In Situ Investigation of Multicomponent MOF Crystallization during
Rapid Continuous Flow Synthesis
Brandon He, Lauren K. Macreadie, James Gardiner, Shane G. Telfer, and Matthew R. Hill*

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ABSTRACT: Access to the potential applications of metal−
organic frameworks (MOFs) depends on rapid fabrication. While
there have been advances in the large-scale production of single-
component MOFs, rapid synthesis of multicomponent MOFs
presents greater challenges. Multicomponent systems subjected to
rapid synthesis conditions have the opportunity to form separate
kinetic phases that are each built up using just one linker. We
sought to investigate whether continuous flow chemistry could be
adapted to the rapid formation of multicomponent MOFs,
exploring the UMCM-1 and MUF-77 series. Surprisingly, phase
pure, highly crystalline multicomponent materials emerge under these conditions. To explore this, in situ WAXS was undertaken to
gain an understanding of the formation mechanisms at play during flow synthesis. Key differences were found between the ternary
UMCM-1 and the quaternary MUF-7, and key details about how the MOFs form were then uncovered. Counterintuitively, despite
consisting of just two ligands UMCM-1 proceeds via MOF-5, whereas MUF-7 consists of three ligands but is generated directly from
the reaction mixture. By taking advantage of the scalable high-quality materials produced, C6 separations were achieved in
breakthrough settings.

KEYWORDS: metal−organic frameworks, X-ray diffraction, synthetic methods, crystal growth, adsorption

■ INTRODUCTION

Metal−organic frameworks (MOFs) are highly porous
materials and have accumulated great interest due to their
versatility of potential and actual applications. Consisting of
judiciously selected metal ions or clusters and organic linkers,
these materials can be synthesized for specific purposes. The
idea of incorporating multiple functionalities into one MOF
has always been attractive due to the promise of increased
MOF complexity and specificity for target applications.1

Examples of these are multivariate MOFs, which are
isoreticular analogues of a parent system created through
employing multiple linkers with different substituents but
identical lengths.1,2 Since the linkers are not sufficiently distinct
from one another, they become randomly distributed in the
crystalline lattice causing disorder in the structure.2−5 This
contrasts with multicomponent MOFs which use multiple
topologically distinct linkers to form a MOF. The linkers are
arranged with regularity in the MOF structure, enabling a
higher degree of control in functional group distribution. For
example, in catalysis, fine control of the pore chemistry
through the inclusion of catalytic and modulating functional
groups, on separate linkers, facilitates control of the catalytic
reaction rate, regioselectivity, and/or stereoselectivity of the
product.6,7 Furthermore, the tunable nature of the pore
chemistry can be extended to applications in luminescence,
selective gas separation, and gas storage.6−16

The synthesis of multicomponent MOFs to date has been
limited to time-intensive, laboratory-scale solvothermal batch
methods. This is because precise molar ratio combinations are
needed to converge on these materials and avoid the formation
of undesired competing phases, such as MOFs comprised of
only one kind of linker. However, the growing interest in
multicomponent MOFs provides motivation to investigate
methods for large-scale synthesis, for example, continuous flow
methods (Figure 1). UMCM-1 {[Zn4O(bdc)(btb)4/3]n} is a
ternary MOF comprised of benzene-1,3,5-tribenzoic acid
(H3btb) and benzene-1,4-dicarboxylic acid (H2bdc), combined
together in a precise molar ratio.14 When this molar ratio is
disregarded, other frameworks can be simultaneously formed,
for instance, MOF-5 {[Zn4O(bdc)3]n} and MOF-177 {[Zn4O-
(btb)2]n}. The formation of multiple products can also be seen
in quaternary systems, such as MUF-7, {[Zn4O-
(btb)4/3(bpdc)1/2(bdc)1/2]n}, comprised of H3btb, H2bdc,
and biphenyl-4,4′-dicarboxylic acid (H2bpdc). The addition
of a third linker increases the number of potential undesired

Received: August 30, 2021
Accepted: October 25, 2021
Published: November 5, 2021

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https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Brandon+He"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdf
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phases that can be formed, including IRMOF-10 {[Zn4O-
(bpdc)3]n} and SUMOF-4 {[Zn4O(bdc)2(bpdc)]n}. In partic-
ular, the rotational flexibility of the terminal phenyl rings in
H3btb contributes to a propensity to form these side phases.
This can be circumvented through use of a planar, tritopic
linker such as 5,5′,10,10′,15,15′-hexamethyltruxene-2,7,12-
tricarboxylic acid (H3hmtt), as seen with the development of
MUF-77 {[Zn4O(hmtt)4/3(bpdc)1/2(bdc)1/2]n}.

