Research Article

ISSN 1998-0124 CN 11-5974/O4

2021, 14(2): 518–525 https://doi.org/10.1007/s12274-019-2571-9

Highly effective H2/D2 separation in a stable Cu-based metal-

organic framework
Yanan Si1,3, Xiang He2 (), Jie Jiang2, Zhiming Duan2, Wenjing Wang1, and Daqiang Yuan1 ()
1
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou
350002, China
2
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China
3
University of the Chinese Academy of Sciences, Beijing 100049, China

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Received: 14 October 2019 / Revised: 12 November 2019 / Accepted: 17 November 2019

ABSTRACT
A three-dimensional copper metal–organic framework with the rare chabazite (CHA) topology namely FJI-Y11 has been constructed
with flexibly carboxylic ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid (H4L). FJI-Y11 exhibits high water stability
with the pH range from 2 to 12 at temperature as high as 373 K. Importantly, FJI-Y11 also shows high efficiency of hydrogen isotope
separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K. Attributed to its excellent structural
stability, FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of
breakthrough experiments.

KEYWORDS
metal–organic framework (MOFs), hydrogen isotope, separation, breakthrough experiments

diversity, adjustable pore size and high specific surface area

1 Introduction
As an essential raw material, deuterium plays an indispensable
role in nuclear fusion reactor [1–4]. Besides, deuterium also
has a wide range of applications in modern industry, especially
in isotope tracing, neutron scattering and proton nuclear
magnetic resonance spectroscopy [5–9]. However, hydrogen
isotope separation is one of the most challenges in the current
separation technology because of their nearly identical molecular
sizes and physicochemical properties. Nowadays, low-temperature
distillation and heavy water electrolysis are mainly used for
the separation of hydrogen isotope on industrial plant scale.
However, current separation technologies still exist problems
of high energy consumption and low separation factors [10].
Recently, porous materials based on physical adsorption for
separating hydrogen isotope at high temperature have drawn
more attention due to their low energy consumption.
Kinetic quantum sieving (KQS), which was first put forward
by Beenakker et al. in 1995 using a cylindrical pore model, has
been used for separation of hydrogen isotope in zeolites, covalent
organic frameworks (COFs) and porous carbon materials due
to the difference of de Broglie wavelength in hydrogen isotopes
that creates different energy barrier at the entrance of the pores
[1, 11–16]. In the confined system, ultra-low temperature can
lead to relatively high diffusion coefficient of the heavy isotope
inside the porous materials, and resulting in the separation
of the hydrogen isotope [17–26]. Compared with the traditional
inorganic porous materials (zeolite, activated carbon, etc.), metal–
organic frameworks (MOFs), also known as porous materials,
which were constructed with organic ligands and metal nodes or
clusters, have been extensively studied owing to their structural
[27–29]. In particular, the variable pore structures and the
high-concentration open metal sites of MOFs make them as
ideal materials for hydrogen isotope separation. Recent researches
about separating hydrogen isotope were mainly focused on
regulating the channel size of MOFs based on KQS or changing
the open metal sites interacting with hydrogen isotope based
on chemical affinity quantum sieve (CAQS) [19, 21, 30–41].
Based on these two mechanisms, some MOFs have been
successfully used for improving the separation efficiency of
hydrogen isotope, such as MFU-4 [31], Cu(I)-MFU-4l, COP-
27-Co, etc. [33, 42]. Another strategy is integrating KQS and
CAQS into the same MOFs via the post-modification method.
For example, the reaction of completely activated MOF-74-Ni
and imidazole molecules can synthesize imidazole partially
coordinated MOF-74-Ni-IM, which retained partial open
metal sites and decreased the pore size at the same time [35].
Although some achievements have been made in MOFs for
hydrogen isotope separation, high capacity and good separation
performance of stable MOFs are still rare.
Not only the separation performance, but also structural
stability of MOFs plays a vital role in practical applications.
Among various MOF structures, some of these are very stable,
such as UiO [43, 44], MIL [45, 46] and ZIFs [47–49], which
are widely used because of their stability. In 2014, Yaghi first
reported a series of ZIFs based on the chabazite (CHA) zeolite
topology using mixed-link, which exhibit high stability [47].
Herein, we reported a new Cu-based MOF FJI-Y11 with CHA
topology by single ligand, which also exhibits excellent chemical
and thermal stability. Surprisingly, experimental and theoretical
results show that the exposed open Cu sites on the paddlewheel

