Hindawi

Journal of Nanomaterials
Volume 2019, Article ID 1015876, 12 pages
https://doi.org/10.1155/2019/1015876

Research Article
Synthesis and Characterization of ZnO-ZrO2 Nanocomposites for
Photocatalytic Degradation and Mineralization of Phenol

M. C. Uribe López,1 M. A. Alvarez Lemus ,1 M. C. Hidalgo,2 R. López González ,1

P. Quintana Owen,3 S. Oros-Ruiz,4 S. A. Uribe López,5 and J. Acosta1
1
Juárez Autonomous University of Tabasco, Nanotechnology for Biomedicine and Environmental Applications, Academic Division of
Engineering and Architecture, Carr. Cunduacán Jalpa de Méndez Km 1, Col. La Esmeralda, CP 86690 Cunduacan, Tabasco, Mexico
2
Instituto de Ciencia de Materiales de Sevilla (ICMS), Consejo Superior de Investigaciones Científicas (CSIC)-Universidad de Sevilla,
Américo Vespucio 49, 41092 Sevilla, Spain
3
CINVESTAV Unidad Mérida, Departamento de Física Aplicada, AP. 73 Cordemex, 97310 Mérida, Yucatán, Mexico
4
Autonomous Metropolitan University-Iztapalapa, CONACYT-Research Fellow-Department of Chemistry, ECOCATAL Group,
Av. San Rafael Atlixco No. 186, Col. Vicentina, Iztapalapa 09340, Mexico
5
Juárez Autonomous University of Tabasco, CONACYT-Research Fellow, Academic Division of Engineering and Architecture,
Carr. Cunduacán Jalpa de Méndez Km 1, Col. La Esmeralda, CP 86690 Cunduacan, Tabasco, Mexico

Correspondence should be addressed to M. A. Alvarez Lemus; [email protected]

Received 18 June 2018; Revised 8 October 2018; Accepted 1 November 2018; Published 10 January 2019

Guest Editor: Zhen Yu

Copyright © 2019 M. C. Uribe López et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

ZnO-ZrO2 nanocomposites using zinc (II) acetylacetonate and different ZnO contents (13, 25, 50, and 75% mol) were synthesized
through sol-gel method. The synthesis process was strongly related to nanocomposite properties especially on their structural
composition. The obtained ZnO-ZrO2 nanomaterials presented tetragonal crystalline structure for zirconia whereas hexagonal
one was formed in ZnO. Raman spectroscopy and XRD patterns confirmed the formation of tetragonal zirconia whereas
inhibition of monoclinic structure was observed. Addition of ZnO affected the pore size distribution of the composite, and the
measured specific surface areas were from 10 m2/g (for pure ZnO) to 46 m2/g (pristine ZrO2). Eg values of ZrO2 were modified
by ZnO addition, since calculated values using Kubelka-Munk’s function varied from 4.73 to 3.76 eV. The morphology and size
of the nanomaterials investigated by electron microscopy showed formation of nanorods for ZnO with sizes ranging from 50 nm
to 300 nm while zirconia was formed by smaller particles (less than 50 nm). The main advantage of using the nanocomposite for
photocatalytic degradation of phenol was the mineralization degree, since 75ZnO-ZrO2 nanocomposite surpassed mineralization
reached by pure ZnO and also inhibited formation of undesirable intermediates.

1. Introduction improved physicochemical properties than the pure oxides.

Usually, composites enhance photocatalytic activity [4, 5],
Zirconium oxide (ZrO2) known as zirconia is an interesting produce new crystallographic phases with quite different
material due to its application in various photochemical het- properties than the original oxides, create defect energy levels
erogeneous reactions. ZrO2 is an n-type semiconductor with in the band gap region [6], change the surface characteristics
a wide band gap energy between 5.0 and 5.5 eV [1]. Because of the individual oxides due to the formation of new sites in
of this, ZrO2 requires UV-C light (<280 nm) to be excited the interface between the components [7], and also increase
and generate electron-hole pairs [2]. A strategy to overcome the stability of a photoactive crystalline phase [8]. In order
this is by doping ZrO2 with different transition metal ions or to enhance optical properties of ZrO2 several semiconductors
coupling with other metal oxides with dissimilar band edge like SiO2, TiO2, ZnO, WO3, and NiO have been coupled to
[3]. Composites made of two metal oxides have attracted ZrO2. Together with TiO2, zin oxide is one of the most inves-
much attention in different researches because they possess tigated n-type semiconductor materials due to its low-cost,
2 Journal of Nanomaterials

