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Syntheses, Structures, and Photocatalytic and Sonocatalytic


Degradations of Methyl Blue of Cu(II) and Mn(II) Coordination
Polymers Based on Tri(triazole) and Dicarboxylate Ligands
Chao Yin, Xing Wang, Jian-Gang Ding, Bao-Long Li * , Bing Wu and Chuan-Jiang Hu

College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, Suzhou 215123, China;
[email protected] (C.Y.); [email protected] (X.W.); [email protected] (J.-G.D.);
[email protected] (B.W.); [email protected] (C.-J.H.)
* Correspondence: [email protected]

Abstract: Cu(II) and Mn(II) coordination polymers [Cu(ttpa)(sub)]n (Cuttpa or 1) and


{[Mn2 (ttpa)2 (nip)2 (H2 O)2 ]·3H2 O}n (Mnttpa or 2) (ttpa = tris(4-(1,2,4-triazol-1-yl)phenyl)amine, H2 sub
= suberic acid, nip = 5-nitroisophthalicate) were hydrothermally prepared and the structures were
characterized. Cuttpa exhibited a 2D (4,4) network based on [Cu2 (COO)4 ] dimers with upper and
lower dangled ttpa ligands and a 2D → 3D polythreaded network. Mnttpa showed a 2D (4,4) network
with dangled uncoordinated triazole rings from ttpa ligands and nitro groups from nip2− ligands
and a 2D → 3D polythreaded network. Eg data of Cuttpa and Mnttpa were 1.88 eV and 2.11 eV.
Cuttpa and Mnttpa exhibited good catalytic activity for the decomposition of methyl blue (MB)
under visible light and supersound irradiation. The decomposition mechanism using Cuttpa was
explored. The holes (h+ ) and • OH hydroxyl radicals played the main roles, and the • O2 − superoxide
radicals played certain auxiliary roles in the decomposition of MB within the Cuttpa catalyst.

Keywords: coordination polymer; polythreaded; photocatalysis; sonocatalysis; catalytic mechanism

Citation: Yin, C.; Wang, X.; Ding, J.-G.;


Li, B.-L.; Wu, B.; Hu, C.-J. Syntheses, 1. Introduction
Structures, and Photocatalytic and In recent years, more and more inorganic chemistry and materials scientists have
Sonocatalytic Degradations of Methyl become interested in coordination polymers, not only due to their greatly varying and inter-
Blue of Cu(II) and Mn(II) esting structures [1], but also due to their multifunctional materials for use in applications
Coordination Polymers Based on such as chemical sensors [2], gas storage and adsorption [3], adsorbents for the elimina-
Tri(triazole) and Dicarboxylate tion of toxic chemicals and pollutants [4], catalysis [5], magnetism [6], luminescence [7]
Ligands. Molecules 2024, 29, 5289.
and biology [8]. Entanglement is an important topic related to coordination polymers
https://doi.org/10.3390/
which usually allows for improvement in their packing efficiency when one single network
molecules29225289
has large free voids [9]. In addition to interpenetration, polycatenation and polyknots,
Received: 12 October 2024 polythreaded systems represent one more intriguing subgroup of entanglement [9–11].
Revised: 3 November 2024 Polythreaded frameworks are usually constructed from low-dimensional networks such as
Accepted: 7 November 2024 0D, 1D and 2D networks with dangled side arms which are frequency assembled by longer
Published: 8 November 2024 organic ligands [9–11]. Even now, polythreaded systems are still less commonly explored.
Examples of 2D → 3D polythreaded networks are scarcely documented [12–16].
With the population increasing and social development, the increasing prevalence of
organic wastewater is a serious environmental topic. In the past two decades, the effective
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
treatment of organic wastewater has been an important topic. Compared with other meth-
This article is an open access article
ods, such as membrane technology, coagulation and flocculation, to remove dyes from dirty
distributed under the terms and
water, photocatalysis has its own unique advantages, such as simple manipulation proce-
conditions of the Creative Commons dures, low energy consumption, no secondary pollution and high degradation efficiency,
Attribution (CC BY) license (https:// and it can use photocatalysts to degrade organic dyes into non-toxic small molecules with
creativecommons.org/licenses/by/ solar energy [17]. Nevertheless, the traditional inorganic semiconductor photocatalysts
4.0/). such as TiO2 and ZnO with high band gaps (Eg ) (3.2 eV for TiO2 , 3.4 eV for ZnO) only

Molecules 2024, 29, 5289. https://doi.org/10.3390/molecules29225289 https://www.mdpi.com/journal/molecules


Molecules 2024, 29, 5289 2 of 12

could utilize a small amount of ultraviolet light (<4%) or visible light or sunlight from solar
energy [18,19]. Sunlight contains approximately 45% visible light. Coordination polymer
catalysts showing low band gaps could degrade organic dyes under visible light irradiation
or sunlight with high efficiency [20–25]. This is one good example of utilizing solar energy.
Meanwhile, the sonocatalytic degradation of organic dyes under ultrasound also is one
good method of removing organic dyes [26].
The topologies and properties of coordination polymers are strongly dependent on
central metal cations and ligands [27–30]. N-donor ligands (containing pyridine, triazole,
imidazole) and O-donor carboxylate co-ligands are widely employed for constructing
coordination polymers [27–30]. Tris(4-(1,2,4-triazol-1-yl)phenyl)amine (ttpa) contains three
triazole rings around the triphenylamine center and can strongly coordinate to metal ions
with its three four-position triazole N atoms [31–33]. Multicarboxylate ligands such as
suberic acid (H2 sub) and 5-nitroisophthalic acid (H2 nip) containing two carboxylate groups
can link metal ions with diverse coordination modes and can deprotonate to balance the
charge of the coordination network [34,35]. Herein, copper(II) and manganese(II) coor-
dination polymers, [Cu(ttpa)(sub)]n (Cuttpa or 1) and {[Mn2 (ttpa)2 (nip)2 (H2 O)2 ]·3H2 O}n
(Mnttpa or 2), were hydrothermally successfully prepared by employing the N-donor
ligand ttpa and O-donor ligands H2 sub and H2 nip. Their structures were characterized.
Cuttpa has a 2D (4,4) network with a Cu2 (COO)4 ] unit and a 2D → 3D polythreaded
framework. Mnttpa has a 2D (4,4)-network and a 2D → 3D polythreaded framework. The
catalytic decomposition of methyl blue (MB) under visible light and supersound irradiation
were observed. The decomposition mechanism using Cuttpa was studied.

