crystals

Article
The Decoloration of Anionic and Cationic Dyes Using
ZnO and ZnO-Cu2O
Jiang Dong Dai, Luo Gan, Hai Yan Zhang and Chun Ming Liu *
School of physics, University of electronic science and technology of China, Chengdu 610054, China;
dajiade2000@163.com (J.D.D.); 201821120114@std.uestc.edu.cn (L.G.); 15520793203@163.com (H.Y.Z.)
* Correspondence: cmliu@uestc.edu.cn; Tel.: +86-028-8320-2590




Received: 29 March 2019; Accepted: 26 April 2019; Published: 28 April 2019


Abstract: ZnO and ZnO-Cu2 O were grown on aluminum foam using hydrothermal method. Due to
the positively charged sites on the surface, both ZnO and ZnO-Cu2 O show higher adsorption capability
towards anionic dyes, but poorer adsorption capability towards cationic dyes. The adsorption ability
of ZnO-Cu2 O is smaller than that of ZnO since there is a depletion layer at the interface. In order to
decolorize cationic dyes, ZnO and ZnO-Cu2 O are used as sono-catalyst with ultrasonic irradiation.
The ZnO-Cu2 O is better than ZnO in sono-catalysis decoloration of cationic dyes. This may be due to
the enhanced piezoelectricity and electrochemical activity, as the free electrons in ZnO are reduced in
the depletion layer.

Keywords: decoloration; dyes; ZnO; ZnO-Cu2 O; adsorption; sono-catalyst

1. Introduction
Dye-related environmental pollution is a serious problem. Dyes are becoming severe contaminants
due to their toxicity and low biodegradability. Dyes are widely used in textile, paper, leather, food,
plastics, cosmetics, and pharmaceutical industries. In order to eliminate dye pollution, ZnO is widely
investigated as photo-catalysis [1,2], adsorbents [2–4], vibration catalysis [5], thermo-catalysis [6],
piezo-photo-catalysis [7], photo-electro-catalytic [8], sono-catalysis [9], and photo-sono-catalysis [9].
Among all these methods, adsorption is considered as one of the most attractive methods due to its
simplicity, low cost, ease of operation, and efficiency [10]. However, due to the positively charged sites
at a ZnO surface, ZnO only exhibits high adsorption capability towards some negatively charged dyes
(anionic dyes), but has poor adsorption capability towards positive charged dyes (cationic dyes) [3]. It is
evident that a new method other than adsorption should be taken to eliminate positive charged dyes.
Cu2 O is one of the few materials showing a mechano-catalytic effect [11]. Cu2 O was used
to split water [11] and mineralize dyes [12]. Furthermore, ZnO-Cu2 O heterojunction shows
enhanced photo-catalytic performance and stable and fast response photodetectors [13–15]. The p-n
junction structure of Cu2 O-ZnO provides a depletion layer at the interface of junction [14].
The depletion layer was demonstrated to be beneficial for the enhancement of the output of
piezoelectricity [16]. The piezoelectricity is useful in vibration catalysis [5] and piezo-photo-catalysis [7].
The positive–negative charges are easier to get apart because of the small exciton binding energy with
built-in polarization due to piezoelectric effect. The negative (or positive) charges on the surface can
produce superoxide radicals (or hydroxyl radicals) to degrade dyes [5]. The piezoelectric field can
separate the photo-generated electrons/holes by driving them to migrate along opposite directions [7].
While ZnO-Cu2 O heterojunction has been widely studied, there is little work on vibration catalysis
or sono-catalysis. To our knowledge, most work about the mechano-catalytic effect and piezo-catalysis
is focused on single-phase material [5,11]. There is little work about the influence of depletion
layers at the interface on sono-catalysis and piezo-catalysis. It is interesting to study whether the

Crystals 2019, 9, 229; doi:10.3390/cryst9050229 www.mdpi.com/journal/crystals

Crystals 2019, 9, 229 2 of 9

enhancement of piezoelectricity of ZnO-Cu2 O heterojunction is beneficial for the decoloration of dyes.

