Synthesis, crystal structures and catalytic properties of three-dimensional nickel(II) and manganese(II) coordination polymers with dicarboxylate and semi-rigid bis(imidazole) ligands

Article abstract of DOI:10.1007/s11243-016-0070-3

Two coordination polymers (CPs), namely [Ni(L)(chdc)]_n (1) and [Mn(L)(ndc)(H₂O)]_n (2) (L?=?4,4′-bis(imidazol-1-ylmethyl)biphenyl, H₂chdc?=?1,2-cyclohexanedicarboxylic acid, H₂ndc?=?2,6-naphthalenedicarboxylic acid), have been hydrothermally synthesized and characterized by physicochemical and spectroscopic methods and also by single-crystal diffraction. Both CPs feature 3D-diamond-like networks with point symbol of 6⁶; CP-1 displays a 2-fold interpenetrated net, while CP-2 presents a non-interpenetrated framework. The thermal stabilities, solid-state luminescence properties and catalytic activities of both CPs for degradation of methyl orange in a Fenton-like process were investigated.

Full text of DOI:10.1007/s11243-016-0070-3

Transition Met Chem
DOI 10.1007/s11243-016-0070-3
Synthesis, crystal structures and catalytic properties of three-
dimensional nickel(II) and manganese(II) coordination polymers
with dicarboxylate and semi-rigid bis(imidazole) ligands
Hai-Ning Chang1 Yong-Guang Liu1 Zeng-Chuan Hao1 Guang-Hua Cui1
Sheng-Chun Wang1
•
•
•
•
Received: 27 April 2016 / Accepted: 3 June 2016
Ó Springer International Publishing Switzerland 2016
Abstract Two coordination polymers (CPs), namely
[Ni(L)(chdc)]n (1) and [Mn(L)(ndc)(H2O)]n (2) (L = 4,40-
bis(imidazol-1-ylmethyl)biphenyl, H2chdc = 1,2-cyclo-
hexanedicarboxylic acid, H2ndc = 2,6-naphthalenedicar-
boxylic acid), have been hydrothermally synthesized and
characterized by physicochemical and spectroscopic
methods and also by single-crystal diffraction. Both CPs
feature 3D-diamond-like networks with point symbol of 66;
CP-1 displays a 2-fold interpenetrated net, while CP-2
presents a non-interpenetrated framework. The thermal
stabilities, solid-state luminescence properties and catalytic
activities of both CPs for degradation of methyl orange in a
Fenton-like process were investigated.
catalysis [1–4]. Among the numerous strategies for con-
struction of CPs, the self-assembly of transition metal salts
with dicarboxylic acids and neutral N-donor co-ligands
under hydrothermal or solvothermal conditions has become
an effective approach [5–12]. 4,40-Bis(imidazol-1-yl-
methyl)biphenyl, (L) as a typical semi-rigid N-donor ligand
can bend or rotate to adopt appropriate conformations
when coordinated with metal ions in target CPs [13–21].
As with heterocyclic 4,40-biphenyl-based ligands, the
donor N atoms are sufficiently well separated to allow for
the construction of interpenetrating motifs. However, to the
best of our knowledge, 4,40-biphenyl-based CPs rarely
display interpenetrating frameworks [14]. In continuation
of our ongoing research into bis(imidazole)-based CPs, we
selected the semi-rigid bis(imidazole) L together with 4,40-
biphenyl-based spacers as ligands. This approach afforded
two CPs, [Ni(L)(chdc)]n (1) and [Mn(L)(ndc)(H2O)]n (2)
(H2chdc = 1,2-cyclohexanedicarboxylic acid, H2ndc =
2,6-naphthalenedicarboxylic acid, Scheme 1). The crystal
structures of these CPs are reported here. In addition, their
thermal stabilities, luminescence properties and catalytic
performances for the degradation of methyl orange in a
Fenton-like process using sodium persulfate as the primary
oxidant have been investigated.
Introduction
The current interest in coordination polymers (CPs) is
stimulated not only by their intriguing topological struc-
tures, but also by their potential utilization in areas such as
molecular recognition, magnetism, gas adsorption and
Electronic supplementary material The online version of this
article (doi:10.1007/s11243-016-0070-3) contains supplementary
material, which is available to authorized users.
