 CO2 adsorption on MF-MOF-801
MF-MOF-801
Adsorbed amounts (mmol/g)

CO2 adsorption on MF-MOF-804

MF-MOF-804
CO2 adsorption on MF-DUT-67

CO2/N2 selectivity
1.5 MF-DUT-67
CO2 adsorption on MF-MOF-808 40 MF-MOF-808
N2 adsorption on MF-MOF-801
1.0 N2 adsorption on MF-MOF-804
N2 adsorption on MF-DUT-67
20
0.5 N2 adsorption on MF-MOF-808

0.0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Pressure (bar) Pressure (bar)

Fig. 4. (a) CO2 and N2 adsorption isotherms on MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808 at 298 K and 0-1 bar; (b) The predicted CO2/N2
selectivity of MF-MOF-801, MF-MOF-804, MF-DUT-67 and MF-MOF-808 at different pressures.
Scheme 1. Schematic representation of the general microdroplet flow reaction.

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