easy fabrication, wide band-gap, and photocatalytic activity 2. Materials and Methods
for degrading several organic pollutants into less harmful
products [9]. The main advantage of ZnO is that it 2.1. Reagents. Zirconium (IV) butoxide (80 wt. % in 1-buta-
absorbs a larger fraction of the solar spectrum than TiO2 nol), phenol (ReagentPlus ≥99%), and Zinc Acetylacetonate
[10]. The band gap of ZnO is ~3.37 eV, and its exciton- hydrate were purchased from Sigma-Aldrich; hydrochloric
binding energy is about 60 meV [11]. Many reports have acid (36.5–38%) was obtained from Civeq (México). In all
been published about the good physicochemical properties cases, deionized water was used.
given by the use of ZnO in composites. For instance, a 2.2. Synthesis of ZrO2. 81.2 mmol of de Zirconium (IV)
composite made by nanostructures transparent conducting butoxide were added dropwise to 48.9 mL of deionized
metal-oxides (TCMOS) as ZnO/NiO resulted in an excel- water and ethanol mixture (1 : 8) preheated at 70°C. Before
lent candidate for acetone sensing [12]. Nanocomposites of addition of the alkoxide, pH was adjusted at pH 3 with
Zn(1−x)MgxO/graphene showed an excellent performance hydrochloric acid (2.5 M). The white suspension was kept
to remove methylene blue dye under natural sunlight illu- under temperature at 70°C, with continuous stirring and
mination [13]. TiO2/ZnO nanocomposites with different reflux for 24 h. The gel was dried at 70°C for 8 h afterwards.
contents of ZnO showed an improvement in the degradation Finally, the obtained powder was ground and then calcined
of the organic dyes brilliant green and methylene blue under at 500°C for 4 h.
solar light irradiation [14]. ZnO/TiO2 photocatalyst exhib-
ited much higher photocatalytic activity than pure TiO2, 2.3. Synthesis of ZnO. 11.38 mmol of Zinc Acetylacetonate
ZnO, and P-25 in the degradation of 4-chlorophenol under hydrate (powder, Sigma-Aldrich) were added into 50 mL
low UV irradiation [15]. The composites of ZnO/Ag2CO3/ of ethanol (96%, Civeq) previously heated at 70°C and
Ag2O demonstrated a potential effect in the photodegra- adjusted at pH 3 with chlorhydric acid (2.5 M) (36.5–38%,
dation of phenol under visible light irradiation due to the Civeq) during 30 min. The suspension was stirred for 4 h
facilitate charge transfer and suppress recombination of at 70°C and then being aged for 24 h under continuous agita-
photogenerated electrons and holes [16]. tion. Later, the resulting gel was washed several times with
Recently, composites of ZrO2 with ZnO have attracted ethanol and deionized water. Finally, the white powders were
much attention because of their excellent properties as a dried at 70°C during 6 h, ground, and then calcined at 500°C
semiconductor material, especially for the degradation reac- for 4 h.
tions of recalcitrant organic pollutants. The enhancement
in photocatalytic activity of ZnO-ZrO2 composites has been 2.4. Synthesis of ZnO-ZrO2 Nanocomposites. Different molar
associated with the changes in their structural, textural, and percentages (13%, 25%, 50%, and 75%) of ZnO were incorpo-
optical properties, such as surface area, particle size, forma- rated into ZrO2 and named as 13ZnO-ZrO2, 25ZnO-ZrO2,
tion of a specific crystalline phase, and low band gap energy 50ZnO-ZrO2, and 75ZnO-ZrO2. The photocatalysts were
[4, 17, 18]. In addition, the improved electron-hole pair prepared as follows: the appropriated amount of Zinc Acetyl-
enhances the photocatalytic efficiency. Under illumination, acetonate hydrate was dissolved into 50 mL of ethanol previ-
both the semiconductors of nanocomposite are simulta- ously heated at 70°C and adjusted at pH 3 (HCl, 2.5 M). ZrO2
neously excited, and the electrons slip to the low-lying con- sols were prepared separately as previously described but just
duction band of one semiconductor, while holes move to the before the addition of the half of the total amount of alkoxide
less anodic valence band. Sherly et al. [19] attributed the effi- was completed, the corresponding ZnO sol was incorporated
ciency of Zn2Zr (ZnO and ZrO2 in 2 : 1 ratio) photocatalyst into the mixture, followed by the dropwise of the rest of the
in the degradation of 2,4-dichlorophenol to the good stability zirconium alkoxide. The mixture was kept under vigorous
and the efficient separation of photogenerated electron-hole stirring and reflux at 70°C during 24 h. The obtained gels
pairs. Aghabeygi and Khademi-Shamami [4] stated that the were washed several times with ethanol and deionized water,
good properties of 1 : 2 molar ratio of ZrO2 : ZnO as photoca- then they were, dried, ground, and calcined at 500°C during
talyst in the degradation of Congo Red dye could be by the 4 h. The proposed reactions are presented in Supplementary
decrease in the rate of the hole-electron pairs recombination Materials (Figures S1, S2, and S3).
when the excitation takes place with energy lower than Eg.
2.5. Characterization of the Nanocomposites. X-ray diffrac-
Besides, they proposed that ZnO could increase the concentra-
tion (XRD) patterns were obtained on a Bruker D8 Advance
tion of free electrons in the CB of ZrO2 by reducing the charge
diffractometer using CuKα radiation (1.5418 Å) in the 2θ
recombination in the process of electron transport. Gurush-
scan range of 10–90°. The average crystallite size of the
antha et al. [20] demonstrated a photocatalytic enhancement
samples was estimated using the Debye-Scherrer equation
in the ZrO2/ZnO (1 : 2) nanocomposite for the degradation
(equation (1)).
of acid orange 8 dye under UV light irradiation (254 nm).
They observed that the reduction of energy gap, the increase
of the density states, and the stability of the composite 0 89λ
increased the photocatalyst efficiency. D= , 1
β cos θ
In this work, we investigated the effect of ZnO on the
photocatalytic properties of ZnO-ZrO2 nanocomposites
obtained by sol-gel method in the photodegradation of phe- where λ is the wavelength of CuKα radiation, β is the peak
nol in water under UV-A irradiation. width at half maximum, and θ is the diffraction angle.
Journal of Nanomaterials 3