2. Results and Discussion


2.1. Structures
Cuttpa has a 2D (4,4)-network with a Cu2 (COO)4 ] unit and a 2D → 3D polythreaded
framework. The Cuttpa crystal was monoclinic and P21 /c. The unsymmetric units were
the Cu(II) (Cu(1)), the ttpa, as well as the sub2− . Cu(1) was in distorted square pyramidal
coordination through four COO− O atoms (O(1), O(2A), O(3B), O(4C)) of four sub2− (Cu(1)-
O(1) 1.962(3) Å; Cu(1)-O(2A) 1.984(3) Å; Cu(1)-O(3B) 1.969(2) Å; Cu(1)-O(4C) 1.965(2) Å) in
the square plane and one triazole N atom (N(3)) of one ttpa (Cu(1)-N(3) 2.172(2) Å) at the
axis (Figure 1a).
Each oxygen atom of two carboxylates from one sub2− coordinates a copper(II) atom.
A sub2− connects four copper(II) atomc, forms a [Cu2 (COO)4 ] unit, and assembles a
[Cu(sub)]n 2D (4,4) network with a [Cu2 (COO)4 ] unit (Figure 1b). The point symbol for
this 2D network is 44 ·62 [36].
The ttpa ligand contains three triazole rings based on the tris(phenyl)amine frame. But
only a four-position triazole N (N3) of one ttpa ligand coordinates a copper(II) atom. Two
other four-position triazole N atoms (N6, N9) do not coordinate. Therefore, uncoordinated
triazole rings serve as dangling arms which are located above and below the [Cu(sub)]n 2D
network (Figure 1c). The dangling arms thread into the windows of adjacent 2D networks
and yield the 2D → 3D polythreaded framework (Figure 1d).
Mnttpa has a 2D (4,4)-network and a 2D → 3D polythreaded framework. Crystal Mnttpa
is a triclinic crystal system and a P1 space group. The unsymmetric unit is two Mn(II) atoms
(Mn(1), Mn(2)), two ttpa ligands, two nip2− ligands, as well as two coordinated H2 O atoms
(O(7), O(14)). The Mn(1) is in the distorted octahedral coordination with three carboxylate O
atoms (O(1), O(10A), O(11A)) of two nip2− ligands (Mn(1)-O(1) 2.1357(16) Å; Mn(1)-O(10A)
2.3936(17) Å; Mn(1)-O(11A) 2.2382(17) Å), one oxygen atom, O(7), of coordinated water
(Mn(1)-O(7) 2.1469(17) Å), and two triazole N atoms (N(3), N(16B)) of two ttpa ligands (Mn(1)-
N(3) 2.238(2) Å; Mn(1)-N(16B) 2.225(2) Å) (Figure 2a). The Mn(2) is in the distorted octahedral
coordination with three COO− O atoms (O(3), O(4), O(8)) of two nip2− ligands (Mn(1)-O(3)
2.2362(17) Å; Mn(1)-O(4) 2.2340(17) Å; Mn(1)-O(8) 2.1537(17) Å), one oxygen atom, O(14), of
coordinated water (Mn(1)-O(14) 2.1652(18) Å), and two triazole N atoms (N(6C), N(13)) of
two ttpa ligands (Mn(1)-N(6C) 2.249(2) Å; Mn(1)-N(13) 2.247(2) Å) (Figure 2a).
Molecules 2024,
Molecules 29, 29,
2024, 5289x FOR PEER REVIEW 3 of 13 3 of 12