Address correspondence to Daqiang Yuan, ydq@fjirsm.ac.cn; Xiang He, hxiang@shu.edu.cn

Nano Res. 2021, 14(2): 518–525
clusters are not the priority adsorption sites. Indeed, the oxygen
atoms in the carboxyl group and the oxygen atoms connected
with methylene on the ligand play a major role in the adsorption
of hydrogen and deuterium. Furthermore, a real-time cryogenic
breakthrough device is used to verify the feasibility of FJI-Y11
for hydrogen isotope separation in a dynamic condition close
to those used in the industrial environment.
2 Experimental
2.1 Materials
The ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diiso-
phthalic acid (H4L) was prepared according to previously
reported literature [50]. All other chemicals were analytical
reagent grade and used as purchased without further purification.
2.2 Instruments
The single-crystal X-ray diffraction data of FJI-Y11 was collected
on a Bruker APEX-II diffractometer equipped with Mo Kα
radiation (λ = 0.71073 Å). Powder X-ray diffraction (PXRD)
patterns were recorded on a Rigaku Mini Flex 600 X-ray
diffractometer with Cu Kα radiation (λ = 1.5418 Å) in the
scanning angle (2θ) range of 4°–50° at 293 K. Thermogravimetric
analyses (TGA) were completed on a Netzsch STA 449C thermal
analyzer at a heating rate of 10 °C/min in nitrogen. Elemental
analyses (EA) for C, H and N were performed on a Vario EL
III analyzer. 1H NMR spectra were carried out on a Burker
AVANCE 400 spectrometer.
2.3 Synthesis of [Cu2(L)(H2O)2]n·nDMF·2nH2O (FJI-Y11)
A mixture of Cu(NO3)2·3H2O (0.15 mmol), H4L (0.05 mmol),
N,N-dimethylformamide (DMF) (2 mL), H2O (6 mL) and 2 M
HNO3 (0.5 mL) was sealed in a 20 mL Teflon-lined reactor.
The mixture was ultrasonicated until homogeneous and
then heated at 85 oC for 72 h. Green block crystals were
separated and washed with water (3 × 10 mL). The yield
based on ligand is about 40%. Elemental microanalysis
for Cu2(C24H14O8)(H2O)2·C3H7NO·2H2O (C27H29NCu2O15), calc.
(%): C, 44.15; H, 3.98; N, 1.91; found (%): C, 44.08; H, 4.11; N,
1.90. IR (KBr pellet, cm−1): 3,242 w, 2,959 w, 2,918 w, 2,776 w,
1,659 s, 1,609 s, 1,550 s, 1,448 m, 1,374 s, 1,261 s, 1,132 m,
1,070 w, 1,020 w, 927 w, 786 m, 712 m.
2.4 Gas sorption measurements
The adsorption isotherms of N2, H2 and D2 were measured
using an automatic volumetric adsorption apparatus (Micro-
meritics ASAP 2020+) at 77 and 87 K. Before the gas sorption
measurements, the sample was degassed under dynamic
vacuum (≤ 10 μmHg) at 100 °C for 10 h after solvent exchange
with methanol and dichloromethane six times over three days,
respectively. The specific surface area of FJI-Y11 was determined
using the Brunauer–Emmett–Teller (BET) model from the N2
adsorption isotherm data between the relative pressure of 0.05
and 0.3 at 77 K.
2.5 Dynamic column breakthrough separation
experiments
The breakthrough curves were performed on a real-time low-
temperature apparatus coupled with a mass spectrometer
(PFEIFFER VACUUM) using the gas mixtures of H2/D2/Ne
(10/10/80, vol.%) and H2/D2/Ne (1/1/98, vol.%) at 77 K and
101 kPa (Fig. S1 in the Electronic Supplementary Material
(ESM)). In a typical breakthrough experiment for the H2/D2/
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519
Ne (10/10/80, vol.%) or H2/D2/Ne (1/1/98, vol.%) gas mixtures,
dry FJI-Y11 powders (0.33 g) were packed into a stainless-steel
column (diameter = 2 mm, length = 110 mm) with silica wool
filling the void space. The column filled with the sample was
degassed under dynamic vacuum at 373 K for 5 h and then a
constant Ne flow (10 mL/min) was used to purge the adsorption
column for 2 h at 373 K to make certain that the adsorption
column was full of Ne. In order to ensure the accuracy of
the breakthrough experiments, the adsorption column and
pre-cooling line must be immersed into a liquid nitrogen tank
for 20 min before tests. The raw gas mixtures at a flow rate of
10 mL/min for H2/D2/Ne (10/10/80, vol.%) or 15 mL/min for
H2/D2/Ne (1/1/98, vol.%) were passed through the packed
column. The gas flows were controlled by a mass flow meter
at the inlet and the composition of the effluent gas from the
adsorption column was continuously monitored by mass spec-
trometry. All of the samples for breakthrough experiments
were regenerated with a Neon flow (10 mL/min) at 373 K for
30 min.
2.6 Computational method
The grand canonical Monte Carlo (GCMC) simulations were