To calculate the percentage of monoclinic and tetragonal TOC f inal

phases of pure ZrO2, we used the monoclinic phase fraction % Mineralization = 1 − ∗ 100, 3
TOCinitial
X m and the following equation described by Garvie and
Nicholson [21]: where TOCinitial and TOC f inal are the total organic carbon
concentrations in the media before and after the photocata-
I m −111 + I m 111 lytic reaction, respectively.
Xm = × 100, 2
I m −111 + I m 111 + I t 101
3. Results
where I m and I t represent the integral intensities of mono- 3.1. X-Ray Diffraction Analysis. X-ray patterns of the photo-
clinic 111 and −111 and tetragonal 101 peaks. catalysts are depicted in Figure 1(a). All the diffractograms of
Raman spectroscopy was performed with an XploRA the samples containing ZnO exhibited sharp and strong
PLUS Raman system equipment (HORIBA) with a CCD peaks at 31.70°, 34.30° y 36.20 (2θ) which correspond to
detector, an optical microscope (Olympus BX), and solid- (100), (002), and (101) reflections, respectively, and agree
state laser (532 nm/25 mW). Fourier transformed infrared with the characteristic peaks of ZnO wurtzite-type hexagonal
spectra (FT-IR) were collected in a Shimadzu IRAffinity-1 crystalline structure (JCPDS 36-1451). The high intensity of
spectrophotometer. The powders (<5%wt) were pressed into the (101) peak suggests anisotropic growth and orientation
100 mg wafers together with KBr (J.T.Baker, Infrared grade). of the crystals [22, 23].
Diffuse reflectance UV-Vis spectroscopy (UV-Vis/DRS) On the other hand, pristine ZrO2 showed broad peaks
was carried out on Shimadzu UV-2600 spectrophotometer located at 28.20°, 30.20°, and 31.50° (2θ). The peak centered
equipped with an integrating sphere accessory and BaSO4 at 30.20°(101) is characteristic of tetragonal crystalline phase
as reference (99% reflectance). The band-gap (Eg) values (t-ZrO2) according to JCPDS 79-1771 card, whereas those at
were calculated using Kubelka-Munk function, F(R), by the 28.20°(−111) and 31.5°(111) are representative of monoclinic
construction of a Tauc’s plot: (F(R)∗ hν)2 or (F(R)∗ hν)1/2 phase (m-ZrO2, JCPDS 37-1484). These results suggest a
versus energy (eV), for a direct and indirect allowed transi- mixture of both tetragonal and monoclinic crystalline phases,
tion, respectively. The BET specific surface areas (SBET) which is commonly observed on ZrO2 materials when cal-
and pore volume (BJH method) of the samples were deter- cined at similar temperatures [24, 25].
mined by N2 adsorption-desorption isotherms at 77°K using When ZnO was added to ZrO2, the corresponding peaks
a Quantachrome Autosorb 3B instrument. Degasification of to monoclinic phase were not observed, indicating inhibition
the samples was performed at 100°C during 12 h. Surface of monoclinic phase. As the content of ZnO increases, the
morphology of the materials was analyzed by field emis- reflection (101) observed at 30.20° (2θ) appeared slightly
sion scanning electron microscopy (FESEM) using a Hitachi shifted towards 30.38° except for the 50ZnO-ZrO2 sample;
S-4800 microscope, whereas high-resolution transmission therefore, the peaks observed for all the ZnO-ZrO2 materials
electron microscopy (HRTEM) was performed in a JEOL are assigned to the presence of tetragonal phase. To distin-
JSM-2100 electron microscope operated at 200 kV, with a guish between the diffraction patterns of cubic and tetragonal
0.19 nm resolution. phases of ZrO2, the 2θ region at 71–77° was carefully exam-
ined. The asymmetric doublets at ~74° indicated the forma-
2.6. Photocatalytic Activity. Synthesized particles were tested tion of tetragonal ZrO2 [26–28]. Figure 1(b) shows the
in the photodegradation of phenol. The photocatalytic tetragonal doublets for all ZnO-ZrO2 materials. Crystallite
study was carried out in a 250 mL pyrex reactor covered size and percentage of phases for pure ZnO and ZrO2 and
with a UV-transparent Plexiglas (absorption at 250 nm); ZnO-ZrO2 nanocomposites were determined using Debye-
the intensity of the radiation over the suspension was Scherrer equation and Garvie and Nicholson method.
90 W/m2. For each test, 200 mg of photocatalyst were sus- Because monoclinic phase was not observed in ZnO-ZrO2
pended into 200 mL of phenol solution (50 ppm). The sus- composites, we considered only the integral intensities of
pension was magnetically stirred in the dark with oxygen tetragonal and wurtzite peaks of ZrO2 and ZnO, respectively.
flow of 20 L/h until adsorption-desorption equilibrium was The obtained values are presented in Table 1.
reached (ca. 20 min). Then the suspension was illuminated
with an Osram Ultra-Vitalux lamp (300 W, UV-A, λ = 365 3.2. Raman Spectroscopy. The theory of groups predicts
nm). Aliquots of 3 mL were taken and filtered (Millipore six Raman-active modes of vibrations for tetragonal (A1g +
Milex-HV 0.45 μm) for further analysis. Variations in phe- 2B1g + 3Eg ) and 18 for monoclinic (9Ag + 9Bg ) of ZrO2,
nol concentration were tracked by high-performance liquid whereas for ZnO there are 4 Raman-active modes, although
chromatography (HPLC) using an Agilent Technologies splitting of E2 modes into longitudinal optical (LO) and
1200 chromatograph equipped with a UV-Vis detector and transversal optical (TO) gives place to 6 active modes. In
Eclipse XDB-C18 column 5 μm, 4 6 mm × 150 mm. The Figure 2, Raman spectra of the photocatalysts are pre-
mobile phase was water/methanol (65 : 35) at a flow rate of sented. For ZnO, two peaks can be clearly observed, the first
0.8 mL/min. Mineralization of phenol was measured by the one at 99 cm−1 and the second at 434 cm−1, corresponding
total organic content (TOC) in a Shimadzu 5000 TOC ana- to E2 mode characteristic of wurtzite-type structure; two
lyzer. The percentage of mineralization was estimated using additional weak bands at 326 and 380 cm−1 were also
the equation (equation (2)): observed which are related to 2-phonon and A1(TO) mode,
4 Journal of Nanomaterials