Molecules 2024, 29, x FOR PEER REVIEW 4 of 13

Figure 1.
Figure 1. (a)
(a)The
Thecoordination
coordination of Cu(II) in Cuttpa.
of Cu(II) (b) The
in Cuttpa. (b)2D
Thenetwork [Cu(sub)]
2D network n in Cuttpa. (c) The
[Cu(sub)] n in Cuttpa. (c) The
2D and
Å), network
two [Cu(ttpa)(sub)]
triazole N n in Cuttpa. (d) Scheme showing the 2D3D polythreaded framework
atoms (N(6C), N(13)) of two ttpa ligands (Mn(1)-N(6C) 2.249(2) Å;framework
2D network [Cu(ttpa)(sub)]n in Cuttpa. (d) Scheme showing the 2D→3D polythreaded
in Cuttpa.
Cuttpa. 2.247(2) Å) (Figure 2a).
Mn(1)-N(13)
in
Each oxygen atom of two carboxylates from one sub2− coordinates a copper(II) atom.
A sub2− connects four copper(II) atomc, forms a [Cu2(COO)4] unit, and assembles a
[Cu(sub)]n 2D (4,4) network with a [Cu2(COO)4] unit (Figure 1b). The point symbol for this
2D network is 44·62 [36].
The ttpa ligand contains three triazole rings based on the tris(phenyl)amine frame.
But only a four-position triazole N (N3) of one ttpa ligand coordinates a copper(II) atom.
Two other four-position triazole N atoms (N6, N9) do not coordinate. Therefore, uncoor-
dinated triazole rings serve as dangling arms which are located above and below the
[Cu(sub)]n 2D network (Figure 1c). The dangling arms thread into the windows of adja-
cent 2D networks and yield the 2D  3D polythreaded framework (Figure 1d).
Mnttpa has a 2D (4,4)-network and a 2D  3D polythreaded framework. Crystal
Mnttpa is a triclinic crystal system and a P1 space group. The unsymmetric unit is two
Mn(II) atoms (Mn(1), Mn(2)), two ttpa ligands, two nip2− ligands, as well as two coordi-
nated H2O atoms (O(7), O(14)). The Mn(1) is in the distorted octahedral coordination with
three carboxylate O atoms (O(1), O(10A), O(11A)) of two nip2− ligands (Mn(1)-O(1)
2.1357(16) Å; Mn(1)-O(10A) 2.3936(17) Å; Mn(1)-O(11A) 2.2382(17) Å), one oxygen atom,
O(7), of coordinated water (Mn(1)-O(7) 2.1469(17) Å), and two triazole N atoms (N(3),
N(16B)) of two ttpa ligands (Mn(1)-N(3) 2.238(2) Å; Mn(1)-N(16B) 2.225(2) Å) (Figure 2a).
The Mn(2) is in the distorted octahedral coordination with three COO− O atoms (O(3),
O(4), O(8)) of two nip2− ligands (Mn(1)-O(3) 2.2362(17) Å; Mn(1)-O(4) 2.2340(17) Å; Mn(1)-
O(8) 2.1537(17) Å), one oxygen atom, O(14), of coordinated water (Mn(1)-O(14) 2.1652(18)

Figure (a)The
Figure 2.2.(a) Thecoordination
coordination Mn(II)
Mn(II) atoms
atoms in Mnttpa.
in Mnttpa. (b) The(b)
2DThe 2D network
network in (c)
in Mnttpa. Mnttpa.
The (c) The
2D →3Dpolythreaded
2D3D polythreaded framework
framework in Mnttpa.
in Mnttpa. Thedashed
The blue blue dashed lines the
lines present present the hydrogen
hydrogen bonding bonding
interaction from
interaction fromadjacent 2D2D
adjacent networks. The dashed
networks. lines show
The dashed lines the hydrogen
show bonding bonding
the hydrogen interactions.
interactions.

The carboxylate (O(1)O(2) or O(8)O(9)) of one nip2− ligand exhibits monodentate. The
other carboxylate (O(3)O(4) or O(10)O(11)) of one nip2− ligand serves as a chelating coor-
dinated mode (Figure 2a). Each nip2− ligand behaves as a bridge and links two Mn(II) at-
oms. The ttpa ligand contains three triazole rings based on the tris(phenyl)amine frame.
But two four-position triazole N atoms (N(3)N(6) or N(13)N(16)) of one ttpa ligand serve
bridging functions and link two Mn(II) atoms. One other four-position triazole N (N(9) or
2−
Molecules 2024, 29, 5289 4 of 12

The carboxylate (O(1)O(2) or O(8)O(9)) of one nip2− ligand exhibits monodentate.


The other carboxylate (O(3)O(4) or O(10)O(11)) of one nip2− ligand serves as a chelating
coordinated mode (Figure 2a). Each nip2− ligand behaves as a bridge and links two Mn(II)
atoms. The ttpa ligand contains three triazole rings based on the tris(phenyl)amine frame.
But two four-position triazole N atoms (N(3)N(6) or N(13)N(16)) of one ttpa ligand serve
bridging functions and link two Mn(II) atoms. One other four-position triazole N (N(9)
or N(19)) was uncoordinated. Therefore, the Mn(II) atoms are linked by nip2− and ttpa
bridging and assemble the 2D (4,4) network (Figure 2b). The point symbol of this 2D
network is 44 ·62 [36].
Therefore, uncoordinated triazole rings from the ttpa ligands and nitro groups from the
nip2− ligands serve as dangling arms which are located above and below the 2D network
(Figure 2c). The dangling arms thread into the windows of adjacent 2D networks and
yield a 2D → 3D polythreaded framework (Figure 2c). The hydrogen bond interactions
between coordinated H2 O molecules and carboxyl O and triazole N atoms from adjacent
2D networks (O(7). . .O(2) (1 − X, 1 − Y, −Z) 2.701(3) Å; O(7). . .N(19) (–X, 1 − Y, –Z) 2.788(3)
Å; O(14) . . .O(9) (1 − X, 2 − Y, 1 − Z) 2.675(3) Å; O(14). . .N(9) (–X, 1 − Y, –Z) 2.834(3) Å) have
important roles in the stability of 3D polythreaded supramolecular architecture (Figure 2c).
A polythreaded framework is an interesting topic within crystal engineering [9–16]. The 2D
→ 3D polythreaded frameworks are uncommon, and few have been documented [12–16].
This research gave two new examples of 2D → 3D polythreaded frameworks.