performed using RASPA2.0 code [51] to explore H2 physisorption
in FJI-Y11. Lennard-Jones (LJ) parameters for the framework
atoms were taken from the DREIDING Force Field [52] except
Cu atom from UFF Force Field [53], and the H2 LJ parameters
from the TraPPE force field. Lorentz-Berthelot mixing rules
were used for all cross terms, and LJ interactions beyond 12.8 Å
were neglected. Feynman-Hibbs corrections were used in the
simulations. Coulomb interactions were calculated using partial
charges on the framework atoms. The Ewald sum method was
used to compute the electrostatic interactions. 100000 Monte
Carlo equilibration cycles were performed plus 100000 production
cycles to calculate the ensemble averages. In one cycle, an
average of N moves was performed, where N is the number of
molecules in the system. Monte Carlo moves used with equal
probability were translation, rotation, insertion, deletion, and
random reinsertion of an existing molecule at a new position.
The adsorption energy of H2 in MOF was investigated within
the framework of the density function theory (DFT) method.
Due to the large number of atoms, the calculations were
performed based upon the primitive cells. Firstly, a reasonable
crystal structure was obtained by geometry optimization with
fixed cell parameters. Then, according to the GCMC results,
a hydrogen molecule was placed at the position where the
adsorption was largest. Thus, two possible adsorbate-MOF
models (i.e. site I and site II models) were constructed for our
calculation. The PBE gradient-corrected functional with the
Grimme correction as well as the all-electronic DNP basis
sets was employed for all calculations. As for the geometry
optimizations of the adsorbate-MOF models, the lattice
parameters and the atomic fraction positions of the MOF
crystal were kept fixed and only the H2 molecule was allowed
to relax. All of calculations were performed by the CASTEP and
Dmol3 modules integrated in the Material Studio 7.0 program
package. The adsorption energy was calculated in terms of the
equation
Eads  EMOFH2  EMOF  EH2
where EMOFH stands for the energy of the optimized adsorbate-
2
MOF structure, and EMOF, and EH denote the energies of the
2
bare MOF structure and the isolated H2 molecule, respectively.
According to this equation, the more negative adsorption
energy means more favorable binding.
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3 Results and discussion
3.1 Structural analysis of FJI-Y11
X-ray crystallography shows that FJI-Y11 crystallizes in the
trigonal space group R 3 . The asymmetric unit consists of two
crystallographically independent Cu(II) ions, one completely
deprotonated organic ligand and two coordinated water. As
shown in Fig. 1(b), each Cu(II) center adopts a square pyramidal
geometry, and the equatorial Cu−O distances span the range of
1.922(7)–1.990(7) Å, which suggests strong metal−carboxylate
bonding. The axially bound water molecules show the Cu1−O12
and Cu2−O11 distances to be 2.161(7) and 2.150(7) Å, respec-
tively. Two Cu(II) ions are linked by four bridging carboxylates
to form the well-known [Cu2(CO2)4(H2O)2] paddlewheel unit,
with the Cu···Cu separation of 2.6277 Å. Each L is coordinated
to four paddlewheel units, which shows μ8-η1:η1:η1:η1:η1:η1:η1:η1
coordination mode. The dihedral angle between isophthalic
rings is 84.97°. The central phenyl ring twists away from
the two isophthalic rings with dihedral angles are 81.88° and
81.24°, respectively. So the Cu2(CO2)4(H2O)2 unit can be viewed
as a 4-connected node. While each L coordinates to four
paddlewheel secondary building units (SBUs) can also act as
a 4-connected node. Extension of the coordination geometry
around these 4-connected nodes will produce the final CHA
framework with three-dimensional percolated channels
(Figs. 1(c) and 1(d)). Figure S2 in the ESM shows the pore
surface structure of activated FJI-Y11, and it can be clearly
Figure 1 Structure introduction of FJI-Y11. (a) The ligand H4L and SBU
for constructing FJI-Y11. (b) The coordination environments of Cu(II)
ion as the paddlewheel dimer. (c) The three-dimensional channels. (d)
CHA topology of FJI-Y11.
Figure 2 Stability of FJI-Y11. (a) VT-PXRD patterns measured in air; (b) PXRD patterns after treatment with acid/alkali solution (pH = 2–12) for 3 days
at 100 °C.
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Nano Res. 2021, 14(2): 518–525