(220)

(F)

(E)

Intensity (a.u)
(004)
Intensity (a.u)

(D)

(C)
(101)
(111)

(112)
(111)

t
m
(020)

(211)
(110)
(110)

(−112)

(220)

(202)

m t
(310)

(301)
(003)

(220)
(211)

(023)
(120)

m mt t
mm m m mm t m t t (B)
(101)
(100)

71 72 73 74 75 76 77
(002)

(110)

2 Theta (degree)
(103)
(102)

(112)
(201)
(200)

(004)

(202)

(104)

(A) 13ZnO-ZrO2 50ZnO-ZrO2

25ZnO-ZrO2 75ZnO-ZrO2
20 30 40 50 60 70 80 90
2 Theta (degree)
(a) (b)

Figure 1: (a) XRD pattern of (A) ZnO, (B) ZrO2, (C) 13ZnO-ZrO2, (D) 25ZnO-ZrO2, (E) 50ZnO-ZrO2, and (E) 75ZnO-ZrO2 calcined at
500°C. t = tetragonal and m = monoclinic of ZrO2; w = wurtzite for ZnO. (b) XRD pattern of the samples evaluated in the region of 71–77°
to identify the tetragonal doublets of ZrO2.

Table 1: Crystallite size and percentage of phase content of

nanocomposites obtained from Debye-Scherrer equation and
z
Garvie and Nicholson method, respectively. m represents 93 t t
z
142 265 t
monoclinic and t tetragonal phase of ZrO2. w indicates the 313 434 t
wurtzite structure of ZnO. 461
Intensity (a.u)

Sample Crystallite size (nm) hkl Phase content (%)

ZnO 33.2 (101) 100%
m m
14.3 (101)m 59.7% 176 t
474 600
ZrO2 m
m m +
15.4 (−111)t 40.3% 100 m t
190 m 333
306 m
380 m 638
18.2 (101)t m
m 613
13ZnO-ZrO2 100% 217 m
z z 501 m 553
— — 434 534