2.2. Syntheses, PXRDs, FT-IR, and Eg


Cuttpa and Mnttpa were successfully synthesized by using ttpa, H2 suc, or H2 nip
and Cu(II) or Mn(II) with the hydrothermal method. The reaction conditions (solvent
H2 O/DMF, the reaction temperature, the ratio of reactants, and pH (the reactant NaOH))
were first employed according to our previous synthesis experience. The ratios of
ttpa:H2 suc:Cu(II) = 1:2:3 and ttpa:H2 nip:Mn(II) = 1:2:3 were used due to the need to
improve yield based on the expensive ttpa ligand. The reaction products from different
reaction temperatures and different reaction times were observed. The different reaction
temperatures and reaction times for syntheses of Cuttpa and Mnttpa were selected because
of the high quality of single crystals suitable for single-crystal X-ray diffraction (91 ◦ C and
3.1 days for the synthesis of Cuttpa; 101 ◦ C and 2.2 days for the synthesis of Mnttpa) that
were obtained for these reactions. Meanwhile, the synthesis of coordination polymers was
not successful when using ttpa, H2 nip, and Cu(II). No coordination polymer was obtained
by using ttpa, H2 suc, and Mn(II).
The powder X-ray diffraction (PXRD) patterns of Cuttpa and Mnttpa were recorded at
room temperature (Figures S1 and S2). The peak positions of the simulated and experimen-
tal PXRD patterns are in agreement with each other, which confirms their phase purities.
The FT-IR spectra of Cuttpa and Mnttpa were recorded. For Cuttpa, the peaks at 1615,
1592, and 1495 cm−1 are attributed to the asymmetric and symmetric stretching vibrations
of carboxylate. There are no absorptions in the 1690~1730 cm−1 region, indicating the
complete deprotonation of H2 suc [34]. The peaks at 1515 and 1275 cm−1 are attributed
to the stretching vibration region of C=N bonds of the ttpa ligand. For Mnttpa, the
broad absorption (3112 cm−1 ) is due to the O-H group stretching vibration from the water
molecules. The peaks at 1604, 1376, and 1349 cm−1 are attributed to the asymmetric and
symmetric stretching vibrations of carboxylate [34]. The peak at 1558 cm−1 is attributed
to the nitro group from nip2− . The peaks at 1517 and 1274 cm−1 are attributed to the
stretching vibration region of C=N bonds of the ttpa ligand.
UV spectra for Cuttpa and Mnttpa showed that the Eg data of Cuttpa and Mnttpa
were 1.88 and 2.11 eV, respectively (Figure 3).
cules. The peaks at 1604, 1376, and 1349 cm−1 are attributed to the asymmetric and sym-
metric stretching vibrations of carboxylate [34]. The peak at 1558 cm−1 is attributed to the
nitro group from nip2−. The peaks at 1517 and 1274 cm−1 are attributed to the stretching
vibration region of C=N bonds of the ttpa ligand.
Molecules 2024, 29, 5289 UV spectra for Cuttpa and Mnttpa showed that the Eg data of Cuttpa and Mnttpa5 of 12
were 1.88 and 2.11 eV, respectively (Figure 3).

Figure 3.
Figure 3. The
The UV
UV spectra
spectraofofCuttpa
Cuttpa(1)(1)and
andMnttpa
Mnttpa(2).(2).

2.3. Photocatalytic
2.3. Photocatalytic and
andSonocatalytic
SonocatalyticDecomposition
Decompositionof MB
of MB
Molecules 2024, 29, x FOR PEER REVIEW 6 of 13
Molecules 2024, 29, x FOR PEER REVIEW The photocatalytic
The photocatalytic and andsonocatalytic
sonocatalyticdecomposition
decomposition of of
methyl
methyl blue (MB)
blue waswas
(MB) 6inves-
of investi-
13
tigated within Cuttpa and Mnttpa catalysts under visible light and supersound
gated within Cuttpa and Mnttpa catalysts under visible light and supersound irradiation. irradia-
tion.decomposition
The The decomposition efficiencies
efficiencies of trade
of trade TiO2 (60 2 (60and
TiOnm) nm)TiOand TiO2 (20 nm) were also
2 (20 nm) were also measured.
The decomposition efficiencies of MB were 92.5% within Cuttpa, 68.8% within
measured.
The decomposition
The decomposition efficiencies ofofMBMBwerewere92.5% within Cuttpa, 68.8% within Mnttpa,
Mnttpa, 38.2% within TiOefficiencies 92.5% within Cuttpa,
2 (60 nm), 64.3% within TiO2 (20 nm), and 19.9% within blank
68.8% within
38.2%
Mnttpa, within TiO
38.2% within
2 (60 nm), 64.3% within TiO
TiO2 (60 nm), 64.3% within 2 (20 nm), and 19.9% within blank
TiO2 (20 nm), and 19.9% within 2blankH O 2 within
H 2O2 within visible light after 90 min (Figures 4–6). After the photocatalytic decomposi-
visible light after
H2O2experiments,
within visible90 min (Figures
light after 4–6). After
90 min (Figures the photocatalytic decomposition experiments,
tion Cuttpa and Mnttpa sustained4–6).theirAfter the photocatalytic
structures (Figures S1 and decomposi-
S2). The
Cuttpa and Mnttpa sustained their structures (Figures S1 and(Figures
S2). TheS1catalytic efficiency
catalytic efficiency with decomposition MB was Cuttpa > Mnttpa > TiO2 (20 nm)S2).
tion experiments, Cuttpa and Mnttpa sustained their structures and The2
> TiO
with decomposition
catalytic efficiency MB
with was Cuttpa
decomposition > Mnttpa
MB was > TiO
Cuttpa2 (20
> nm)
Mnttpa > TiO
> TiO
2 (60
(60 nm) within visible light. These results showed that Cuttpa is a good photocatalyst, and nm)
2 (20 within
nm) > TiO visible
2

light.
(60 nm)These results
within showed
visible light. that
These Cuttpa
results is a
showedgood photocatalyst,
that
Mnttpa is an effective photocatalyst with the decomposition of MB. Cuttpa is a and
good Mnttpa is
photocatalyst, an effective
and
photocatalyst with thephotocatalyst
Mnttpa is an effective decomposition withofthe
MB.decomposition of MB.