seen that the channels of the framework are not regularly
distributed along the axial direction. For activated FJI-Y11, its
global cavity diameter and largest cavity diameter have the same
value of 8.4 Å, and the pore limiting diameter is 3.8 Å [54, 55].
To our knowledge, FJI-Y11 is the first case of MOF with CHA
topology based on single ligand. The guest solvent molecules,
including DMF and H2O, are highly disordered in the channels,
so the diffraction intensity contributed by the disorder solvents
molecules has been squeezed with Platon [56]. The reasonable
solvent composition was calculated on the basis of the
thermogravimetric weight loss analysis and elemental analysis.
3.2 Stability
In order to evaluate the thermal stability of FJI-Y11, TGA were
carried out under an N2 environment (Fig. S3 in the ESM).
The result shows that FJI-Y11 can be stable up to about 275 °C
and has nearly 19% weight loss before 275 °C, corresponding
to the removal of one DMF molecule and four water molecules.
The thermal stability of FJI-Y11 can also be verified by variable
temperature powder X-ray diffraction (VT-PXRD) results
(Fig. 2(a)). The slight difference in collapse temperature between
TGA and VT-PXRD maybe because the VT-PXRD pattern is
obtained in air while the TGA spectrum is measured in N2.
It should be noted that FJI-Y11 not only exhibits good water
stability but also has acid/alkali stability. When treated by
boiling water for one week or acid/alkali solution (pH = 2–12)
for three days at 100 °C, FJI-Y11 still retains its stability of the
framework, which can be proved by the PXRD results (Fig. 2(b)
and Fig. S5 in the ESM). The excellent stable behaviour of FJI-Y11
is crucial for its further practical applications. Generally speaking,
Cu-based MOFs only with traditional paddle-wheel structure
is usually hydrolysed in the presence of water, and only a few
known MOFs have such excellent chemical stability [57]. Even
for the famous material HKUST-1, its crystallinity was lost after
treated with boiling aqueous solution only one hour (Fig. S14
in the ESM). Note that the stability of FJI-Y11 and HKUST-1
discussed above is for the synthetic framework where water
molecules are coordinated to the Cu center in the paddlewheel
cluster. The coordinated water molecules can be removed during
activation, resulting in the color change from the initial green
to the final dark blue due to the change of crystal field (Fig. S7
in the ESM). We performed the same acid/alkali tests on the
activated FJI-Y11 as the original hydrated form, and the results
showed that the activated FJI-Y11 still maintained its stability
(Fig. S6 in the ESM). We speculate this unusual chemical stability
of FJI-Y11 is due to its small pore size. On rehydration, the
pore limiting diameter is narrowed from 3.8 to 3.3 Å as each
open Cu site is re-occupied by a water molecule (Fig. S8 in the
ESM), which may prevent more water molecules from further
attacking metal–carboxylate oxygen bonds, resulting in high
Nano Res. 2021, 14(2): 518–525
chemical stability of FJI-Y11.
3.3 Permanent porosity and N2 adsorption
The crystallinity of FJI-Y11 was retained after the removal of
guest molecules and coordinated water molecules on the Cu
paddlewheel cluster, as indicated by PXRD result (Fig. S4 in
the ESM). The Zeo++ calculation (probe radius = 1.86 Å) reveals
that the potential solvent-accessible void fraction of activated
FJI-Y11 is 36.3%, which encourages us to investigate its permanent
porosity. As shown in Fig. 3, the N2 adsorption curve exhibits
typical type I adsorption isotherm with a maximum uptake of
190 cm3/g at 1 bar. The N2 adsorption curve increases steeply
below relative pressure 0 and saturates at relative pressure 0.2.
In the desorption process, the N2 is desorbed totally when
the pressure reduces, which clearly indicates the micropores
characteristic of FJI-Y11. The BET and Langmuir surface
areas are 719 and 828 m2/g, respectively. Accordingly, the total
pore volume computed by the nitrogen isotherm is 0.30 cm3/g
at p/p0 = 0.99. Based on the N2 adsorption data, pore size
distribution calculated by the model of nonlocal density functional
theory (NLDFT) shows a narrow distribution of micropores
(about 5.9 Å), which is closed to the value calculated by Zeo++.
3.4 Adsorption and separation properties of hydrogen
isotope