14.5 (101)t 88.0%

25ZnO-ZrO2
44.7 (101)w 12.0%
100 200 300 400 500 600 700
14.4 (101)t 82.0%
50ZnO-ZrO2 Raman shift (cm−1)
48.3 (101)w 18.0%
13.8 (101)t 60.9% Figure 2: Raman spectra of ZnO-ZrO2 nanocomposites. (A) ZnO,
75ZnO-ZrO2
44.6 (101)w 39.1% (B) ZrO2, (C) 13ZnO-ZrO2, (D) 25ZnO-ZrO2, (E) 50ZnO-ZrO2,
and (F) 75ZnO-ZrO2. m indicates monoclinic and t tetragonal
structures for ZrO2 whereas z indicates wurtzite crystalline
respectively [29]. The ZrO2 spectrum showed several peaks structure of ZnO.
located at 100, 176, 217, 306, 333, 380, 474, 501, 534, 553,
613, and 638 cm−1, which are very close to those reported the peaks between 640 and 641 cm−1 are shared by mono-
for monoclinic phase. The peaks attributed to tetragonal clinic and tetragonal structures [30, 31]. Since cubic structure
structure were located at 142 and 265 cm−1 whereas two addi- of zirconia usually exhibits one strong peak around 617 cm1,
tional bands reported for this structure around 318 and the absence of this signal indicates the presence of a mixture
461 cm−1 seemed to be overlapped with monoclinic signals; of only two structures (monoclinic and tetragonal) in pristine
Journal of Nanomaterials 5

100
100 3424 744 576 498
(A) 90

80
95 (D)
(B) 70 (A)

Transmittance (%)
(D)
Transmittance (%)

(C)
60 (C)
90 (E)
50 (E)
(F)
85 40 (B)

30 (F)

80 20

10

75 0
4000 3800 3600 3400 3200 3000 2800 2600 1300 1200 1100 1000 900 800 700 600 500 400
Wavenumber (cm−1) Wavenumber (cm−1)
(a) (b)

Figure 3: (a) FT-IR full spectra of (A) ZnO, (B) ZrO2, (C) 13ZnO-ZrO2, (D) 25ZnO-ZrO2, (E) 50ZnO-ZrO2, and (F) 75ZnO-ZrO2
composites with different content of ZnO. (b) FTIR region from 1300 to 400 cm−1.

ZrO2. For the ZnO-ZrO2 composites, Raman spectra did not 3.4. Specific Surface Area. Figure 4 shows the N2 adsorption-
show sharp peaks. As the content of ZnO increased, we desorption isotherms of the nanocomposites as well as their
observed the broadening of the peaks that correspond to corresponding pore size distribution (insets). The isotherms
tetragonal structure modes; this broadening is related to the for all the samples presented type IV(a) shape according to
decrease in the crystallite size of this crystalline phase, usually IUPAC classification [36] which corresponds to mesoporous
due to phonons associated with the nanosized particles. structures where capillary condensation takes place and is
On the other hand, the absence of representative signals for accompanied by hysteresis. The adsorbed volume in all cases
monoclinic structure in both Raman spectra and XRD is relatively low which explains the observed values for spe-
patterns leads us to conclude that ZnO inhibited the forma- cific surface area. It has been reported that ZnO usually
tion of this structure in ZnO-ZrO2 composites. Addition- exhibits poor BET surface areas ranging from 1 to 15 m2/g
ally, Rietveld refinement of 13ZnO-ZrO2 was performed when no additives are used to improve this property. In our
(Supplementary Materials, Figure S4 and Table S1). This samples, pure ZnO showed a SBET = 10 m2 /g while ZrO2
analysis confirmed the absence of both solid solution and exhibited 46 m2/g.
cubic crystalline phase formation; the estimated percentages The isotherms of both ZnO and ZrO2 pure oxides
of each crystalline structure are shown in Table 1. showed a narrow hysteresis loop, which for ZrO2 starts at
0.4 (P/P0) and for ZnO this occurs at higher relative pressures
3.3. FTIR Analysis. Figure 3 shows the spectra of pure ZnO, (0.8) (Figure 4(a)). When composites were analyzed, hyster-
ZrO2, and ZnO-ZrO2 composites with different content of esis loop for all the composition was slightly broader than
ZnO. FTIR spectra of all materials presented wide bands at pure oxides, indicating changes in porosity (Figure 4(b)).
3410–3450 cm−1 which correspond to O-H stretching vibra- ZnO showed H3-type hysteresis loop at high relative pres-
tions of physical adsorbed water on the catalyst surface sure. However, ZrO2 and all ZnO-ZrO2 composites exhibited
[32]. Compared to the ZrO2 band, a shift of the O-H band H2-type hysteresis which is associated with the presence of
to lower frequencies occurs as the percentage of ZnO bottle-shaped mesopores that can be explained as a conse-
increases in the ZnO-ZrO2 composites. Pure ZnO spectrum quence of the interconnectivity of pores [1]. The specific sur-
showed an intense band centered at 423 cm−1. This band is face area decreased from 46 to 8 m2/g when 25% of ZnO was
characteristic for Zn-O vibrations [23, 32]. Two intense incorporated, and for 75ZnO-ZrO2, SBET value was 36 m2/g,
bands appeared at 744 cm−1 and 576 cm−1 have been associ- and its N2 isotherm showed a broader hysteresis loop than
ated with vibrations of Zr-O in monoclinic structure. An the observed pure oxides. Additional effect of ZnO incorpo-
additional band located at 498 cm−1 was also present in ration was observed in BJH pore size distribution: pristine
ZrO2 spectrum; this signal corresponds to Zr-O-Zr vibra- ZrO2 showed a wide pore size distribution from meso- to
tions in tetragonal structure [33–35], which appears slightly macropores, whereas ZnO presented pores around 30 nm
shifted for all ZnO-ZrO2 nanocomposites. This behavior and also macroporosity; when both oxides were coupled,
can be attributed to the addition of divalent oxides like pore size distribution for all composites showed unimodal
ZnO (Zn+2) to ZrO2. Also, the incorporation of these oxides distribution with very close pore size average.
may produce a lattice deformation on the crystalline struc-
ture, with subsequent modification on the force constants 3.5. Diffuse Reflectance UV-Vis Spectroscopy. The absorption
of Zr–O and related bonds [33]. spectra of the oxides are depicted in Figure 5(a). The Uv-Vis
6 Journal of Nanomaterials