The adsorption of dyes using ZnO and ZnO-Cu2 O as adsorbents is firstly investigated in this paper.
Then the decolorization of cationic dyes using ZnO and ZnO-Cu2O as a sono-catalyst under ultrasonic
irradiation is studied. Ultrasonic irradiation is widely used as mechanical energy in the study of
sono-catalysis and piezo-catalysis [5,7]. Ultrasonic irradiation has many advantages including high
penetrability in a water medium and no generation of secondary pollutants [17].

2. Experiments
The aluminum (Al) foam is available from SuZhou JiaYiSheng electronics CO., LTD (SuZhou,
JiangSu, China). The porosity of the sample is about 68–78%. The surface area of foam is about
0.3 m2 /g. The size of the alumina foam sample is about 3 × 40 × 40 mm3 . The foam sample is in
turn cleaned in ethanol and deionized water using an ultrasonic cleaner. ZnO nano-sheets were
fabricated on Al foam substrate by hydrothermal method. The precursor solution for growth ZnO
nano-sheets was prepared by equal volume mixing of zinc nitrate water solution (50 mL, 50 mmol L−1 )
and hexamethlylenetetramine water solution (50 mL, 15 mmol L−1 ). The substrate was put into the
precursor solution and kept at 80 ◦ C for 6 h to grow ZnO nano-sheets. After the growth of ZnO
nano-sheets, the substrate was taken out and rinsed using deionized water and dried in air.
The precursor solution for growth Cu2 O was prepared by the mixing of cupric acetate water
solution (50 mL, 50 mmol L−1 ) and hexamethlylenetetramine water solution (50 mL, 15 mmol L−1 ).
The Al foam substrates with and without ZnO nano-sheets were put into the precursor solution
and kept at 60 ◦ C for 2–6 h to grow Cu2 O and ZnO-Cu2 O samples. The samples’ stoichiometry
was measured by X-ray photoelectron spectroscopy (XPS; Kratos X SAM 800, Kratos Analytical Ltd,
Manchester, UK).
Methyl orange (MO) and methylene blue (MB) aqueous solution were used as anionic dye and
cationic dye for decolorization, respectively.
The optical absorption of MO and MB aqueous solution was measured by Ultraviolet-Vis
spectrophotometer (SHIMADZU UV-2550, Shimadzu Corporation, Kyoto, Japan). The optical
absorption of MO solution and MB solution with various concentrations was measured. It is found
that the intensity of the optical absorption peak, at about 463 (662) nm, is proportional to the MO (MB)
concentration. Thus the intensity of the optical absorption peak at 463 nm (662 nm) is used to calculate
the concentration of the MO (MB) solution. In the decoloration experiments, the initial concentration
of the MO and MB water solution is about 20 mg/l. The ultrasonic irradiation is performed in a
KQ-300VDE ultrasonic cleaner. The power and frequency of the ultrasonic cleaner is about 100 W and
100 kHz, respectively. The samples’ morphology is measured using Inspect F50 scanning electron
microscopy (SEM). The atomic ratio of sample is measured using energy disperse spectroscopy (EDS)
equipped on SEM. The decoloration rate (DR) of MO and MB is calculated using Equation (1):

C0 − Ct
DR = × 100 (1)
C0

where C0 is the initial concentration of MO (MB), Ct is the concentration of MO (MB) after t hours
of decoloration. The concentration of MO (MB) is proportional to optical absorption intensity (I) at
463 nm (662 nm), i.e.,
C = kI (2)