11 The com-
plexity of synthesizing multicomponent MOFs increases with
the number of components present, leading to different
potential phase combinations of organic linkers.11

Continuous flow chemistry is typically performed in a plug
flow reactor, which exhibits tightly controlled reaction
parameters, a smaller footprint compared to batch reactors,
and enhanced process safety from requiring lower solvent
volumes.17−19 MOF synthesis (Figure 1) using continuous
flow is typically performed by mixing the metal and linker
solutions which lead to reduced reaction times as a result of
leveraging high reactor surface area to volume ratios and
improved heat and mass transfer.20−22 The versatility of flow
chemistry to synthesize a variety of MOFs with high space time
yields (STYs) has been demonstrated by numerous
groups.23−30 STY is the mass of product per unit volume of
reactor in a 24 h period and, along with production rates, a key
metric in determining the viability of a process.
MOF formation is known to undergo a number of

transitions between reaction intermediates before forming
the thermodynamic product.31−33 For example, the solvother-
mal synthesis of MIL-53(Al) undergoes phase transitions from
reaction intermediates, MOF-235 and MIL-101, before
transitioning into MIL-53(Al).34 Continuous syntheses are
often optimized to maximize product yield and throughput,
which is a result of the reaction kinetics and can be an issue for
MOFs that require phase transitions. Therefore, careful
management of residence time is needed to tune continuous
flow synthesis and achieve the desired pure product. Previous
continuous synthetic experiments of MOFs indicate that the
kinetic product in some cases can be the thermodynamic
product (i.e., Cu-BTC, UiO-66, and MIL-53(Al)) obtained in
solvothermal syntheses.24,30 While this is ideal, it remains
unknown whether this is true for the synthesis of multi-

component MOFs, where there is the potential for numerous,
undesired single-component kinetic products to be formed.
In addition to monitoring phase transitions, the kinetics of

nucleation and growth have been obtained for single-
component MOFs such as Cu-BTC, ZIF-8, Zr-Fum, and
MIL-53(Fe).31,35−37 The growth of these MOFs has been
modeled using Avrami−Erofe’ev as a base model and also
either the Gualtieri or Finke−Watzky model.38−41 These
models describe the formation mechanisms, with previous
findings showing that the formation mechanism of these MOFs
typically varies between nucleation rate limited or phase
boundary (surface reaction) rate limited.37

Herein, we report the use of a continuous flow chemistry
approach for the synthetic optimization of two multi-
component MOFs, UMCM-1 and MUF-77-methyl (Figure
1), with high phase purity. We demonstrate for the first time
the suitability of continuous flow chemistry for the synthesis of
multicomponent MOFs of this type. In situ synchrotron wide-
angle X-ray scattering (WAXS) was employed to determine the
mechanism of crystal growth and associated kinetic parameters
for ternary and quaternary MOFs. Exploiting this new
synthetic avenue toward bulk multicomponent MOF produc-
tion, we demonstrate its industrial practicality. Here, 2,3-
dimethylbutane (2,3-DMB), a C6 isomer, was separated under
breakthrough conditions using magnetic induction swing
adsorption (MISA).

■ EXPERIMENTAL SECTION
Materials. The reagents zinc acetate dihydrate (Zn(OAc)2.2H2O),

terephthalic acid (H2bdc), 4,4′-biphenyldicarboxylic acid (H2bpdc),
aluminum chloride, acetyl chloride, 1,3,5-triphenylbenzene, sodium
hydroxide (NaOH), anhydrous magnesium sulfate (MgSO4),
bromine, and 1-indanone were purchased from Sigma-Aldrich and
used without further purification. The solvents dimethylformamide
(DMF), dichloromethane (DCM), ethanol, and 1,4-dioxane were of
analytical grade and were purchased from Sigma-Aldrich and used as
received. 4,4′,4″-Benzene-1,3,5-triyl-tribenzoic acid (H3btb) and
requisite precursors were synthesized as described in the literature.42

5,5′,10,10′,15,15′-Hexamethyltruxene-2,7,12-tricarboxylic acid
(H3hmtt) and requisite precursors were synthesized as described in
the literature.9,11