The permanent micropores of FJI-Y11 prompted us to study
its gas uptake capacity, especially for hydrogen and deuterium.
Moreover, we investigated hydrogen and deuterium adsorption
of FJI-Y11 at 77 and 87 K, respectively. As shown in Fig. 4,
activated FJI-Y11 show remarkable hydrogen and deuterium
uptakes, the adsorption capacity up to 183 and 205 cm3/g at
77 K and 1 bar, and the values reaching 146 and 167 cm3/g at
87 K and 1 bar. The hydrogen uptake exceeds many famous
MOFs at low pressure, such as MOF-74-Zn (144 cm3/g) [58],
MIL-53 (Al) (21 cm3/g) [59], UiO-66 (151 cm3/g) and ZIF-8
(143 cm3/g) [60–63]. Compared with similar BET and pore
size of pores materials, the hydrogen adsorption amount of
FJI-Y11 is at a high level. The high hydrogen and deuterium
uptakes of FJI-Y11 may be ascribed to the adsorption sites and
suitable pore space. The adsorption capacity of deuterium gas
is higher than that of hydrogen, which is owing to the fact that
the heavier isotope has lower zero energy and smaller de Broglie
wavelength as compared to hydrogen. Additionally, high
hydrogen and deuterium uptakes are beneficial for hydrogen
Figure 3 Nitrogen sorption isotherm of FJI-Y11 at 77 K (filled symbols:
adsorption; open symbols: desorption); the inset graph shows its pore size
distribution analysed by NLDFT method.
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521
Figure 4 H2 and D2 sorption isotherms of FJI-Y11 at 77 and 87 K (filled
symbols: adsorption; open symbols: desorption).
isotope separation, because the adsorption capacity is also an
important parameter in practical applications. In order to
evaluate the affinity between framework and hydrogen isotopes,
the adsorption enthalpies of hydrogen and deuterium were
calculated by Viral equation based on the adsorption isotherm
data at 77 and 87 K with values of 7.13 and 7.88 kJ/mol at zero
coverage, respectively (Fig. 5(a)). It is worth noting that hydrogen
isotopes adsorption capacities of HKUST-1 are much larger
than that of FJI-Y11 (Fig. S15 in the ESM), but FJI-Y11 possesses
higher adsorption enthalpies, which indicates that FJI-Y11 has
stronger interaction with hydrogen isotopes (Fig. S16 in the
ESM) [64]. Furthermore, the ideal adsorption solution theory
(IAST) was used to calculate the selectivity of equimolar D2/H2
mixtures at atmospheric pressure. As shown in Fig. 5(b), the
selectivity of FJI-Y11 is 1.76 at 77 K and 100 kPa, while the
selectivity of HKUST-1 is only 1.42 under the same conditions
(Fig. S17 in the ESM) [65, 66]. Compared with HKUST-1, the
better selective property of FJI-Y11 may be caused by its relatively
smaller pore size. Meanwhile, FJI-Y11 still shows better selective
performance than that of zeolite 5A which has similar pore
size (Figs. S19 and S20 in the ESM), indicating that the adsorption
sites on FJI-Y11 play an essential role in the separation of
hydrogen isotope. Thus, the highly selective adsorption of D2
over H2 for FJI-Y11 further illustrates that the combination of
suitable pore space and strong binding sites has a positive effect
on the selective adsorption of D2. Therefore, FJI-Y11 could be
acted as a candidate material for hydrogen isotope separation.
It is noted that the reported hydrogen adsorption performance
of HKUST-1 varies quite substantially, for example, Bordiga et
al. [67] and Li et al. [68] both reported hydrogen adsorption
capacity of 6 mmol/g, while Yaghi et al. reported hydrogen uptake
of 7.9 mmol/g in one paper and 12.4 mmol/g in another paper
[69–71]. All the results about HKUST-1 in this paper are based
on the highly crystalline material with hydrogen uptake of
12.4 mmol/g.
3.5 The hydrogen isotopes adsorption sites in activated
FJI-Y11
To confirm hydrogen and deuterium adsorption sites, the
hydrogen isotopes adsorption behaviours of activated FJI-Y11
was studied by multilevel computational simulations. The GCMC
simulations show that the simulated hydrogen and deuterium
adsorption isotherms of activated FJI-Y11 are in agreement
with the experimental data at 77 K (Figs. S9 and S10 in the
ESM), whereas the adsorption capacities are almost the same
at atmospheric pressure. As shown in the Figs. S11 and S12 in
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Figure 5 (a) The isosteric heat of D2 (black) and H2 (red) for FJI-Y11. (b) IAST selectivity of FJI-Y11 for 1:1 D2/H2 mixture at 77 K (black) and 87 K (red).