Figure 4. Absorption intensities for MB solution within photocatalytic process within Cuttpa (1)
Figure 4. Absorption
catalyst.4.
Figure Absorption intensities
intensities for
forMB
MBsolution
solutionwithin
withinphotocatalytic
photocatalytic process
process within
within Cuttpa
Cuttpa (1)(1)
catalyst.
catalyst.

Figure
Figure 5. Absorption
5. Absorption intensities
intensities for MB
for MB solution
solution within
within photocatalytic
photocatalytic processprocess within (2)
within Mnttpa Mnttpa
Figure 5. Absorption intensities for MB solution within photocatalytic process within Mnttpa (2)
catalyst.
(2) catalyst.
catalyst.
Molecules 2024, 29, 5289 Figure 5. Absorption intensities for MB solution within photocatalytic process within Mnttpa (2)6 of 12
catalyst.

Figure 6.
Molecules 2024, 29, x FOR PEER REVIEW 6. The
Thedecomposition
decompositionefficiencies forfor
efficiencies MBMB
within catalyst
within Cuttpa
catalyst (1), Mnttpa (2), TiO
(1), Mnttpa (2),772, TiO
and
of 13
Figure
Molecules 2024, 29, x FOR PEER REVIEW Cuttpa of 132 , and
blank in the photocatalytic process.
blank in the photocatalytic process.

The decompositionefficiencies
decomposition
The decomposition efficiencies with
with MBMB were
were 91.3%
91.3% within
within Cuttpa,
Cuttpa, 54.9%54.9% within
within
The efficiencies with MB were 91.3% within Cuttpa, 54.9% within
Mnttpa, 45.0%
Mnttpa, 45.0% within
45.0% within TiO
within TiO (60
TiO22 2(60 nm),
(60 nm), 69.2%
nm), 69.2% within
69.2% within
within TiO TiO
TiO22 (20
(20 (20 nm), and 22.8% within
2 nm), and 22.8% within blank blank
Mnttpa, nm), and 22.8% within blank
H O
H222O within
O222 within ultrasound
within ultrasound after
ultrasound after
after 105105 min
105 min (Figures
min (Figures 7–9).
(Figures 7–9). After
7–9). After
After the the sonocatalytic
the sonocatalytic decomposition
sonocatalytic decomposition
decomposition
H
experiments,
experiments, Cuttpaand
Cuttpa and Mnttpa
Mnttpa sustained
sustained theirtheir structures
structures (Figures
(Figures S1 and S1 and
S2). The S2).
cata- The
experiments, Cuttpa and Mnttpa sustained their structures (Figures S1 and S2). The cata-
catalytic
lytic efficiency
efficiency with with
the the decomposition
decomposition of MB of
wasMB was
Cuttpa Cuttpa
> TiO >
2 (20TiO
nm)
lytic efficiency with the decomposition of MB was Cuttpa > TiO2 (20 nm) > Mnttpa > TiO 2 (20
> nm)
Mnttpa >> Mnttpa
TiO22 >
TiO
(60 2nm)(60 nm) within
within ultrasound.
ultrasound. TheseThese experimental
experimental results
results showedshowed
that
(60 nm) within ultrasound. These experimental results showed that Cuttpa is a good that
Cuttpa Cuttpa
is a is
gooda good
sonoocatalyst, and
sonoocatalyst,
sonoocatalyst, and Mnttpa
and Mnttpa
Mnttpais isisan
an effective
aneffective
effectivesonocatalyst
sonocatalyst
sonocatalyst forfor
for thethe
the decomposition
decomposition
decomposition of MB.
of MB.
of MB.

Figure 7.
Figure
Figure 7. Absorption
7. Absorption intensities
Absorption intensities ofofMB
intensitiesof MB solution
MBsolution within
solution sonocatalytic
within
within decomposition
sonocatalytic
sonocatalytic process
decomposition
decomposition within
process
process within
within
Cuttpa (1) catalyst.
Cuttpa (1) catalyst.
catalyst.
Cuttpa

Figure 8.
Figure 8. Absorption
Absorption intensities
intensities of
of MB
MB solution
solution within
within sonocatalytic
sonocatalytic decomposition
decomposition process
process within
within
Figure Absorption
Mnttpa8.(2)
(2) catalyst. intensities of MB solution within sonocatalytic decomposition process within
Mnttpa catalyst.
Mnttpa (2) catalyst.
Molecules 2024, 29, 5289
Figure 8. Absorption intensities of MB solution within sonocatalytic decomposition process within7 of 12
Mnttpa (2) catalyst.

Figure 9. The
Figure
Molecules 2024, 29, x FOR PEER REVIEW Thedecomposition
decompositionefficiencies forfor
efficiencies MB within
MB Cuttpa
within (1) and
Cuttpa Mnttpa
(1) and (2) catalysts
Mnttpa and
(2) catalystsTiO
and
8 of 132 TiO2
and blank
and blank in
in the
thesonocatalytic
sonocatalyticprocess.
process.