UMCM-1 Synthesis. Synthesis of UMCM-1 was performed using
a Vaportec R4 reactor with R2 pump modules. A Zn(OAc)2·2H2O
solution (0.1987 g, 0.905 mmol, 1 equiv) was prepared in 5 mL of
DMF. The ligand solution was prepared in DMF (5 mL) containing
H2bdc (0.0450 g, 0.271 mmol, 0.3 equiv) and H3btb (0.1067 g, 0.243
mmol, 0.27 equiv). The two solutions were each pumped into a 10
mL reactor coil at a rate of 0.5 mL/min for a combined flow rate of 1
mL/min. The reaction was conducted in a Vaportec R4 reactor with
R2 pump modules at 85 °C and 5 bar pressure. The reaction was
cooled to room temperature, and the precipitate was collected
through centrifugation. The collected product was washed twice with
30 mL of DMF and solvent exchanged thrice with 30 mL of DCM
over three days. The samples were dried under flowing N2 to yield a
white solid (average yield 0.1069 g, 57%). All manipulations of the
product while performing solvent exchange with DCM were under
nitrogen atmosphere.

MUF-77-Methyl Synthesis. Synthesis of MUF-77-methyl was
performed using a Vaportec R4 reactor with R2 pump modules. A
Zn(OAc)2·2H2O solution (0.2200 g, 1.002 mmol, 1 equiv) was
prepared in 5 mL of DMF. The ligand solution was prepared in DMF
(5 mL) containing H2bdc (0.0159 g, 0.096 mmol, 0.09 equiv),
H2bpdc (0.0242 g, 0.100 mmol, 0.10 equiv), and 0.0252 M H3hmtt
(0.1408 g, 0.252 mmol, 0.25 equiv). The two solutions were pumped
into a 10 mL reactor coil at a rate of 0.5 mL/min for a combined flow
rate of 1 mL/min. The reaction was conducted in a Vaportec R4
reactor with R2 pump modules at 85 °C and 5 bar pressure. The

Figure 1. Real time in situ X-ray diffraction monitoring of continuous
flow MOF synthesis for UMCM-1 (above) and MUF-77 (below)
showing the difference in formation mechanism between the two
MOF systems.

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collected product was washed twice with 30 mL of DMF and solvent
exchanged thrice with 30 mL of DCM over three days. The samples
were dried under flowing N2 to yield a pale-yellow solid (average yield
0.1152 g, 50%).

■ RESULTS AND DISCUSSION

Synthetic Optimization. UMCM-1, {[Zn4O(bdc)-
(btb)4/3]n}, is a ternary framework that exhibits an muo
topology and possesses both micropores and mesopores which
do not collapse upon desolvation of the framework.14 Based on
the reported solvothermal batch procedure for the synthesis of
UMCM-1, we developed a continuous flow process for the
synthesis of this multicomponent MOF.14,43 For flow syn-
thesis, zinc acetate dihydrate was used in place of zinc nitrate
hexahydrate to minimize any safety concerns related to nitrate
buildup at scale. The reaction conditions were optimized for
reaction temperature and residence time within the reactor as
outlined in Table 1. For each varying condition, the resultant
white suspension was collected from the reactor and washed
with DMF three times followed by solvent exchange with
DCM over three days, with fresh DCM being replaced after
each day.
To determine the phase purity of the UMCM-1 synthesized

under continuous flow conditions, the product was digested
and analyzed by 1H NMR spectroscopy to identify the linker
ratio. A linker ratio of 4/3 btb to 1 bdc was expected for phase
pure UMCM-1, and instead a ratio of 4/3 btb and 5/4 bdc was
observed in the 1H NMR spectra for all samples (Figure S1).
This indicated an excess of 1/4 bdc in the flow-synthesized
UMCM-1 product. This could be a result of bdc remaining
trapped in the pores; however, coformation of MOF-5
{[Zn4O(bdc)3]n} in the reaction is more likely as the MOF
was washed extensively. In this case, the ratio of linkers would
suggest a product ratio of 89% UMCM-1 and 11% MOF-5.
Powder X-ray diffraction (PXRD) (Figure 2A and Figure S3)
of the samples shows the desired UMCM-1 reflections and, to
a lesser extent, the MOF-5 reflection at a 2θ angle of 6.8°
which confirms the coformation of MOF-5.11 Thermal stability
of the UMCM-1 frameworks was examined using thermogravi-
metric analysis (TGA) and corresponded to the reported
UMCM-1 thermal degradation profile by Matzger and co-
workers.14 An initial mass loss was observed at 150 °C,
attributed to DMF remaining in the pores. The following mass
loss at 450 °C was associated with the linker degradation and
subsequent collapse of the framework (Figure S5).
Brunauer−Emmett−Teller (BET) surface areas of the