the ESM, the concentration of deuterium is higher than that of
hydrogen at the same lower pressure, which indicates that
deuterium is easier to enter and adsorb in the hole. Careful
analysis of the simulated density picture of adsorbed hydrogen
molecules shows that there are two preferential adsorption
sites (Figs. 6(b) and 6(c)). The DFT method is used to further
optimize the two adsorption sites. Abnormally, the first
adsorption sites of simulation are located on the oxygen atoms
of Cu paddlewheel clusters rather than the open Cu sites.
In site I (Fig. 6(b)), hydrogen molecule is closest to the oxygen
atom on the Cu paddlewheel cluster with H–O distance of
2.53 Å, while the distance of Cu–H is 3.20 Å. As shown in
Fig. 6(c), the shortest H–O distance of 2.84 Å in site II is
between hydrogen molecule and the oxygen atom connected
with methylene on the ligand, which shows that the additional
O atoms on the ligands (not the O atoms of carboxyl group)
have a positive effect on further promoting hydrogen adsorption.
The calculated hydrogen adsorption energies of adsorption
site I and site II are 21.10 and 19.29 kJ/mol, respectively.
3.6 Dynamic column breakthrough experiments
To further investigate the D2/H2 separation property of FJI-Y11
in the practical application, dynamic breakthrough experiments
were performed at 77 K and 1 bar, in which a mixed gas of
H2/D2/Ne (10/10/80, vol.%) flowed over the packed column of
activated FJI-Y11 with a total flow of 10 mL/min. As expected,
the challenging separation of hydrogen isotope was realized by
using FJI-Y11. From the breakthrough curve, hydrogen was first
to eluted through the packed column, whereas the adsorption
column retained deuterium for a long time of 17 min/g before
the breakthrough of D2 (Fig. 7(a)). The amount of D2 enriched
in the adsorption bed from the mixed gas of H2/D2/Ne
(10/10/80, vol.%) was up to 4.1 mmol/g, and the separation factor
reached 1.4 which was counted based on the breakthrough
experiments at 77 K and 1 bar. Besides, we also studied the
H2/D2 separation performance using the mixture of H2/D2/Ne
(1/1/98, vol.%) with a flow rate of 15 mL/min and the retention
time of deuterium can be as high as 70 min/g (Fig. 7(b)). For
comparison, breakthrough experiments for HKUST-1 and zeolite
5 A were also carried out. As shown in Figs. 7(c) and 7(d), the
retention time of deuterium was only 10 and 6 min/g for
HKUST-1 and zeolite 5A, respectively. And the trend of the
retention times about three materials for the H2/D2/Ne (1/1/98,
vol.%) mixture is the same as the mixture of H2/D2/Ne
(10/10/80, vol.%) (Figs. S18 and S21 in the ESM). Compared with
HKUST-1 and zeolite 5A, the better separation performance
of H2/D2 for FJI-Y11 could be ascribed to the synergistic effect
of the strong adsorption sites and suitable pore space. It is worth
noting that the pore limiting diameter (3.8 Å) of FJI-Y11 is
small enough, but the KQS effect is difficult to be observed