Experimental
& Guang-Hua Cui
tscghua@126.com
Materials and methods
& Sheng-Chun Wang
tswlhx@126.com
The free ligand L was prepared according to the reported
literature [22]. All other reagents and solvents were com-
mercial products and used without further purification.
Elemental analyses for C, H and N were obtained on a
Perkin-Elmer 240C automatic analyzer. IR spectra were
1
Hebei Key Laboratory for Environment Photocatalytic and
Electrocatalytic Materials, College of Chemical Engineering,
North China University of Science and Technology,
063009 Tangshan, Hebei, People’s Republic of China
123

Transition Met Chem
Catalytic activity test
N
N
N
N
The catalytic performances of the CPs were investigated
for the degradation of methyl orange (MO) in a Fenton-like
process as follows: 0.01 mmol of the solid catalyst (CP-1
or CP-2) and 0.02 mmol of sodium persulfate were mixed
together with 150 mL of MO solution (10 mg/L,
pH = 5.0) in a 250 mL round-bottom flask. The tempera-
ture was maintained at 30 1 °C by water circulation.
During the given time interval, about 3.0 mL of the sus-
pension was taken and separated by centrifugation and then
analyzed with a Puxi 1901 UV–visible spectrometer at
506 nm wavelength. This procedure was repeated with
equal amounts of NiSO4Á6H2O, MnSO4Á2H2O or without
any catalyst as control experiments under the same con-
ditions. The degradation efficiency (%D) is defined as:
L
COOH
COOH
HOOC
HOOC
H2ndc
H2chdc
Sch. 1 Structural formulas of all ligands
obtained with an Avatar 360 (Nicolet) spectrophotometer
in the 4000–400 cm-1 region using KBr pellets. Thermo-
gravimetric analyses (TGA) were carried out on a
NETZSCH TG 209 thermal analyzer from room tempera-
ture to 800 °C under N2 at a heating rate of 10 °C/min.
Luminescence spectra for the powdered solid samples were
investigated with a Hitachi F-7000 spectrophotometer.
X-ray powder diffraction (XRPD) data were recorded on a
Rigaku D/Max-2500 diffractometer at 40 kV, 100 mA for
a Cu-target tube and a graphite monochromator. The
absorptivity value of methyl orange was measured with a
Puxi 1901 UV–visible spectrophotometer.
ðC0 À CtÞ
%D ¼
 100%
ð1Þ
C0
where C0 (mg/L) is the initial concentration of MO, and Ct
(mg/L) is its concentration at reaction time t (min).
In order to study the stability of each catalyst, three
cycles of catalytic degradation experiments were per-
formed under the same conditions as mentioned above.
After each cycle, the catalyst was removed by centrifuga-
tion, washed several times with distilled water, and dried
under vacuum for 10 h.
Synthesis of CP-1
X-ray crystallography
A mixture of NiSO4Á6H2O (52.6 mg, 0.2 mmol), L
(31.4 mg, 0.1 mmol), H2chdc (34.4 mg, 0.2 mmol), NaOH
(16 mg, 0.4 mmol) and H2O (10 mL) was sealed in a
25-mL Teflon-lined stainless-steel autoclave. The mixture
was heated to 140 °C for 3 days and then cooled to room
temperature at 10 °C/h. Green block-shaped crystals were
collected by filtration. Yield: 41.2 % (based on ligand L).
Calc(%). for C28H28N4NiO4 (Mr = 543.25): C 61.9, H 5.2,
N 10.3. Found: C 61.7, H 5.1, N 10.2. IR (KBr pellet,
cm-1): 3117 w, 2906 w, 1543 s, 1517 s, 1415 m, 1400 w,
1090 w, 735 w.
Single-crystal X-ray diffraction data for both CPs were
collected at 293(2) K on a Bruker Smart CCD diffrac-
tometer using graphite-monochromated Mo-Ka radiation
˚
(k = 0.71073 A) with x scan mode. Semiempirical
absorption corrections were applied using the SADABS
program [23]. The structural data were refined by full-
matrix least-squares methods on F2 using the SHELXL-97
program [24]. All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms of water molecules
could be located from the difference Fourier maps, while
the other hydrogen atoms were included in calculated
positions and refined with isotropic thermal parameters
riding on the corresponding parent atoms. Crystal data and
refinement parameters for both CPs are given in Table 1.