where k is a constant. The k of MO and MB is about 19 mg L−1 and 6.4 mg L−1 , respectively. The pH
of MO and MB aqueous solution is about 7.2 and 6.8, respectively. The mass of ZnO and ZnO-Cu2 O
catalyst is about 0.23 g and 0.24 g, respectively.
where k is a constant. The k of MO and MB is about 19 mg l−1 and 6.4 mg l−1, respectively. The pH
of MO and MB aqueous solution is about 7.2 and 6.8, respectively. The mass of ZnO and ZnO-Cu2O
catalyst is about 0.23 g and 0.24 g, respectively.
Crystals 2019, 9, 229 3 of 9
3. Results and Discussion
Figure 1 shows
3. Results the SEM of ZnO, Cu2O, and ZnO-Cu2O sample in parts a–c, respectively. The
and Discussion
ZnO nano-sheetsFigure 1have
shows a thethickness
SEM of ZnO,ofCuabout 90 nm. The nano-sheets are perpendicular to the
2 O, and ZnO-Cu2 O sample in parts a–c, respectively. The ZnO
substrate. There arehave
nano-sheets many micrometer-sized
a thickness of about 90 nm. voids
The in the sample.
nano-sheets The voids size
are perpendicular in substrate.
to the Cu2O is smaller
than thatThere are many
in ZnO. Themicrometer-sized
granule shapevoids in Cuin 2the
O issample. The voids
irregular. The size in Cu22O
ZnO-Cu Oisshows
smallernano-sheets
than that and
in ZnO. The granule shape in Cu2 O is irregular. The ZnO-Cu2 O shows nano-sheets and irregular
irregular particles. The thickness of ZnO-Cu2O nano-sheets is about 160 nm. The voids size is smaller
particles. The thickness of ZnO-Cu2 O nano-sheets is about 160 nm. The voids size is smaller than that
than thatin in ZnO. The surface of ZnO is smoother than that of ZuO-Cu2O. The shape change in
ZnO. The surface of ZnO is smoother than that of ZuO-Cu2 O. The shape change in nano-sheets
nano-sheets
should should
be duebe duegrowth
to the to theCugrowth Cu2O on surface of ZnO nano-sheets. The atomic ratio of
2 O on surface of ZnO nano-sheets. The atomic ratio of Cu to Zn of
Cu to ZnZuO-Cu
of ZuO-Cu 2O sample
2 O sample determined
determined by EDS
by EDS is about 9:1. is about 9:1.

(a) (b)

(c)
Figure 1. The scanning electron microscopy (SEM) of ZnO (a), Cu2 O (b), and ZnO-Cu2 O (c) sample.

Figure 1. The scanning

Figure electron
2 shows the XRD ofmicroscopy (SEM)
Al foam, ZnO, ofand
Cu O ZnO (a), Cu2O
ZnO-Cu Osample.
(b), andThe
ZnO-Cu O (c) (220),
(111), 2(200), sample.
2 2
and (311) diffraction peaks of Al foam are from Al metal (JCPDS: 03-0932. The (214), (413), and (244)
Figure 2 shows
diffraction theofXRD
peaks Al foam of are
Al from
foam, Al2ZnO, Cu2O
O3 oxides and ZnO-Cu
(JCPDS: O sample.
02-1373). 2The The
diffraction (111),
peaks of Cu(200),
2O (220),
◦ ◦ ◦ ◦ and：03-0932.
and (311)at diffraction
about 36.7 , 42.4
peaks , 61.7
of ,Al
andfoam
73.6 are
aredue
fromto (111),
Al metal（ JCPDS
(200), (220), (311) planesThe
of cubic Cu2(413),
(214), O and
(JCPDS:77-0199), respectively. The crystal size of Cu2 O is determined to be about 160 nm using (111)
(244) diffraction peaks of Al foam are from Al2O3 oxides (JCPDS: 02-1373). The diffraction peaks of
diffraction with Scherrer formula. The new diffraction peak at about 10.8◦ in the ZnO sample may be
Cu2O at from
about 36.7°, 42.4°, 61.7°, and 73.6° are due to (111), (200), (220), and (311) planes of cubic
Al2 O3 oxides (JCPDS: 02-1373). This indicates that partial aluminum metal is oxidized during the
Cu2O (JCPDS
growth:77-0199),
of ZnO. Therespectively.
peaks at aboutThe20.5crystal size
◦ and 34.8 ◦ areof Cu2(102)
form O is and
determined toofbe
(104) planes about 160
hexagonal nm using
ZnO
(111) diffraction with Scherrer
(JCPDS:01-1136), respectively.formula. The new diffraction peak at about 10.8° in the ZnO sample
may be from Al2O3 oxides (JCPDS: 02-1373). This indicates that partial aluminum metal is oxidized
during the growth of ZnO. The peaks at about 20.5° and 34.8° are form (102) and (104) planes of
hexagonal ZnO (JCPDS:01-1136), respectively.
 Crystals 2019, 9 FOR PEER REVIEW 4

Crystals 2019, 9 FOR PEER REVIEW 4

1000
Crystals 2019, 9, 229 4 of 9

111
1000 ZnO-Cu2O

200

220
111
Intensity (a.u.)
ZnO-Cu2O

200

220
500
Cu2O
Intensity (a.u.)