UMCM-1 MOFs were calculated from nitrogen adsorption
isotherms recorded at 77 K (Table 1, Figure S7). The UMCM-
1 BET surface areas ranged from 3375 to 3690 m2/g, with the
room temperature (25 °C) conditions providing the highest
surface area. These surface areas were below that reported in
the literature by Matzger and co-workers at 4160 m2/g.14 This

decrease could possibly be attributed to the rapid formation of
MOF and due to the zinc acetate precursor employed.44

Scanning electron microscopy (SEM, Figure 3C and Figure
S9) was used to determine the particle size and morphology of
the MOFs. Micrographs of the MOFs showed fibrous crystals
with diameters of 100 nm, compared to that of UMCM-1
reported by Walton and co-workers with 30 μm diameter
crystals.45 This was a result of using the zinc acetate salt in the
synthetic reaction, as opposed to zinc nitrate salts, which
increased the nucleation rate and limited crystal growth.46

With respect to synthetic optimization, the space−time
yields (STY) and production rates were higher when a 5 min
residence time was employed; however, this was the result of
higher throughputs of reagents through the reactor. Further
increasing the residence time to 10 min results in a higher
percentage yield of MOF for reactions at 85 and 130 °C, which
are comparable with the reported yields by Matzger and co-
workers.14

To extend these investigations and include an additional
linker dimensionality, flow synthesis of a quaternary multi-

Table 1. UMCM-1 Synthesis Optimizationa

parameter reaction 1 reaction 2 reaction 3 reaction 4 reaction 5 reaction 6

temperature (° C) 85 85 130 130 25 25
residence time (min) 10 5 10 5 10 5
BET surface area (m2/g) 3380 3460 3500 3500 3550 3690
yield (%) 57 51 44 42 48 67
STY (kg/m3·day) 1539 2759 1208 2281 1310 3600
production rate (g/h) 0.64 1.15 0.50 0.95 0.55 1.50

aYield % is based on H3BTB as the limiting reagent.

Figure 2. PXRD patterns of (A) UMCM-1 and (B) MUF-77
synthesized at various temperatures with 10 min residence time (*
denotes MOF-5 reflection at 6.8°). Background peaks are observed in
(A) due to the presence of petroleum jelly (X-alliance GMBH) used
to mitigate moisture sensitivity during data collection.

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c ompon en t s y s t em , MUF - 7 7 -me t h y l { [Zn 4O -
(hmtt)4/3(bpdc)1/2(bdc)1/2)]n}, was explored. MUF-77 exhib-
its three distinct pore sizes due to its ith-d topology. The
reaction conditions, temperature, and residence time were
varied according to Table 2. A pale yellow suspension was
collected from the reactor, which was washed with DMF three
times followed by solvent exchange with DCM over three days
with fresh DCM being replaced after each day.
To determine the phase purity of MUF-77-methyl, the

product:linker ratios were determined through 1H NMR
spectroscopy of samples digested in base (Figure S2). This
confirmed the expected ratio of 4/3 hmtt, 1/2 bpdc, and 1/2
bdc in MUF-77-methyl. PXRD of the products further
confirmed the MOF pure phase formation, matching simulated
MUF-77-methyl patterns reported by Telfer and co-workers
(Figure 2B and Figure S4).6 The absence of XRD diffraction
peaks from undesired MOF phases contrasted with the flow
synthesis of UMCM-1. TGA of MUF-77-methyl showed
structural degradation occurring at 435 °C (Figure S6).6

Nitrogen adsorption isotherms (Figure S8) recorded at 77 K
for MUF-77-methyl exhibited a broad range of BET surface
areas (Table 2). For MUF-77-methyl synthesized at high
temperatures, a BET range of 3340−3558 was observed,
consistent with literature surface areas reported at 3600 m2/
g.11 Comparatively, MUF-77-methyl synthesized at 25 °C
resulted in poorer quality products. This was evident in the
PXRD patterns with respect to peak broadening as a result of
smaller crystallites and lower BET surface areas that are less
than 2000 m2/g. SEM micrographs of MUF-77-methyl
synthesized at 25 °C (Figure 3B) showed spherical
particulates, with a decrease in size to 50 nm. The smaller
crystallite size indicates rapid nucleation with insufficient
growth which necessitated the elevated temperatures to
promote the crystal formation process.47

With respect to synthetic optimization (Table 2), the room
temperature synthesis gave good yields at 10 min residence
time but poor surface areas. Increasing the reaction temper-
ature to 85 °C resulted in an increase in the surface area up to
3340 m2/g and a yield of 50%, which is comparable with
reported yields by Telfer and Liu.11 Further increasing the
reaction temperature to 130 °C resulted in higher surface areas
and yields with longer residence times. This indicates that a

temperature over 85 °C is required for high surface area MUF-
77-methyl formation, and residence time influences the yield.