200
0.08 120 0.30
180 0.25 13Zn O-ZrO2
0.07 110 0.25 25Zn O-ZrO2
160 0.06 100 50Zn O-ZrO2
0.20
0.20
Adsorbed volume (cm3/g)

dV(logd) (cc/g)
dV(logd) (cc/g)

dV(logd) (cc/g)
Adsorbed volume (cm3/g)
140 0.05 90 75Zn O-ZrO2
0.04 0.15 80 0.15
120
0.03 70 0.10
100 0.02
0.10
60
0.05
80 0.01 ZnO 50
ZnO 0.05
2 0.00
60
0.00 40
10 100 10 100
30
40 Diamter (nm) Diamter (nm)
20
20 10
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0) Relative pressure (P/P0)

(a) (b)

Figure 4: N2 adsorption-desorption BET isotherms of (a) pure oxides and (b) different ZnO-ZrO2 composites; the insets represent BJH pore
size distribution from desorption branches.

1.8 4.00E-009
209-211 nm(A) 370 nm
1.6 3.50E-009 I
1.4 208 nm
365 nm 3.00E-009
1.2 228 nm (F)
(E) 363 nm
2.50E-009
((F(R)⁎hv)1/2
Absorbance

1.0 (D) 361 nm II (E)

2.00E-009 (D)
0.8 (C)
1.50E-009
0.6
(C) 358 nm
1.00E-009
0.4 (B)

0.2 5.00E-010
(B) (A)
0.0 0.00E-000
200 300 400 500 600 700 800 2 3 4 5 6
Wavelength (nm) Band gap energy (eV)
(a) (b)

Figure 5: (a) UV-Vis/DR absorption spectra of (A) ZnO, (B) ZrO2, (C) 13ZnO-ZrO2, (D) 25ZnO-ZrO2, (E) 50ZnO-ZrO2, and (F) 75ZnO-
ZrO2 composites; (b) Kubelka-Munk function of (A) ZrO2, (B) 13ZnO-ZrO2, (C) 25ZnO-ZrO2, (D) 50ZnO-ZrO2, and (E) 75ZnO-ZrO2
composites. (I) represents the first and (II) the second edge of the samples considered for Eg estimations.

spectrum of ZnO shows an absorption edge at 370 nm, which upon UV light excitation [40]. There was no other absorption
is in good agreement with literature [37]. This characteristic band observed in the UV-Vis region. It has been reported
band can be assigned to the intrinsic band-gap absorption that the identification of ZrO2 phases can be possible by
of ZnO due to the electron transitions from the valence band using UV range of DRS. The two bands observed in pure
to the conduction band (O2p → Zn3d) [38]. ZrO2 spectrum ZrO2 are typically observed since ZrO2 has two band-to-
showed a small absorption band at 208 nm and another large band transitions. According to Sahu and Rao [41], the first
band at 228 nm, which appeared at lower wavelengths than transition corresponds to values around 5.17–5.2 eV that
the characteristic bands reported for ZrO2, usually observed can be associated with m-ZrO2. In the ZrO2 here prepared,
~240 nm [39]. These bands correspond to the presence of we observed by DRX that monoclinic and tetragonal phases
Zr species as the tetrahedral Zr+4, and it is electronically pro- are presented in pure oxide. The band at high energy cannot
duced by the charge transfer transition of the valence band be observed when the content of ZnO increases, not only due
O2p electron to the conduction band Zr4d (O2 → Zr4+) level to the disappearance of monoclinic phase but also for the
Journal of Nanomaterials 7