500 ZnO

200

311
220
Cu2O

111

222
413
214

244
0 Al foam
ZnO
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95

200

311
220
111

222
2θ (degree)

413
214

244
0 Al foam
Figure 2. The XRD
5 10of15
aluminum
20 25 30 (Al) foam,
35 40 ZnO,
45 50 Cu65
55 60 2O and ZnO-Cu2O sample.
70 75 80 85 90 95
2θ (degree)
Figure 2. The XRD of aluminum (Al) foam, ZnO, Cu2 O and ZnO-Cu2 O sample.

ZnO-Cu
Figure 2. The XRD of aluminum (Al) foam, ZnO,
2
O Cu2O and ZnO-Cu2O sample.

ZnO-Cu2O
Intensity (a.u.)

ZnO
Intensity (a.u.)

ZnO
1000 1010 1020 1030 1040 1050 1060 1070
Binding Energy (eV)

Figure 3. The Zn 2p X-ray photoelectron spectroscopy (XPS) of ZnO and ZnO-Cu2 O.

FigureFigure 3. The
3 shows theZnZn2p2pX-ray
XPS ofphotoelectron
ZnO and ZnO-Cu spectroscopy (XPS) of ZnO and ZnO-Cu2O.
2 O. The binding energy of Zn 2p3/2 of ZnO and
ZnO-Cu2 O is about 1021.47 and 1021.61 eV, respectively. The binding energy of Zn 2p1/2 of ZnO and
Figure 23Oshows
ZnO-Cu is aboutthe Zn 2p
1044.57 andXPS of ZnO
1044.74 and ZnO-Cu
eV, respectively. 2O.binding
The The binding
energyenergy
of Zn 2pofinZn 2p3/2 2of
ZnO-Cu O ZnO
1000 1010 1020 1030 1040 1050 1060 1070
andshifts
ZnO-Cu 2O is about
to higher energy1021.47
compared and 1021.61
with ofeV,
that Binding
ZnO.respectively.
The shift
Energy The binding
of binding
(eV) energy energy of Zn 2pto
was attributed of ZnO
1/2the
andelectronic
ZnO-Cuinteraction
2O is about 1044.57
between two and 1044.74
materials [18]. eV, respectively.
Therefore, The
the shift in binding
binding energyenergy of Zn 2p in
of Zn indicates
that there
ZnO-Cu should
2O shifts tobehigher
intimate contactcompared
energy between the two that
with materials.
of ZnO. The shift of binding energy was
Figure
attributedFigure 4 shows the
to the3.electronic optical
The Zn 2pinteractionabsorption of MO
between two
X-ray photoelectron decolorized
materials
spectroscopy by(XPS)
adsorption using
[18]. Therefore,
of ZnO andZnO,
the Cu2 O,
shift
ZnO-Cu O.and
2in binding
ZnO-Cu
energy of Zn O as adsorbents in parts a–c, respectively. There are two main
2 indicates that there should be intimate contact between the two materials. optical absorption bands with
peaks located at about 463 nm and 272 nm. The band at wavelength of 463 nm was attributed to the
Figure
Figure 4 showsthe
3 shows theZn optical
2p XPS absorption
of ZnOofand MOZnO-Cu
decolorized by adsorption
2O. The binding energyusing ZnO,
of Zn Cu2p 2O,
3/2and
of ZnO
conjugated structure constructed via azo bond [19]. The peak’s intensity decreases with decolorization
andZnO-Cu
ZnO-Cu 2O2Oasisadsorbents
time increasing about
from1021.47
in parts a–c,
0 s to 20and
respectively.
s. A1021.61
There are The
eV, absorption
new optical respectively. two binding
peak appears
main opticalenergy
at about
absorption
370 nmof Zn 2pbands
for the 1/2 of ZnO
andwith peaks2located
ZnO-Cu O is about
Cu2 O adsorbents.
atThe
about 463
1044.57
new
nmand
andpeak
absorption
272 nm.
1044.74 The
is noteV,
band at wavelength
due respectively.
to the losing of Cu The of 463 nm was
binding
2 O in
attributed
energy
solution as there isof
to
no Zn 2p in
the
ZnO-Cu conjugated
2O shiftspeak
absorption structure
to higher
in the same constructed
energy
treated via
compared azo bond
withThis
water solution. [19].
that The
of ZnO.
indicates peak's
thatThe intensity
thereshift decreases
of binding
are other mechanisms with
energy was
decolorization time increasing from 0 s to 20 s. A new optical absorption peak appears at about 370
attributed to the electronic interaction between two materials [18]. Therefore, the shift in binding
energy of Zn indicates that there should be intimate
4 contact between the two materials.
Figure 4 shows the optical absorption of MO decolorized by adsorption using ZnO, Cu2O, and
ZnO-Cu2O as adsorbents in parts a–c, respectively. There are two main optical absorption bands
Crystals 2019, 9 FOR PEER REVIEW 5