The stability of the catalyst could be observed in the recycling experiments. After
The stability of the catalyst could be observed in the recycling experiments. After
each cycling experiment, the Cuttpa (1) catalyst was recovered by centrifugation, filtration,
each cycling experiment, the Cuttpa (1) catalyst was recovered by centrifugation, filtra-
washing with with
tion, washing deionized
deionizedwater andand
water ethanol several
ethanol times,
several and
times, then
and thendrying
dryingunder
underroom
temperature.
room temperature.FigureFigure
10 is a10graph of five
is a graph of cycles of the
five cycles photocatalytic
of the degradation
photocatalytic degradation of of
MB by
Cuttpa (1) under visible light irradiation. It can be seen that the catalytic
MB by Cuttpa (1) under visible light irradiation. It can be seen that the catalytic activity activity decreased
slightly
decreased after five after
slightly cycles,fiveand theand
cycles, finalthedegradation efficiency
final degradation reached
efficiency 86.2%
reached 86.2%after
af- five
cycles.
ter five cycles. The suspension after the last cycle of the degradation experiment was taken out,
The suspension after the last cycle of the degradation experiment was taken
centrifuged, andand
out, centrifuged, filtrated
filtratedto to
give
giveaaclear
clear solution. Theamount
solution. The amount of copper
of copper species
species in thein the
solution was
solution was measured by ICP. The concentration
The concentration of the copper species
species in the solution
solution was
low (0.13 mg/L). The removal rate of Cu(II) ions from the Cuttpa
was low (0.13 mg/L). The removal rate of Cu(II) ions from the Cuttpa (1) catalyst (1) catalyst waswas0.35%,
indicating the stable
0.35%, indicating and reusable
the stable nature
and reusable of theofCuttpa
nature (1) catalyst.
the Cuttpa (1) catalyst.

Figure 10.
Figure 10. Five
Five cycles
cyclesof
ofphotocatalytic
photocatalyticdegradation
degradationofofMB
MBbyby Cuttpa
Cuttpa (1)(1) under
under thethe visible
visible light
light ir-
irradiation.
radiation.
The photocatalytic and sonocatalytic mechanisms are similar [37]. The photocatalytic
The photocatalytic
experiments and sonocatalytic
within Cuttpa, scavenger mechanisms are similar [37].(BQ),
mannitol, benzoquinone The photocatalytic
and ammonium
experiments within Cuttpa, scavenger mannitol, benzoquinone (BQ), and
oxalate (AO) were carried out (Figures 11 and 12). The decomposition efficiency ammonium ox- was
of MB
alate (AO) were carried out (Figures 11 and 12). The decomposition efficiency
92.5% with Cuttpa. However, the decomposition efficiencies declined to 69.0% with BQ, of MB was
92.5% with
37.5% with mannitol,
Cuttpa. However,
and 27.7%the with
decomposition
AO. Here,efficiencies
the holes (h declined
+ ) and •to
OH69.0% with BQ,
hydroxyl radicals
37.5% with mannitol, and 27.7% with AO. Here, the holes (h +) and •OH hydroxyl
played the main roles, and the • O2 − superoxide radicals played certain auxiliary radicals
roles in
played the main roles, and the •O2− superoxide radicals played certain auxiliary roles in
the decomposition of MB within the Cuttpa catalyst.
the decomposition of MB within the Cuttpa catalyst.
The photocatalytic and sonocatalytic mechanisms are similar [37]. The photocatalytic
experiments within Cuttpa, scavenger mannitol, benzoquinone (BQ), and ammonium ox-
alate (AO) were carried out (Figures 11 and 12). The decomposition efficiency of MB was
92.5% with Cuttpa. However, the decomposition efficiencies declined to 69.0% with BQ,
37.5% with mannitol, and 27.7% with AO. Here, the holes (h+) and •OH hydroxyl radicals
Molecules 2024, 29, 5289
played the main roles, and the •O2− superoxide radicals played certain auxiliary roles in8 of 12
the decomposition of MB within the Cuttpa catalyst.

Molecules 2024, 29, x FOR PEER REVIEW 9 of 13

Figure
Figure 11. The decomposition
11. The decompositionefficiencies
efficiencies
of of
MB MB with
with (1) (1)
Cuttpa
Cuttpa andand within
within the scavengers
the scavengers and and
blanks within
blanks within the
the photocatalytic
photocatalyticdecomposition
decomposition process.
process.

Figure 12. The decomposition efficiencies of MB with Cuttpa (1) and within the scavengers within
Figure 12. The decomposition
the photocatalytic efficiencies
decomposition of MB with Cuttpa (1) and within the scavengers within
process.
the photocatalytic decomposition process.
The catalytic mechanism using Cuttpa and Mnttpa catalysts was supposed. When the
The catalytic
Cuttpa or Mnttpamechanism using
catalyst was Cuttpa to
exposed and Mnttpa
visible catalysts was supposed.
radiation/supersound, theWhen
electrons of
the CuttpaororMnttpa
Cuttpa Mnttpacould
catalyst
bewas exposed
emitted awayto visible
from theradiation/supersound,
valence band (VB)the electrons
to the conduction
ofband
Cuttpa or Mnttpa
(CB), leadingcould besame
to the emitted away from
amounts the valence
of holes (h+ ) inband
VB. (VB)
The to the conduction
photoexcited electrons
band (CB), leading to the same amounts of
• holes (h+) in VB. The photoexcited electrons
could react with H2 O2 to result in the OH hydroxyl radicals and react with oxygen and
could
resultreact
in •with
O2 − H 2O2 to result in the •OH hydroxyl
superoxide. radicals and
The holes (h+ ), • OH hydroxyl, andreact
• O with
− oxygen and
2 superoxide radicals
result in •O 2 superoxide. The holes (h+), •OH hydroxyl, and •O2− superoxide radicals per-