In Situ X-ray Analysis of Flow Product Formation. In
situ synchrotron wide-angle X-ray scattering (WAXS) analysis
was performed to observe the formation of multicomponent
MOFs during continuous flow. A variety of in situ analytical
techniques such as XRD and small-angle X-ray scattering
(SAXS) have been performed on MOF syntheses to investigate
particle and crystal growth formation mechanisms.32,35,36,48,49

However, they have been typically performed under static
solvothermal conditions with few reports of in situ flow
synthesis analysis.50−52

To investigate the in situ flow syntheses of multicomponent
MOF sys tems , UMCM-1 and MUF-7 {[Zn4O-
(btb)4/3(bpdc)1/2(bdc)1/2)]n} were selected as candidate
materials. MUF-7 is a variant of MUF-77, where H3hmtt was
substituted by H3btb and was selected as the quaternary
representative for practical purposes.10 Under steady state
conditions, the length along a flow reactor is equivalent to
reaction time progression, and as such, diffraction data were
obtained at various positions along the reactor.53 The steady
state conditions also allowed for syntheses to be studied where
the progression is on the order of seconds to minutes, which
can be difficult to achieve under static solvothermal conditions.
The apparatus shown in Figure S11 was used to perform the

experiment where the sample cell (Figure S12) was mounted
with brackets on an aluminum post and aligned to the center of
the beam and the detector positioned 742 mm past the sample
cell. The sample cell was fed by the continuous flow reactor
positioned adjacent to the beamline which was connected via
Touhy Borst adapters which enabled connection to the reactor
setup and allowed for manipulation of the reactor length. This
allowed for the sample cell to be fixed and enabled the control
of the residence time through the substitution of tubing with
known lengths (i.e., 505 mm = 30 s, 1142 mm = 60 s). The
minimum reaction time measurable was 6.2 s due to the swept
volume of the fittings and sample cell (quartz capillary) used to
obtain the measurements. The maximum time point studied
was 10 min and equivalent to the maximum residence time
used in the flow synthesis optimization. For each data
collection, Bragg peak intensities were obtained, plotted, and
fitted to the Avrami−Erofe’ev (AE) model and Finke−Watzky

Figure 3. SEM micrographs of (A) UMCM-1 synthesized at 130 °C, (B) MUF-77 synthesized at 25 °C, (C) MUF-77 synthesized at 85 °C, and
(D) MUF-77 synthesized at 130 °C.

Table 2. MUF-77-Methyl Synthesis Optimizationa

parameter reaction 1 reaction 2 reaction 3 reaction 4 reaction 5

temperature (° C) 85 130 130 25 25
residence time (min) 10 10 5 5 10
BET surface area (m2/g) 3340 3530 3560 1850 1360
yield (%) 50 65 36 21 86
STY (kg/m3·day) 1659 1955 1187 1365 2855
production rate (g/h) 0.69 0.81 0.49 0.57 1.19

aYield % is based on H3hmtt as the limiting reagent.

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(FW) model to determine crystal growth kinetic parameters
(see the Supporting Information for additional informa-
tion).39,41,54−56

The obtained time-resolved diffraction patterns (Figure 4A)
show that the (002) reflection from MOF-5 appears initially.
This is followed by the respective reflections from UMCM-1,
with (111) and (010) being the prominent Bragg peaks, which
increase in intensity over time. Comparing the Scherrer
crystallite size between UMCM-1 and MOF-5 (Figure S15),
the size of MOF-5 remains constant after 100 s of reaction
time, whereas there is an increase in crystallite size for UMCM-
1 until 200 s reaction time. The kinetic parameters of the AE
and FW fitted curves (Figure 4D and Figure S13) were
obtained and highlight a difference in growth limitation during
flow synthesis. Here the AE growth exponent shows that
growth in the [010] direction is limited by nucleation,
compared to [111] being phase boundary limited (see Table
S3 and the Supporting Information for discussion). The FW
kinetic parameters for [010] also support this, suggesting a
higher rate of growth compared to nucleation. Considering the
crystallite sizes calculated for the two Bragg peaks at the
maximum residence time of 10 min, the average calculated
(010) crystallite size was 770 nm as compared with the average
(111) crystallite size of 680 nm. The larger overall crystallite
sizes observed in the [010] direction can be a result of the
faster rate of growth as determined by the FW kinetic model.
Upon further investigating the difference in the growth kinetics
between the two planes, the ratio between the peak intensity of
the (010) and (111) planes changed over time (Figure S14).
Overall, the growth kinetics and mechanism indicate a
preferential growth in the [010] direction.
MUF-7 time-resolved diffraction patterns (Figure 4B and C)

were obtained at 26 and 80 °C, at a maximum reaction time of
10 min. The minimum reaction time attainable for the 80 °C
experiment was 30 s due to the minimum required length that
can be heated and plumbed within the reactor housing. The
progression of the prominent Bragg peaks, (022), (042), and