(a) (b)

Figure 6: FESEM (a) and the corresponding HRTEM (b) micrographs of pure oxides and ZnO-ZrO2 composites.

incorporation of ZnO affecting the shape of the spectrum. wavelength region, due to the introduction of energy levels
The spectrum of pure ZrO2 also depicts a small shoulder with in the interband gap [17]. Kubelka-Munk function was
an onset at 310 nm that can be attributed to t-ZrO2 crystal- used to estimate the band gap of the nanocomposites
line structure [42]. The shape as well as the intensity of this (Figure 5(b)). The band gap values of pure ZnO and ZrO2
band changes as the content of ZnO increases and slightly were evaluated by using n = 2 (direct transitions) and n =
shifts towards lower energy region, due to the effect of ZnO. 1/2 (indirect transitions), respectively, and their values are
The addition of ZnO modified the absorption edge of summarized in Table S2 (Supplementary Materials).
ZrO2 towards lower values. A red shift was observed in For ZnO-ZrO2 materials, it can be noticed the presence of
the last band of all ZnO-ZrO2 materials towards longer two edges instead of only one; the bandgap was estimated
8 Journal of Nanomaterials

80
50
70

60 40

% Mineralization
% Degradation

50
30
40

30 20
20

10 10

0
0
0 20 40 60 80 100 120

13ZnO-ZrO2

25ZnO-ZrO2

50ZnO-ZrO2

75ZnO-ZrO2
ZnO

ZrO2
Time (min)

Photolysis 25ZnO-ZrO2
ZnO 50ZnO-ZrO2
ZrO2 Photocatalyst
75ZnO-ZrO2
13ZnO-ZrO2

(a) (b)

Figure 7: (a) Degradation curves of phenol by ZnO, ZrO2, and different ZnO-ZrO2 composites (experimental conditions: phenol = 50 ppm,
volume of phenol = 200 mL, and catalyst dosage = 200 mg). (b) TOC results obtained after 120 min of illumination in the UV.

using n = 1/2. The obtained value for ZnO was 3.26 eV Table 2: Kinetic parameters estimated from pseudofirst order
(Supplementary Materials, Figure S5) whereas 4.53 and kinetics.
5.06 eV were calculated for ZrO2 (for the two edges Photocatalyst k (min−1) R2 t1/2 (min)
observed in the corresponding spectrum), these values −3
changed to 4.73, 4.35, 3.76, and 4.16 eV by the addition of ZrO2 0 7 × 10 0.9585 1155
different contents of ZnO (indicated as I in Figure 5(b)), 13ZnO-ZrO2 1 3 × 10−3 0.9193 533
being 50ZnO-ZrO2 the one with the lowest value. With 25ZnO-ZrO2 1 5 × 10 −3
0.9808 462
regard to the low-energy shoulder observed in ZnO-ZrO2 −3
spectra (indicated as II in Figure 5(b)), the calculated values 50ZnO-ZrO2 5 3 × 10 0.9939 130
−3
were 3.07, 3.10, 3.15, and 3.16 eV for the composites with 75ZnO-ZrO2 10 3 × 10 0.9964 67
13, 25, 50, and 75% of ZnO, respectively, allowing ZnO 11 2 × 10 −3
0.9810 62
nanocomposites to be excited at lower energy.

3.6. Electron Microscopy. Morphology of the nanocomposites

was investigated using electron microscopy, and the images Figure 7(a). Here, we observed that pure ZrO2 degraded
are shown in Figure 6. We observed that ZnO nanoparticles only 5% of phenol even after 120 min; when ZnO was incor-
are rod-like shaped with sizes ranging from 100 to 300 nm porated, a slight increase in photodegradation with 13 and
producing agglomerates. On the other hand, ZrO2 is made 25% of ZnO was observed, but they barely degraded around
of smaller particles nonuniform in shape and size. In 15% of the pollutant. By increasing the ZnO content up to
13ZnO-ZrO2 nanocomposite, we observed that ZnO parti- 50% mol, 47% of phenol was degraded, whereas 71% of deg-
cles change in shape whereas some ZrO2 agglomerates grew radation was achieved using 75ZnO-ZrO2 composite. For the
up to 1 μm but also smaller quasispherical particles around prepared ZnO, 74% of degradation was obtained during the
300 nm were observed. The most significant change was same time. The kinetic parameters were also calculated
exhibited by 75ZnO-ZrO2 nanocomposite, since agglomer- assuming pseudofirst order kinetics (Table 2) where we
ates of particles with smaller sizes were obtained. observed that t1/2 for 75ZnO-ZrO2 composite was very close
to that calculated for ZnO.
3.7. Photocatalytic Test. Previous to the test, adsorption- It is well known that ZnO can be activated under UV-
desorption equilibrium was reached after stirring the sus- A light and generally exhibits good photodegradation rates,
pensions for 20 minutes in the dark, of which in general but it is also needed to assess the mineralization of the
all the composites presented low adsorption of the pollut- pollutant. For this purpose, TOC analysis was performed
ant. The results of photocatalytic degradation are shown in and the results are tabulated in Figure 7(b). Pure ZrO2
Journal of Nanomaterials 9