Selected bond lengths and angles are listed in Table 2.
Synthesis of CP-2
The preparation of CP-2 was similar to that of CP-1, except
H2chdc was substituted by H2ndc (43.2 mg, 0.2 mmol) and
NiSO4Á6H2O was replaced by MnSO4Á2H2O (33.8 mg,
0.2 mmol). Light yellow block-shaped crystals were col-
lected by filtration. Yield: 50.1 % (based on ligand L).
Anal. Calc (%). for C32H26N4MnO5 (Mr = 601.52): C
63.9, H 4.4, N 9.3 %. Found: C 63.7, H 4.2, N 9.1. IR (KBr
pellet, cm-1): 3405 w, 3120 w, 1683 s, 1602 m, 1570 m,
1402 w, 1262 m, 1190 w, 931 w, 789 w, 659w.
Results and discussion
Crystal structure of CP-1
Single-crystal X-ray diffraction analyses reveals that CP-1
crystallizes in the orthorhombic space group Aba2. The
123

Transition Met Chem
Table 1 Crystal and refinement
data for two CPs
Complex
CP-1
CP-2
Empirical formula
Formula weight
Crystal system
Space group
C28H28N4NiO4
543.25
C32H26MnN4O5
601.51
Orthorhombic
Aba2
Monoclinic
P21/n
˚
a, A
25.1320 (2)
16.2343 (13)
12.4725 (13)
90
18.1263 (12)
6.0575 (4)
25.9020 (17)
90
˚
b, A
˚
c, A
a, deg
b, deg
c, deg
90
93.4410 (10)
90
90
3
˚
V, A
5088.7 (8)
8
2838.9 (3)
4
Z
Calculated density, g/cm3
Absorption coefficient/mm-1
F (000)
1.418
1.407
0.805
0.514
2272
1244
Crystal size, mm
h range, deg
0.22 9 0.19 9 0.18
1.62–27.49
-32/30, -21/14, -16/15
15,243
0.19 9 0.17 9 0.15
2.25–27.52
-23/23, -7/7, -33/33
25,037
Index range h, k, l
Reflections collected
Independent reflections (Rint
Data/restraint/parameters
GOF on F2
)
5669 (0.0605)
5669/1/334
0.945
6512 (0.0578)
6512/0/379
1.014
Final R1, wR2 (I [ 2r (I))
Largest diff. peak and hole/e A
0.0447, 0.0791
0.281, -0.333
0.0479, 0.1204
0.837, -0.281
3
˚
asymmetric unit contains one Ni(II) atom, one chdc2-
ligand and two halves of L ligands. Each Ni(II) center is
surrounded by two nitrogen atoms (N1, N3) from two L
ligands and four carboxylate oxygen atoms (O1A, O2A,
O3, O4, symmetry code: A = -x ? 1/2, y, z ? 1/2) from
two different chdc2- ligands, generating a distorted octa-
hedral coordination geometry (Fig. 1a). The Ni1–O bond
the topological method has been used to analyze the 3D
structure by using TOPOS 4.0 software [26]. The Ni atoms
are defined as 4-connected nodes, and the L and chdc2-
ligands are regarded as linkers. Hence, the 3D network can
be classified as a classical uninodal dia net with a point
symbol 66. CP-1 has a 3D network with quadrilateral
channels formed by connecting four linear ligands to the
Ni(II) centers. The diamond cage exhibits dimensions of
˚
lengths are in the range of 2.052(3) A–2.219(3) A, and the
˚
˚
Ni1–N bond distances are 2.040(3) A (Ni1–N1) and
˚
6.403 9 12.787 9 14.892 A, as measured by through-
˚
2.043(3) A (Ni1–N3). All the bond lengths and angles
space Ni1–Ni distances. Inspection of the structure of CP-1
shows that the potential voids are filled via identical net-
works, resulting in a 2-fold interpenetrated network
(Fig. 1e). The two-interpenetrated nets are related by a
single translational vector (Class Ia) [9], with Zt = 2 and
Zn = 1, where Zt represents the number of interpenetrated
nets related by translation and Zn denotes the number of
interpenetrated nets related by crystallographic symmetry.
around Ni(II) center are in the normal ranges [25].