Figure 6 (a) Slices through the calculated potential fields for adsorbed hydrogen in activated FJI-Y11 under 77 K. The slice is viewed along the
crystallographic c axis. The simulated adsorption (b) site I and (c) site II in activated FJI-Y11 obtained from the GCMC simulation and DFT optimization.
Some atoms are omitted for clarity.

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Nano Res. 2021, 14(2): 518–525
Figure 7 The dynamic breakthrough curves of FJI-Y11 at 77 K for the mixed gases of (a) H2/D2/Ne (10/10/80 vol.%); (b) H2/D2/Ne (1/1/98 vol.%). The
dynamic breakthrough curve for a H2/D2/Ne (10/10/80 vol.%) mixture at 77 K in a packed column with (c) HKUST-1 and (d) zeolite 5A.
due to the relatively high temperature used for the breakthrough
experiment [32]. However, there is no doubt that the suitable
pore space does play a positive role in the process of hydrogen
isotope separation, which has been confirmed by above
experiments.
In practical application, adsorbent should have good structural
stability and regeneration ability [29]. Thus, breakthrough
experiments of the ternary mixed gas of H2/D2/Ne (10/10/80
vol.%) were executed to evaluate the recycling performance of
FJI-Y11. As shown in Fig. 8, there is no significant loss in the
D2 adsorption capability and breakthrough time for FJI-Y11.
In addition, FJI-Y11 retained its crystallinity and its BET did not
change obviously after three cycling breakthrough experiments
(Figs. S4 and S13 in the ESM). In short, enriched deuterium can
be recovered at a relatively high level of purity as compared to
the raw mixture during the regeneration process, and all these
results suggest that FJI-Y11 is a promising candidate material
for H2/D2 purification.
Figure 8 The recyclability of FJI-Y11 in multiple mixed-gas column
breakthrough tests for a H2/D2/Ne (10/10/80 vol.%) mixture with a total
flow of 10 mL/min at 77 K.
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4 Conclusions
In summary, we have successfully synthesized a microporous
Cu-based MOF which has rare chabazite topology and exhibits
excellent chemical and thermal stability. This MOF possesses
high hydrogen and deuterium adsorption amounts due to
the presence of two special adsorption sites. Interestingly,
the adsorption site I is not the exposed open Cu site on the
paddlewheel cluster due to the mismatch between the direction
of open metal sites and the diffusion path of gas molecules.
Furthermore, breakthrough experiments at high temperature
of 77 K certifies that the heavy hydrogen isotope can be effectively
separated and stored inside the pores of FJI-Y11 by combining
with suitable space and adsorption sites in one framework. As far
as we know, this is the first time that using MOF as adsorbent
bed to explore hydrogen isotope separation by breakthrough
experiment. Overall, high hydrogen isotopes adsorption capacity,
good gas separation property and excellent regenerative stability
enable that FJI-Y11 as excellent adsorbent for separating hydrogen
isotope may be used in the industrial application. In addition,
breakthrough separation technology as the promising gas
separation technology with the advantage of low-cost and
low-energy can be further extended to solve the challenge of
separating hydrogen isotope. By introducing strong binding
sites into the micropores materials and controlling the pore
size at the same time, highly selective adsorption of D2 over H2
will be possible. The rational design of material FJI-Y11 will
provide a new synthetic strategy for the future hydrogen isotope
separation materials.
Acknowledgements
This work was financially supported by the Strategic Priority
Research Program of CAS (No. XDB20000000), the Key Research
Program of Frontier Sciences, CAS (No. QYZDB-SSW-SLH019),
and the Natural Nature Science Foundation of China (Nos.
21771177, 51603206 and 21203117).
Research
524
Electronic Supplementary Material: Supplementary material
(attached with all the supporting figures mentioned in this
work) is available in the online version of this article at https://
doi.org/10.1007/s12274-019-2571-9.
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