(422), for MUF-7 and (002) for MOF-5 was tracked. The
reflections from the possible impurities (MOF-177, IRMOF-
10, UMCM-1, and SUMOF-4) (Figure S16) were not
observed in the data collected and therefore were not tracked.
In this case, the formation of MUF-7 occurs without the
formation of an intermediate phase, and the observed pathway
was simply escalating crystal growth. The kinetic parameters
(Table S4) obtained for the various MUF-7 reflections (022),
(042), and (422) at 26 and 80 °C were consistent with each
other. This indicates a nonpreferential direction of growth for
the MOF. Increasing the reaction temperature to 80 °C
resulted in doubling the 26 °C reaction AE rate constant for
each of the Bragg peaks. With respect to the FW model
parameters, the 26 °C reaction exhibited a nucleation rate
lower than the growth rate, indicating a nucleation-limited
reaction. The 80 °C reaction, conversely, exhibited a higher
nucleation rate than the growth rate, indicating a phase
boundary-limited reaction. In absolute terms, the intensities
observed for the (042) Bragg peak (Figure S17) between 26
and 80 °C showd an increase in the overall intensity at similar
time points with the higher reaction temperature. The Scherrer
crystallite size (Figure S18) was obtained using the (042)
Bragg reflection and was at a maximum size of 900 and 800 Å
for temperatures of 80 and 26 °C respectively.
Overall, the synthesis of UMCM-1 and MUF-7 show two

different pathways. The UMCM-1 initially formed an
intermediary phase in MOF-5 before the formation of the
multicomponent phase, whereas a direct formation of the
multicomponent MOF was observed for MUF-7.

Breakthrough Experiments. The observations made
using in situ X-ray diffraction revealed that the quaternary
multicomponent MOFs do not undergo phase transitions
throughout synthesis. In addition, the kinetic information
allows further optimization of the reactions for future scale-up
of multicomponent MOF synthesis. To test that the measured
structural parameters were amenable to practical use, the
continuous-flow-synthesized MUF-77 vapor adsorption experi-

Figure 4. Diffraction patterns at various points of time within the flow reactor for (A) UMCM-1 at 26 °C, (B) MUF-7 at 26 °C, and (C) MUF-7 at
80 °C (red dash line denotes (002) reflection from MOF-5). Extent of crystallization over time, AE and FW model fits for (D) UMCM-1 based on
peak height at (010) reflection at 26 °C, (E) MUF-7 based on peak height at (042) reflection at 26 °C, and (F) MUF-7 based on peak height at
(042) reflection at 80 °C.

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ments were investigated, as these are typical processes which
require large quantities of adsorbent material. Adsorption
processes with zeolites, and more recently MOFs, have been
proposed as energy efficient alternatives for gas separation
processes.57,58 These adsorptive processes have been applied in
a variety of separations with varying feedstocks for the purpose
of separating different gas mixtures. Recently, Macreadie et al.
demonstrated the remarkable ability for a multicomponent
MOF, CUB-30, to separate benzene and cyclohexane through
in silico breakthrough measurements.9 This study highlighted
the industrial potential of multicomponent MOFs, further
supporting our investigation to discover high-throughput
strategies for their synthesis. To extend this investigation, we
explored the separation of 2,3-dimethylbutane (2,3-DMB)
from nitrogen due to the pressing need to adopt alternative
separation processes to distillation methods, particularly in the
case of C6 isomers.59 The adsorption of 2,3-DMB has
previously been performed at elevated temperatures (343−
473 K) using zeolites and MOFs (UiO-66, Fe2(BDP)3).

57,58,60

In the two analogous MOF systems, MOF-5 and CUB-5, the
selective adsorption of 2,3-DMB, among other hexane isomers,
was observed at 298 K at low pressures.61 Using these vapor
sorption investigations as a model, the effectiveness of flow-
synthesized MUF-77-methyl to adsorb 2,3-DMB was verified
using breakthrough experiments. A comparison of 2,3-DMB
adsorption capacity for MUF-77-methyl at vapor pressures of 3
and 25 kPa was made with the previously reported materials
(Tables S8 and S9).
Initially, low-pressure vapor sorption and nitrogen sorption

isotherms were obtained at 298 K (Figure 5A). The 2,3-DMB

isotherm exhibited a high capacity, as expected, while MUF-
77-methyl maintained a low affinity for nitrogen at 298 K.9 For
the breakthrough experiments, magnesium ferrite (MgFe2O4)
nanoparticles were incorporated with the flow-synthesized
MUF-77-methyl at 10 wt % loading to form a MgFe2O4@
MUF-77-methyl composite. The magnetic nanoparticles with-
in the composite cause localized heating within the adsorption
bed and enable the use of magnetic induction swing adsorption