perhaps decompose MB to result in CO2 , H2 O, and other inorganic substances.
haps decompose MB to result in CO2, H2O, and other inorganic substances.
3. Experimental Section
3.3.1.
Experimental Section
Materials and Methods
3.1. Materials and Methods
All other reagents were commercial and used without further purification. The spectra
wereAllmeasured
other reagents
on awereVariancommercial andspectrometer
1000 FT-IR used without further
(Varian,purification. The spec-
Inc., Palo Alto, CA, USA)
tra were measured on −a 1Varian 1000 FT-IR spectrometer (Varian, Inc.,
in the 4000–400 cm region. Powder X-ray diffractions (PXRDs) were performedPalo Alto, CA, USA) using
inwith
the 4000–400
a D2 Phaser region. Billerica,
cm−1(Bruker, Powder X-ray diffractions
MA, USA) X-ray (PXRDs) were performed
diffractometer with Cu-Kα using
radiation
with a D2 Phaser (Bruker, Billerica, MA, USA) X-ray diffractometer with Cu-Kα
(λ = 1.5406 Å) was used at room temperature. C, H and N were carried out on a Perkin- radiation
(λElmer
= 1.5406
240CÅ)analyser
was used(Perkin-Elmer,
at room temperature.
Waltham,C, MA,
H and N were
USA). Thecarried
UV-visout on a were
spectra Perkin-
collected
Elmer 240C analyser (Perkin-Elmer, Waltham, MA, USA). The UV-vis spectra were col-
using a Cary 500 spectrometer (Agilent, Santa Clara, CA, USA). The amount of copper
lected using a Cary 500 spectrometer (Agilent, Santa Clara, CA, USA). The amount of cop-
was measured using the inductively coupled plasma (ICP) spectrometer Optima 2100
per was measured using the inductively coupled plasma (ICP) spectrometer Optima 2100
(Perkin-Elmer, Ningbo, China).
(Perkin-Elmer, Ningbo, China).
3.2. Preparation of [Cu(ttpa)(sub)]n (Cuttpa or 1)
3.2. Preparation of [Cu(ttpa)(sub)]n (Cuttpa or 1)
The reactants of ttpa (0.10 mmol, 0.045 g), H sub (0.20 mmol, 0.035 g), Cu(NO ) ·3H2 O
The reactants of ttpa (0.10 mmol, 0.045 g), H2sub2(0.20 mmol, 0.035 g), Cu(NO3)2·3H32O2
(0.30 mmol, 0.075 g), NaOH (0.037 mmol, 0.015 g), H2 O (3.6 mL), and DMF (1.7 mL) were
(0.30 mmol, 0.075 g), NaOH (0.037 mmol, 0.015 g), H2O (3.6 mL), and DMF (1.7 mL) were ◦
placed into one hard glass tube (8.0 mL). The mixed reactants were heated to 91 C for
placed into one hard glass tube (8.0◦mL). The mixed reactants were heated to 91 °C for 3.1
3.1 days, and then chilled to 19 C. The blue crystals [Cu(ttpa)(sub)] were obtained and
days, and then chilled to 19 °C. The blue crystals [Cu(ttpa)(sub)]n weren obtained and
weighed asas
weighed 0.038
0.038 gg with
with a yield
a yield of of
56%56% (based
(based onon ttpa).
ttpa). Anal.
Anal. Calc.
Calc. for
for C C CuN
32H3032
H3010CuN
O4 10 O4
(Cuttpa): C, 56.34%; H, 4.43%; N, 20.54%. Found: C, 56.23%; H, 4.37%; N, 20.45%. IR data
(cm−1): 1615 m, 1592 m, 1515 m, 1419 m, 1399 w, 1326 w, 1308 w, 1275 s, 1177 w, 1052 w,
978 m, 954 w, 833 m, 709 w, 654 m, 628 w.

3.3. Preparation of {[Mn2(ttpa)2(nip)2(H2O)2]·3H2O}n (Mnttpa or 2)


Molecules 2024, 29, 5289 9 of 12

(Cuttpa): C, 56.34%; H, 4.43%; N, 20.54%. Found: C, 56.23%; H, 4.37%; N, 20.45%. IR data


(cm−1 ): 1615 m, 1592 m, 1515 m, 1419 m, 1399 w, 1326 w, 1308 w, 1275 s, 1177 w, 1052 w,
978 m, 954 w, 833 m, 709 w, 654 m, 628 w.

3.3. Preparation of {[Mn2 (ttpa)2 (nip)2 (H2 O)2 ]·3H2 O}n (Mnttpa or 2)
The reactants of ttpa (0.10 mmol, 0.045 g), H2 nip (0.20 mmol, 0.042 g), MnSO4 . H2 O
(0.030 mmol, 0.051 g), NaOH (0.037 mmol, 0.015 g), H2 O (3.6 mL), and DMF (1.7 mL) were
placed into the hard glass tube (8.0 mL). The mixed reactants were heated to 101 ◦ C for
2.2 days, and then chilled to 19 ◦ C. The yellow crystals {[Mn2 (ttpa)2 (nip)2 (H2 O)2 ]·3H2 O}n
were obtained and weighed as 0.031 g with a yield of 41% (based on ttpa). Anal. Calc. for
C64 H52 Mn2 N22 O17 (Mnttpa): C, 50.87%; H, 3.47%; N, 20.40%. Found: C, 50.72%; H, 3.41%;
N, 20.29%. IR data (cm−1 ): 3112 m, 1604 m, 1558 m, 1517 s, 1451 w, 1434 w, 1376 m, 1349 m,
1274 m, 1145 w, 1113 m, 1081 w, 979 m, 832 w, 791 w, 733 m, 724 m, 673 m, 652 w.

3.4. X-Ray Crystallography


Crystal diffractions of [Cu(ttpa)(sub)]n (Cuttpa or 1) and {[Mn(ttpe)2 (ttpa)2 (nip)2
(H2 O)2 ]·3H2 O}n (Mnttpa or 2) were explored with one Bruker APEX-II CCD. The structures
were worked out and improved with the SHELXTL-2018 program [38]. The disordering
lattice molecules of Mnttpa were omitted using PLATON (https://www.platonsoft.nl/
xraysoft/, accessed on 6 November 2024). The crystallographic data are shown at Table 1.
Important bond lengths and angles are presented in Table S1.