nm for the2019,
Crystals Cu29,O229
adsorbents. The new absorption peak is not due to the losing of Cu2O in solution 5 of 9 as
there is no absorption peak in the same treated water solution. This indicates that there are other
mechanisms than adsorption presenting in Cu2O adsorbents [12]. It was demonstrated that MO can
than adsorption presenting in Cu2 O adsorbents [12]. It was demonstrated that MO can be decomposed
be decomposed
to xylene andtoethylbenzene
xylene and [12].
ethylbenzene [12].radicals
Carbon center Carbonsuch
center radicals
as methyl such and
radical as methyl
phenyl radical
radical and
phenyl
haveradical have reconnected
reconnected with
with each other each other
to produce to produce
xylene xylene[12].
or ethylbenzene or ethylbenzene [12].

1.0
0s
4s
8s
12s
Absorption (a.u.)

16s
20s
0.5

0.0

240 280 320 360 400 440 480 520 560 600
Wavelength (nm)

(a)

0s
1.0 4s
8s
12s
16s
20s
absorption (a.u.)

0.5

0.0

240 280 320 360 400 440 480 520 560 600
Wavelength (nm)

(b)
1

0s
4s
8s
12s
16s
Absorption(a.u.)

20s

0
240 280 320 360 400 440 480 520 560 600
Wavelenth (nm)

(c)
Figure
Figure 4. The
4. The optical
optical absorptionofofmethyl
absorption methylorange
orange (MO)
(MO) decolorized
decolorizedbyby
adsorption using
adsorption ZnOZnO
using (a), (a),
Cu O (b), and ZnO-Cu O (c) as adsorbents.
Cu2O (b), and ZnO-Cu2O (c) as adsorbents.
2 2

Pseudo-first-order kinetics reaction was applied to simulate the experimental data with the
Langmuir–Hinshelwood model ln(C0/C) = αt, where α is the pseudo-first-order rate constant, and
was determined from a linear fit to the experimental data [13,20]. Figure 5 shows that experimental