(MISA).22,62−65 This minimizes heat transfer losses due to the
thermally insulating nature of MOFs. The MgFe2O4@MUF-
77-methyl was characterized with SEM (backscattered imaging
and energy dispersive X-ray spectroscopy (EDX)) and
vibrating sample magnetometry (VSM). EDX mapping (Figure
S20) shows a good distribution of the magnetic nanoparticles
among the MOF powder, while VSM (Figure S22) of the
composite powder reveals a hysteretic curve with a magnet-
ization strength of 8 emu/g. A temperature rise profile of the
MgFe2O4@MUF-77-methyl powder was obtained by measur-
ing the bed temperature while being subjected to an external
magnetic field with a field strength of 31 mT. When compared
to the bare magnetic nanoparticles, a significant decrease in the
maximum achievable temperature was observed in the
composite, which can be attributed to the insulating nature
of the large pore size and consequent pore volume of the
MOF.66,67 This further highlights the need for localized heat
generation to reduce any heat transfer effects to which
conventional temperature swing adsorption may be suscep-
tible.
2,3-DMB breakthrough experiments were performed with an

experimental setup outlined in Figure 5B (see Figure S23 for a
detailed diagram). 2,3-DMB vapor and nitrogen were delivered
to the MgFe2O4@MUF-77-methyl packed bed. The outlet gas
of the bed was analyzed with a mass spectrometer. After
saturation, the bed was then regenerated by applying an
alternating magnetic field, causing the MgFe2O4 to generate
heat and expel the 2,3-DMB. The breakthrough curves (Figure
6) obtained from the experiments show an immediate
breakthrough of nitrogen when in the adsorption phase for
both 3% and 25% feed concentration experiments. The
breakthrough (Figure 6A) for the 25% 2,3-DMB occurred
after 100 s, with saturation of the bed occurring after 300 s.
The 3% feed concentration (Figure 6C), as expected, showed a
longer residence time before breakthrough at 300 s and
saturation at 850 s.
The calculated capacities based on the break point times for

complete adsorption (usable bed) of 2,3-DMB do not allow for
the mass transfer zone (period between initial detection and
saturation) adsorption capacities (Figure 7). A decrease in the
calculated breakthrough capacity of 176 cm3/g for the 25/75
feed mixture is seen compared with the equilibrium isotherm
capacity at a vapor pressure of 25 kPa of 200 cm3/g. This
decrease can be attributed to discounting the mass transfer
zone capacity from the overall breakthrough capacity zone to
avoid including the volume of potential vapor condensation
within the bed from the saturated feed mixture. A wide mass
transfer zone of 600 s was observed for the 3/97 feed mixture
experiments, which resulted in a substantial decrease in usable
bed capacity. This broad mass transfer zone can be attributed
to the lower concentration of vapor in the feed stream, which
decreases the diffusion kinetics based on a smaller concen-
tration gradient. After the mass transfer zone capacity (i.e.,
total adsorption capacity) was included, the amount adsorbed
was approximately 17 cm3, equating to a capacity of 142 cm3 of
vapor per gram of MOF (Table S7), which is closer to the
equilibrium capacity of 184 cm3/g. This decrease in capacity
can be attributed to a need for further optimization of the mass
transfer zone through adjustment of the bed dimensions and
adsorbent geometry to improve the diffusivity of the vapors to
the pores.
Regeneration was performed by applying an alternating

magnetic field, strength of 31 mT, with a constant flow of 50

Figure 5. (A) Low-pressure adsorption isotherms for MUF-77-methyl
at 298 K. Note: the saturation pressure of 2,3-DMB at 298 K is 31.07
kPa. (B) Simplified flow diagram of a breakthrough apparatus.