Two carboxylate groups of one e, a-cis-chdc2- ligand
display the same chelating coordination mode. The chdc2-
ligands are fully deprotonated and link neighboring Ni(II)
centers to form a 1D zigzag chain, in which the Ni_Ni
˚
separation is 6.403(9) A and Ni_Ni_Ni angle is 153.80
(11)° (Fig. 1b). There are two kinds of L ligands, both of
which adopt cis-conformation with Ndonor_N–Csp3_Csp3
torsion angles of 21.36(3) and 24.09(3)°. The ligands L act
as l2-bridging linkers to connect adjacent Ni(II) into a 1D
left-handed [Ni(L)]n helical chain with a pitch of 16.234(1)
Crystal structure of CP-2
The CP-2 is a 3D network with the monoclinic space group
P21/n. The asymmetric unit contains one Mn(II) atom, one
L ligand, two halves of ndc2– ligands and one coordinated
water ligand. The Mn(II) center is coordinated by three
˚
A (Fig. 1c). The interlacing of the two distinct 1D chains
gives rise to a 3D framework via shared Ni(II) atoms
(Fig. 1d). In order to understand the architecture of CP-1,
123

Transition Met Chem
˚
directions of these chains further give rise to a complicated
3D framework (Fig. 2d). From the topological point of
view, the Mn1 atoms are simplified to 4-connected nodes,
while the ndc2- and L ligands are considered as linkers.
Accordingly, the 3D framework of CP-2 can be simplified
to a 4-connected dia topology with the topological point
symbol of 66 (Fig. 2e). The total void volume of the
framework (after removal of all solvent molecules) reaches
Table 2 Selected bond lengths [A] and angles [°] for CPs 1–2
Parameter
Value
Parameter
Value
CP-1
Ni1–N1
2.040 (3)
2.052 (3)
Ni1–N3
2.043 (3)
2.123 (3)
Ni1–O1A
Ni1–O3
Ni1–O4
2.146 (3)
Ni1–O2A
2.219 (3)
N1–Ni1–N3
N3–Ni1–O1A
N3–Ni1–O3
N1–Ni1–O4
O1A–Ni1–O4
N1–Ni1–O2A
O1A–Ni1–O2A
O4–Ni1–O2A
CP-2
92.24 (12)
94.77 (11)
96.40 (12)
104.44 (11)
153.79 (10)
91.22 (11)
61.56 (10)
100.16 (10)
N1–Ni1–O1A
N1–Ni1–O3
O1A–Ni1–O3
N3–Ni1–O4
O3–Ni1–O4
N3–Ni1–O2A
O3–Ni1–O2A
95.08 (11)
164.85 (12)
96.56 (11)
101.65 (11)
61.65 (10)
156.30 (11)
85.85 (10)
3
˚
35 A , as calculated by PLATON software [26], which is
3
approximately 1.2 % of the unit cell volume(2838.9 A ).
˚
Notably, quadrilateral channels are observed in this man-
ganese organic framework with
a
size of ca.
˚
13.140 9 13.846 9 16.786 A. The crystal structure is
further stabilized by hydrogen-bonding interactions
between the coordinated water and ndc2- ligands, which
˚
refer to O1 W–H1WA_O1C (2.780(3) A) and O1W–
˚
H1WB_O1C (2.592(3) A) (symmetry code: A = x-1/2,
-y ? 1/2, z-1/2; B = 1-x, 1-y, 2-z; C = x, 1 ? y, z).