Table 1. Crystallographic data for Cuttpa and Mnttpa.

Cuttpa Mnttpa
Formula C32 H30 CuN10 O4 C64 H46 Mn2 N22 O14
Fw 682.20 1457.11
T/K 188 (2) 189 (2)
Crystal system Monoclinic Triclinic
Space group P21 /c P1
a/Å 14.7579 (10) 11.5963 (8)
b/Å 18.6867 (13) 17.6243 (11)
c/Å 11.5203 (9) 19.6708 (12)
α (◦ ) 90 113.519 (2)
β (◦ ) 100.047 (2) 94.839 (2)
γ (◦ ) 90 104.434 (2)
V /Å3 3128.3 (4) 3492.6 (4)
F(000) 1412 1492
Z 4 2
ρcalcd (g cm−3 ) 1.448 1.386
µ(mm−1 ) 0.753 0.440
Reflections collected 60030 68,021
Unique reflections 7209 [R(int) = 0.0894] 15,953 [R(int) = 0.0951]
Parameter 424 939
Goodness of fit 1.050 1.050
R1 [I > 2σ(I)] 0.0541 0.0591
wR2 (all data) 0.1519 0.1797

3.5. Photocatalytic and Sonocatalytic Decomposition


The photocatalytic experiment was carried out using a PCR-I multipurpose photore-
actor (Beijing China Education Au-Light Company Limited, Beijing, China) equipped a
CEL-HXF300 Xe lamp with a UV cut-off filter (providing visible light with λ > 400 nm).
The amounts 40 mg of catalyst (Cuttpa or Mnttpa, or trade TiO2 (60 nm), or trade TiO2
(20 nm)) and 0.50 mL of 30% H2 O2 were added into 100 mL of methylene blue (MB) so-
lution (10 mg/L). The suspension solutions were stirred in dark conditions for about 30
min to ensure the complete equilibration of the adsorption/desorption of dyes on the
photocatalyst surface. Then, the mixture was stirred continuously under visible light ir-
Molecules 2024, 29, 5289 10 of 12

radiation. At a given interval, aliquots of the reaction mixtures were periodically taken,
purified by centrifugation, and analyzed with a UV-vis spectrophotometer at an absorption
wavelength of 664 nm for MB. In order to evaluate the reusability of the catalyst Cuttpa for
MB degradation, recycling experiments were carried out.
The sonocatalytic experiment was carried out in an ultrasonic bath (KQ-200VDE,
Kunshan, China) which was operated at a frequency of 100 kHz and with an effective power
output of 100 W. The amounts of 40 mg of catalyst (Cuttpa or Mnttpa, or trade TiO2 (60 nm),
or trade TiO2 (20 nm)) and 0.50 mL of 30% H2 O2 were added into 100 mL of methylene
blue (MB) solution (10 mg/L). The suspension solutions were stirred in dark conditions for
about 30 min to ensure the complete equilibration of the adsorption/desorption of dyes on
the catalyst surface before ultrasonic irradiation was started. The entire catalytic sonication
process took place at 26 ± 2 ◦ C in the dark to prevent the influence of daily or ambient light.
Then, the mixture was submitted for ultrasonic irradiation. At a given interval, aliquots of
the reaction mixture were periodically taken, purified by centrifugation, and analyzed with
a UV-vis spectrophotometer at an absorption wavelength of 664 nm for MB.

4. Conclusions
The copper(II) and manganese(II) coordination polymers were prepared and character-
ized. Cuttpa exhibited a 2D (4,4)-network with [Cu2 (COO)4 ] and a 2D → 3D polythreaded
network. Mnttpa showed a 2D (4,4)-network and a 2D → 3D polythreaded network. The
catalytic decomposition of methyl blue (MB) by visible light and supersound irradiation
were observed. The decomposition mechanism using Cuttpa was studied. The holes (h+ )
and • OH hydroxyl radicals played the main role, and the • O2 − superoxide radicals played
a certain auxiliary role in the decomposition of MB within the Cuttpa catalyst. Cuttpa and
Mnttpa are good catalysts in the decomposition of MB within visible light and supersound.

Supplementary Materials: The following supporting information can be downloaded at https://


www.mdpi.com/article/10.3390/molecules29225289/s1, Figure S1: PXRD patterns of the simulated
and the measured of Cuttpa (1), and after photocatalytic and sonocatalytic degradation. Figure S2:
PXRD patterns of the simulated and the measured of Mnttpa (2), and after photocatalytic and
sonocatalytic degradation. Table S1: Selected bond lengths (Å) and angles (o ) for Cuttpa and Mnttpa.
Author Contributions: C.Y.: Investigation, Data Curation, Writing—Original Draft. X.W.: Methodol-
ogy. J.-G.D.: Conceptualization, Writing—Review. B.-L.L.: Supervision, Review and Editing, Funding
Acquisition. B.W.: Instrument. C.-J.H.: Funding Acquisition. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (22071169),
the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the
State and Local Joint Engineering Laboratory for Functional Polymeric Materials, and the project of
scientific and technological infrastructure of Suzhou (SZS201905).
Institutional Review Board Statement: No applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The crystallographic data have been deposited in the Cambridge
Crystallographic Data Center (CCDC) with CCDC numbers 2094503, 2094504 at July 2021. These data
can be obtained free of charge, either from the CCDC via https://www.ccdc.cam.ac.uk/structures
(accessed on 6 November 2024) or can be obtained from the corresponding authors upon request.
Conflicts of Interest: The authors declare no conflicts of interest.

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