5
 Crystals 2019, 9, 229 6 of 9
Crystals 2019, 9 FOR PEER REVIEW 6

data can be fitted well using the

Pseudo-first-order
Crystals 2019, kinetics
9 FOR PEER REVIEW
pseudo-first-order
reaction was applied to kinetics.
simulate Thethe rate constant α data
experimental is determined
with 6the
to be about 0.02, 0.129, and 0.275 min −1 for Cu2O, ZnO-Cu2O, and ZnO, respectively. The higher
Langmuir–Hinshelwood model ln(C0 /C) = αt, where α is the pseudo-first-order rate constant, and was
data of ZnO
α can
determined indicates
be fitted
from well that
using
a linear fit toZnO
the has the greater
thepseudo-first-order
experimental adsorption
kinetics.
data [13,20]. Theability
Figure 5rate
shows towards
constant αMO. Thedata
is determined
that experimental weaker
can
adsorption
to be
be fitted
aboutwell ability
0.02, 0.129,
using of
theand ZnO-Cu O may
−1 be
0.275 min forkinetics.
2
pseudo-first-order related
Cu2O, ZnO-Cu to the
The rate2O, reduction
and ZnO,
constant in specific
respectively.
α is determined surface
toThe area
higher
be about and
0.02,
positive
of ZnO
α 0.129, charges
andindicates on
−1 for
0.275 minthat surface
ZnO
Cu2 O, has[3].theZnO
ZnO-Cu and
greater
2 O, Cu 2O respectively.
andadsorption
ZnO, are ability
n-type towards
andhigher
The p-type
MO. semiconductors,
α of The
ZnOweaker
indicates
respectively.
adsorption
that ability
ZnO has The
the ofdepletion
ZnO-Cu
greater 2region
O may
adsorption atbe
therelated
ability interface
towards of
thethe
toMO. p-n
reduction
The junction
weaker in [14] may
specific
adsorption reduce
surface
ability the positive
ofarea
ZnO-Cu and2 O
charges
may be on the
related surface.
to the The
reduction adsorption
in specific of MB
surfacefor Cu
area andO, ZnO-Cu
positive
positive charges on surface [3]. ZnO and Cu2O are n-type and p-type semiconductors,
2 O,
charges
2 and ZnO
on is
surface too small
[3]. ZnO to
andbe
detected.
Cu The depletion
2 O are n-type
respectively. weak adsorption
and p-type at of
theMB
semiconductors,
region should be p-n
respectively.
interface of the due
The todepletion
the [14]
junction positively
region atcharged
may reduce surface
the interface
the positiveof theof
p-n junction
adsorbents [14] may
[3,21]. reduce the positive charges on the surface.
charges on the surface. The adsorption of MB for Cu2O, ZnO-Cu2O, and ZnO is too small to be The adsorption of MB for Cu 2 O,
ZnO-CuThe
detected. 2 O, and
weakZnO is too smalloftoMB
adsorption be detected.
should be Thedue
weak to adsorption
the positively of MB should be
charged due toofthe
surface
positively[3,21].
adsorbents charged surface of adsorbents [3,21].

Figure 5. The pseudo-first-order kinetics fit the concentration as a function of time.

Figure 5. The
Figure pseudo-first-order
5. The kinetics
pseudo-first-order fit the
kinetics concentration
fit the as as
concentration a function of time.
a function of time.
4

original MB
4
Al foam
ZnO
ZnO-Cu
original MB 2O
Al foam
Intensity (a.u.)

2 ZnO
ZnO-Cu2O
Intensity (a.u.)

0 400 450 500 550 600 650 700 750 800 850 900
Wavelength (nm)

400 450 of 500

Figure 6. The decolorization 550
methylene 600 650
blue (MB) 700 750foam,
with Al 800 ZnO,
850 and
900 ZnO-Cu2 O as catalyst

under ultrasonic irradiation. Wavelength (nm)

Figure 6. The decolorization of methylene blue (MB) with Al foam, ZnO, and ZnO-Cu2O as catalyst
under ultrasonic irradiation.
Figure 6. The decolorization of methylene blue (MB) with Al foam, ZnO, and ZnO-Cu2O as catalyst
under ultrasonic irradiation. 6

6
 Crystals 2019, 9 FOR PEER REVIEW 7

Crystals 2019, 9, 229

Figure 6 shows the optical absorption of MB decolorized by Al foam, ZnO, and ZnO-Cu72O of 9
as
catalyst under ultrasonic irradiation. The ultrasonic irradiation time is about 24 h. The peak intensity
decreases
Figurefrom
6 shows Al foam, ZnO to
the optical ZnO-Cu2O.
absorption of DR
MB isdecolorized
about 13%,by 40%, and 59%
Al foam, ZnO,forand
Al foam,
ZnO-CuZnO, and
2 O as
ZnO-Cu
catalyst 2O catalyst, respectively. DR of MB decolorized by ZnO and ZnO-Cu2O is larger than that
under ultrasonic irradiation. The ultrasonic irradiation time is about 24 h. The peak intensity
decolorized
decreases from Alby Alfoam,
foam.ZnO The enhancement
to ZnO-Cu2 O.ofDR DRisshould be due
about 13%, to the
40%, andpiezoelectric
59% for Al foam,potential
ZnO,of and
ZnO
and ZnO-Cu 2O.
ZnO-Cu2 O catalyst, respectively. DR of MB decolorized by ZnO and ZnO-Cu2 O is larger than that
Figureby
decolorized 7 shows
Al foam.theThe
decolorization
enhancement ofof
MBDRusing
should ultrasonic
be due toirradiation. As seen
the piezoelectric in Figure
potential 7, the
of ZnO
DR of ZnO-Cu
and ZnO-Cu2 O. 2O is much higher than that of ZnO. With 50 h ultrasonic irradiation, DR of ZnO-Cu2O