Mn1–O4
2.106 (2)
2.215 (2)
2.243 (2)
103.15 (9)
91.77 (9)
85.32 (7)
83.86 (9)
175.89 (9)
115.08 (9)
88.54 (8)
90.12 (8)
Mn1–O1 W
Mn1–O2
2.139 (2)
2.2371 (18)
2.382 (2)
93.18 (9)
171.47 (9)
85.41 (8)
91.69 (9)
97.09 (8)
141.70 (7)
56.52 (7)
Mn1–N4A
Mn1–N1
Mn1–O1
O4–Mn1–O1 W
O1 W–Mn1–N4A
O1 W–Mn1–O2
O4–Mn1–N1
N4A–Mn1–N1
O4–Mn1–O1
N4A–Mn1–O1
N1–Mn1–O1
O4–Mn1–N4A
O4–Mn1–O2
N4A–Mn1–O2
O1 W–Mn1–N1
O2–Mn1–N1
O1 W–Mn1–O1
O2–Mn1–O1
XRPD results and IR spectra analysis
X-ray powder diffraction (XRPD) patterns of both CPs
were in reasonable accordance with those simulated from
their single-crystal structure data, indicating the bulk phase
purity of samples of CP-1 and CP-2 (Fig. S1). The infrared
spectra of both CPs exhibit no absorption peaks around
1700 cm-1, demonstrating that all carboxyl groups of the
dicarboxylate ligands are deprotonated [28]. For CP-2, a
strong broadband at about 3400 cm-1 corresponds to the
O–H stretching vibrations of water molecules. Character-
istic peaks at 1543 and 1415 cm-1 for CP-1, and at 1683,
1520 and 1402 cm-1 for CP-2 may be attributed to the
asymmetric and symmetric vibrations of carboxylate
groups. The separations [mas (COO)–ms (COO)] between
these bands indicate the presence of monodentate
(281 cm-1 for CP-2), and chelating (128 cm-1 for CP-1,
118 cm-1 for CP-2) carboxylate coordination modes.
Strong bands at 1517 cm-1 for CP-1 and 1515 cm-1 for
CP-2 are assigned to the mC=N stretching of the imidazole
rings of the L ligands.
Symmetry codes: for CP-1: A: -x ? 1/2, y, z ? 1/2; for CP-2: A:
x-1/2, -y ? 1/2, z-1/2
carboxylate oxygen atoms (O1, O2 and O4) from two
ndc2- ligands, plus one oxygen atom (O1 W) from the
water ligand and two nitrogen atoms (N1, N3A, symmetry
code: A = x-1/2, -y ? 1/2, z-1/2) from two L ligands,
forming a distorted octahedral geometry (Fig. 2a). The
bond distance of Mn1–O ranges from 2.106(2) to 2.382(2)
˚
A, and the Mn1–N bond lengths are 2.215(2) and 2.243(2)
˚
A, which is in accordance with the values for other
reported Mn(II) complexes [27].
In CP-2, the ndc2- ligands connect neighboring Mn(II)
atoms into a 1D zigzag-like [Mn(ndc)]n chains with
˚
˚
Thermal and luminescence properties
Mn1_Mn1 distances of 13.846(1) A and 13.139(9) A
(Fig. 2b), in which the ndc2- anions show two different
coordination modes (l2-g1:g1 and l2-g2:g2). Moreover,
the ligand L adopts trans-conformation with a Ndonor_N–
Csp3_Csp3 torsion angle of 122.67(2)°. Adjacent Mn(II)
centers are connected by l2-bridging L ligands to form an
infinite a meso-helical [Mn(L)]n motif (Fig. 2c). The
Mn1_Mn1 separations across the L ligands are 16.786(9)
Thermogravimetric analysis was carried out for both CPs
in order to investigate their thermal stabilities. The TGA
curves show that the decomposition of CP-1 from 300 to
630 °C, and the residual weight matches well with the
formation of NiO (obsd.: 14.4 %, calcd.: 13.8 %). For CP-
2, a weight loss in the range of 20–180 °C is attributed to
the loss of water (obsd 2.4 %, calcd 3.0 %). Decomposition
of the organic framework occurs at ca. 320 °C with the
˚
A. Hinging at the metal atoms, the pitch of the meso-helix
˚
is 30.710(2) A. The interlaced connections from different
123

Transition Met Chem
Fig. 1 a The coordination
environment of Ni(II) center in
CP-1 with ellipsoids at 30 %
probability, all hydrogen atoms
are omitted for clarity
(symmetry codes: A: -x ? 1/2,
y, z ? 1/2; B: –x ? 1, -y ? 2,
z). b The 1D ‘‘V’’-like chain.
c The 1D left-handed [Ni(L)]n
helical chain. d View of the 3D
supramolecular framework.
e Twofold interpenetrated 3D
dia topology in CP-1
final residue corresponding to MnO (obsd 12.5 %, calcd
11.8 %) (Fig. S2).
