Molecules 29 05289 v2
Molecules 29 05289 v2
Molecules 29 05289 v2
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]
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.
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 2D3D 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
2D3D 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
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.
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 (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.
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
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.
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