andFigure
ZnO is7 shows
about 70% and 48%, respectively.
the decolorization of MB using This enhancement
ultrasonic of DRAs
irradiation. is seen
related to many
in Figure factors,
7, the DR
such as the cavitation [22] and piezoelectric enhanced vibration catalysis
of ZnO-Cu2 O is much higher than that of ZnO. With 50 h ultrasonic irradiation, DR of ZnO-Cu2 O and[5]. On the one hand, the
ZnO is about 70% and 48%, respectively. This enhancement of DR is related to many factors, such as theto
weak points in MB solution can be increased by putting a catalyst in it, which in turn leads
increasing[22]
cavitation nucleation of the cavitation
and piezoelectric enhanced bubbles, thecatalysis
vibration number [5].
of free
Onradicals generated,
the one hand, and the
the weak rateinof
points
degradation of the organic compound [22]. On the other hand, the depletion layer
MB solution can be increased by putting a catalyst in it, which in turn leads to increasing nucleation of was demonstrated
to cavitation
the be of benefit for the
bubbles, theenhancement
number of freeofradicals
the output of piezoelectricity
generated, and the rate of[16]. The positive–negative
degradation of the organic
charges are[22].
compound easier Ontothe
getother
aparthand,
because theofdepletion
the small layer
excitonwasbinding energy with
demonstrated to bebuilt-in polarization
of benefit for the
due to piezoelectric effect [5]. Due to the p–n junction of ZnO-Cu O, the number
enhancement of the output of piezoelectricity [16]. The positive–negative charges are easier to get apart
2 of excess electrons
in ZnOofcan
because thebe effectively
small exciton reduced, which with
binding energy is beneficial to the piezoelectric
built-in polarization signal output
due to piezoelectric [23].
effect [5].A
13-fold higher output voltage was achieved in ZnO-Cu O nano-generator compared
Due to the p–n junction of ZnO-Cu2 O, the number of excess electrons in ZnO can be effectively reduced,
2 with ZnO [23].
A dramatic
which increase
is beneficial inpiezoelectric
to the H2 production is caused
signal by decreasing
output [23]. the mobile
A 13-fold higher output charge
voltageconcentration
was achievedin
inZnO
ZnO-Cupiezo-catalysis [24]. Low electrical conductivity is desirable in order to enable high
2 O nano-generator compared with ZnO [23]. A dramatic increase in H2 production is
electrochemical activity
caused by decreasing the[24]. The charge
mobile reason concentration
of the larger DR in of ZnO-Cu
ZnO 2O may be[24].
piezo-catalysis due toLowthere being a
electrical
p-n junction and a carrier depletion layer at the interface of ZnO-Cu O. The
conductivity is desirable in order to enable high electrochemical activity [24]. The reason of the larger
2 depletion layer can
DRenhance the piezoelectricity
of ZnO-Cu and electrochemical activity then increase the DR.
2 O may be due to there being a p-n junction and a carrier depletion layer at the interface
of ZnO-Cu2 O. The depletion layer can enhance the piezoelectricity and electrochemical activity then
increase the DR.

80

ZnO-Cu2O+ultrasonic

60

40
DR (%)

ZnO+ultrasonic

20

0 10 20 30 40 50 60
t (hour)

Figure 7. The decolorization of MB using ultrasonic irradiation.