important ecological problem. Recently, advanced oxida-
tion technology based on Fenton-like reactions has been
developed for the degradation of azo dyes [33]. Fenton-like
reactions involve the production of strongly oxidizing
The solid-state luminescence behaviors of both CPs
and the free ligand L have been investigated at room
temperature. As shown in Fig. 3, an emission for the free
N-donor ligand is observed with a kmax of 420 nm on
excitation at 250 nm, which is probably attributable to
p* ? p transitions [29]. A strong emission peak is
observed at about 390 nm (kex = 250 nm) for CP-1 and
400 nm (kex = 280 nm) for CP-2. The emission bands for
both CPs exhibit blue shifts of ca. 30 nm (for CP-1) and
20 nm (for CP-2) relative to the free L ligand, which is
due to the fact that the coordinated ligands are not
allowed to relax by torsional modes on photoexcitation
[30]. The different shifts may result from the different
crystal architectures and coordination environments of the
metal centers.
-
sulfate radicals (SO4Á ) from sodium persulfate in the
presence of CPs as catalysts [4, 8, 10]. Sulfate radicals are
highly active for the decomposition of organic pollutants,
including dyes.
To study the catalytic properties of the present CPs,
methyl orange (MO) was chosen as a model dye to assess
the efficiency of its catalytic degradation. As shown in
Fig. 4 and S3, little decolorization was observed in a blank
experiment, such that the degradation of MO only reached
14.5 % after 100 min, indicating that MO cannot be
effectively oxidized by Na2S2O8. However, when CP-1 or
CP-2 was introduced as a heterogeneous catalyst into the
reaction system, after 100 min, the degradation efficiency
of MO was increased considerably, to 86.9 or 92.7 % for
CP-1 and CP-2, respectively. In the presence of equimolar
amount of H2chdc, H2ndc, free ligand L, NiSO4Á6H2O or
MnSO4Á2H2O as further control experiments, approxi-
mately 17.3, 14.9, 18.7, 48.3 and 44.3 % of MO were
decomposed after 100 min, respectively.
Catalytic degradation behaviors
Due to their extensive industrial use, large amounts of dye
are released into effluent streams [31, 32]. Given their
chemical stability, removal of dyes from wastewater is an
123

Transition Met Chem
Fig. 2 a The coordination
environment of Mn(II) center in
CP-2 with ellipsoids at 30 %
probability, all hydrogen atoms
are omitted for clarity
(symmetry codes: A: x-1/2,
-y ? 1/2, z-1/2; B: -x ? 1,
-y ? 1, -z ? 2). b The 1D
wave-like chain. c The 1D
meso-helical [Mn(L)]n motif.
d View of the 3D network
structure. e The 3D dia network
in CP-2
Fig. 3 Emission spectra of two CPs and free ligand L in the solid
state at room temperature
Fig. 4 Results of CPs, metal salts and no catalyst for the degradation
of methyl orange
As shown in Table 3, after three successive cycles of
degradation experiments under the same conditions, the
activity of the recovered catalyst (CP-1 or CP-2) was
slightly decreased, due to leaching of metal ions. The
recovered catalysts retained the same structure as the
crystals used for X-ray powder diffraction (Fig. S1).
123

Transition Met Chem
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Table 3 Repeated catalytic experiments results of methyl orange
Cycle runs
D (%)
Cycle runs
D (%)
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CP-1
CP-2
1st run
2nd run
3rd run
86.9
82.5
75.4
1st run
2nd run
3rd run
92.7
88.7
82.6
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Therefore, both CPs exhibit not only good catalytic prop-
erties but also reasonable stabilities [34, 35].
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Conclusion
In this work, we have synthesized and characterized Ni and
Mn coordination complexes of N-donor ligands with two
distinct dicarboxylate co-ligands. CPs 1 and 2 have 3D
twofold interpenetrated and non-interpenetrated dia nets,
respectively. CP-2 shows higher catalytic activity and
stability than CP-1 in the Fenton-like decomposition of
methyl orange.
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X-ray crystallographic files in CIF format for CPs 1-2 have
been deposited at the Cambridge Crystallographic Data
Centre with CCDC No: 1472278–1472279. These data can
be obtained free of charge via http://www.ccdc.-
cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2
1EZ,
UK;
fax:
(?44)
or
e-mail:
deposit@ccdc.cam.ac.uk.
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Acknowledgments The work was supported by the National Natural
Science Foundation of China (51474086), Natural Science Founda-
tion–Steel and Iron Foundation of Hebei Province (B2015209299).
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