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mL/min of helium gas. The alternating magnetic field
generates heat through hysteretic losses and rises in temper-
ature, following the temperature rise profile. The released gas
composition was analyzed with the mass spectrometer to
determine the 2,3-DMB content being regenerated. While
nitrogen was detected in this outlet stream, the negligible
increase in nitrogen during the regeneration phase demon-
strates that solely 2,3-DMB is adsorbed to MOF (Figure 6B
and 6D). The flow rate exiting the adsorption bed was
assumed to be 50 mL/min for regeneration calculations. The
average amount was 18.54 cm3 for the 25/75 2,3-DMB/N2
feed mixture over five cycles and 18.18 cm3 for the 3/97 2,3-
DMB/N2 feed mixture over three cycles. This equates to a
regeneration capacity of around 150 cm3/g for both feed
compositions or a production rate of 180 and 169 cm3 2,3-

DMB vapor per gram of MOF per hour of operation for 25/75
and 3/97 feed compositions, respectively.

■ CONCLUSION

This research highlights the use of continuous flow method-
ology for the synthesis of phase pure multicomponent MOFs
on scale. Remarkably, in the time of 10 min for continuous
flow synthesis compared to 72 and 12 h for UMCM-1 and
MUF-77 solvothermal syntheses, respectively, comparable
yields were achieved. Importantly, this result creates a new
foundation for multicomponent MOFs to be rationally
considered for industrial applications. The high phase purity
product obtained for ternary and quaternary MOFs, UMCM-1,
and MUF-77, respectively, exhibited similar physical and
behavioral properties to material obtained by solvothermal
syntheses. Counterintuitively, MOF-5 serves as an intermedi-
ate to the ternary UMCM-1 framework whereas the quaternary
MUF-7 is generated directly from its dissolved components.
This result is promising for the future use of multicomponent
MOFs in large-scale applications with the respective MOF
families potentially synthesizable under similar conditions. In
situ X-ray analysis revealed directed growth for UMCM-1 with
nucleation and phase boundary limited reactions in the two
reflections studied. In contrast, MUF-7 exhibited nonprefer-
ential growth, with formation being highly temperature
dependent. This affects the nucleation rate of the reaction
and, in turn, affects the main mechanism of formation from
being either nucleation limited or phase boundary limited in
the 26 and 80 °C reaction, respectively. Finally, the industrial
importance of multicomponent MOFs was demonstrated
through employing a composite material, MgFe2O4@MUF-
77, to separate 2,3-dimethylbutane from nitrogen. The
breakthrough results obtained from the study showed a

Figure 6. (A and C) Breakthrough plots normalized to the maximum component feed concentration. (B and D) Concentration profile of 2,3-DMB
and N2 overlaid with the adsorption bed temperature.

Figure 7. MUF-77-methyl capacity for 2,3-dimethybutane from
breakthrough experiments. (Green) 25:75 2,3-DMB:N2 feed
concentration. (Purple) 3:97 2,3-DMB:N2 feed concentration.
(Square) Usable bed capacity (cm3/g). (Circle) Regeneration
capacity (cm3/g).

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regenerable material that exhibits similar capacities to that
obtained from equilibrium-based studies.

■ ASSOCIATED CONTENT
*sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c04920.

Synthetic procedures, 1H NMR spectroscopy data,
PXRD data, TGA data, gas sorption data, SEM images,
in situ WAXS experimental setup, kinetic data analysis,
VSM data, breakthrough adsorption setup, and break-
through adsorption data analysis and calculations (PDF)

■ AUTHOR INFORMATION
Corresponding Author
Matthew R. Hill − Department of Chemical Engineering,
Monash University, Clayton, VIC 3800, Australia; CSIRO
Private Bag 10, Clayton South, VIC 3169, Australia;
orcid.org/0000-0001-8897-0324; Email: matthew.hill@

monash.edu, matthew.hill@csiro.au

Authors
Brandon He − Department of Chemical Engineering, Monash
University, Clayton, VIC 3800, Australia; CSIRO Private
Bag 10, Clayton South, VIC 3169, Australia; orcid.org/
0000-0001-5994-1751

Lauren K. Macreadie − School of Chemistry, University of
Sydney, Sydney, NSW 2006, Australia; MacDiarmid
Institute for Advanced Materials and Nanotechnology
Institute of Fundamental Sciences, Massey University,
Palmerston North 4442, New Zealand; orcid.org/0000-
0001-7672-9795

James Gardiner − CSIRO Private Bag 10, Clayton South,
VIC 3169, Australia; orcid.org/0000-0003-0298-5790

Shane G. Telfer − MacDiarmid Institute for Advanced
Materials and Nanotechnology Institute of Fundamental
Sciences, Massey University, Palmerston North 4442, New
Zealand; orcid.org/0000-0003-1596-6652

Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c04920

Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This research was in part undertaken on the SAXS beamline at
the Australian Synchrotron, part of ANSTO. The authors
acknowledge the use of facilities within the Monash X-ray
Platform and Monash Centre for Electron Microscopy.

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