Figure 7. The decolorization of MB using ultrasonic irradiation.
The mechanism of the enhancement of DR by depletion layer is shown in the Figure 8. The density
of an electron in pure ZnO is higher than that in a ZnO-Cu2 O junction boundary due to the forming of a
The mechanism of the enhancement of DR by depletion layer is shown in the Figure 8. The
depletion region [23]. The piezoelectric potential of pure ZnO is smaller than that of ZnO-Cu2 O because
density of an electron in pure ZnO is higher than that in a ZnO-Cu2O junction boundary due to the
of the piezoelectric potential screening effect due to excessive electrons [16,23,25,26]. The piezoelectric
forming of a depletion region [23]. The piezoelectric potential of pure ZnO is smaller than that of
potential [27] and piezoelectrically-induced electric charges [5] could stimulate the decolorization
ZnO-Cu2O because of the piezoelectric potential screening effect due to excessive electrons
reactions via electrochemical redox reaction. The negative charges (or e− ) on the surface attract the
[16,23,25,26]. The piezoelectric potential [27] and piezoelectrically-induced electric charges [5] could
dissolved oxygen in the water and produce superoxide radicals (·O2− ). Meanwhile, hydroxyl radicals
stimulate the decolorization reactions via electrochemical redox reaction. The negative charges (or
(·OH) can be released by positive charges (or h+ ) accumulated on the surface [5,27]. The strong
e ) on the surface attract the dissolved oxygen in the water and produce superoxide radicals (·O2−).
−
oxidative ·O2 − and ·OH can cause the decolorization reactions of dye [5,27].
7
Crystals 2019, 9 FOR PEER REVIEW 8

Meanwhile, hydroxyl radicals (·OH) can be released by positive charges (or h+) accumulated on the
Crystals 2019,
surface 9, 229
[5,27]. 8 of 9
The strong oxidative ·O2− and ·OH can cause the decolorization reactions of dye [5,27].

Figure 8. The mechanism of the enhancement of decoloration rate (DR) by depletion layer.
Figure 8. The mechanism of the enhancement of decoloration rate (DR) by depletion layer.
4. Conclusions
4. Conclusion
It was demonstrated in this paper that the ZnO and ZnO-Cu2 O have good adsorption to anionic
dyes,
It but
washave weak adsorption
demonstrated to cationic
in this paper dyes.
that the ZnOThe
and hybrid
ZnO-Cu structure of ZnO-Cu
2O have good 2 O improves
adsorption the
to anionic
sono-catalysis
dyes, activity
but have weak of ZnO totodecolorize
adsorption cationic
cationic dyes. Thedyes.
hybridThe p-n junction
structure between
of ZnO-Cu ZnO-Cu2 O
2O improves theis
shown to be beneficial
sono-catalysis forZnO
activity of the sonocatalysis
to decolorizedecolorization
cationic dyes.of
Thecationic dyes. Since
p-n junction the free
between electrons
ZnO-Cu in
2O is

the interface
shown of ZnO-Cu
to be beneficial for2 Otheare reduced, it should
sonocatalysis be the polarized
decolorization charges,
of cationic not the
dyes. Since thefree
free charges,
electronsthat
in
play
the the important
interface role 2in
of ZnO-Cu O piezo-catalysis.
are reduced, it should be the polarized charges, not the free charges, that
play the important role in piezo-catalysis.
Author Contributions: C.M.L. conceived and designed the experiments; J.D.D., L.G. and H.Y.Z. performed the
experiments;
Author C.M.L. andC.M.Liu
Contributions: J.D.D. analyzed
conceivedthe and
data designed
and wrotethe
the experiments;
paper. J.D.Dai, L.Gan and H.Y.Zhang
performed the experiments; C.M.Liu and J.D.Dai analyzed the data and wrote the paper. of the Sichuan Province
Funding: This study was supported financially by the Agricultural Public Welfare Project
of China (grant no.2015NZ0098) and the Fundamental Research Funds for The Central Universities (grant
Funding: This study was supported financially by the Agricultural Public Welfare Project of the Sichuan
no.ZYGX2016J062).
Province of China (grant no.2015NZ0098) and the Fundamental Research Funds for The Central Universities
Conflicts of Interest: The authors declare no conflict of interest.
(grant no.ZYGX2016J062).

Conflicts of Interest: The authors declare no conflict of interest.

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