hv = 365 nm

hv
hv
hv hv
hv
hv
e− e− e− O2
e− e− e−
O2.
Phenol
ZrO2 ZnO ZnO-ZrO2 CO2 + H2O
5.06 eV 3.26 eV
H2O
h+ h+ h+ OH.
h+ h+ h+
OH−
OH.

Figure 8: Schematic representation of photocatalytic mechanism of electron-hole pair separation of ZnO-ZrO2 composites for the
degradation of phenol.

mineralized 2.5% of phenol, but the mineralization the phenol until obtaining CO2 and water. As a result, we
increases with increasing ZnO content, which stabilizes obtained an enhancement in photocatalytic performance of
tetragonal crystalline phases of ZrO2. Although ZnO phenol degradation by the composite with the highest ZnO
reached 74% degradation, the mineralization of the pollut- percentage [8, 19, 20, 43].
ant was 40%, while 51% of mineralization was achieved
with 75ZnOZrO2. Tetragonal ZrO2 has been reported as 4. Discussion
the most active polymorph of ZrO2 which also shows high
selectivity in catalytic reactions. These results showed that It is well known that the catalytic and photocatalytic perfor-
at this concentration, ZnO-ZrO2 composite improved the mance of ZrO2 can be affected by crystalline phases.
mineralization of phenol when compared to pure ZnO. Although there are some reports on the catalytic activity of
Besides, it was also confirmed that intermediaries like cat- ZnO-ZrO2 materials, deep structural studies have not been
echol, resorcinol, and hydroquinone were not generated performed so far. The fact that both tetragonal and cubic
during the photodegradation with 75ZnO-ZrO2. phases exhibit similar XRD patterns makes it difficult to dis-
According to the obtained results, a schematic represen- cern these structures based only on X-ray diffraction analysis,
tation of phenol degradation is shown in Figure 8. When and Rietveld refinement or Raman spectroscopy are good
the ZnO-ZrO2 composites were excited by Uv-A irradiation tools for elucidating this ambiguity. In this work, we observed
(365 nm), electrons migrate from the valence band (VB) to that by adding ZnO, only the t-ZrO2 phase was obtained, and
the conduction band (CB) of ZnO, leading to the formation this phenomenon could also be suspected by analyzing
of electron/hole (e−/h+) pairs. Since the energy levels of Raman results. In all composites, t-ZrO2 was detected as well
ZnO fit well into the band gap of ZrO2, the electrons from as zincite (wurtzite-type) structure for ZnO. Formation of the
the CB of ZrO2 can easily be transferred to the CB of ZnO; nanocomposite influenced the crystallite size of both ZnO
conversely, the holes migrate from the VB of ZnO to the and ZrO2, increasing for ZnO but decreasing for t-ZrO2 as
VB of ZrO2, and thereby the electron-hole pair recombina- a function of the ZnO-ZrO2 ratio. The absence of solid solu-
tion may be decreased in ZnO-ZrO2 composites. These e− tion could be explained not only due to the differences in
and h+ react with water and oxygen to produce hydroxyl valence between ions, which depends on the amount of
(OH⋅) radicals which are very reactive and can easily oxidize Zn2+ species [44], but also due to the synthesis procedure
10 Journal of Nanomaterials

here reported. Lattice parameters of the 13ZnOZrO2 nano- Data Availability

composite are provided in Supplementary Materials. We
observed small changes when compared to pure zirconia; this All data obtained from characterizations technics used to
can be attributed to the presence of the divalent oxide, since support this study are available from the corresponding
incorporation of these type of oxides causes lattice deforma- author upon request.
tion on the crystalline structure of ZrO2, with subsequent
modification on the force constants of Zr–O and related Conflicts of Interest
bonds [33].
Since band gap is one important feature to consider in The authors declare that they have no conflicts of interest.
photoactivity, many attempts to improve this property have
been made. By coupling ZnO and ZrO2, radiation of low
energy can be absorbed by the ZnO-ZrO2 composites. From Acknowledgments
the calculated Eg values, it can be assumed that the energy We are grateful to D.H. Aguilar and A. Marín for their
levels for both the valence band (VB) and conduction band technical assistance, and acknowledge the financial support
(CB) in ZnO fit in with the bandgap of ZrO2. When the elec- of the projects UJAT-IB-43, CONACYT-INFR-269701, SEP-
trons are excited, most of the electrons from the conduction CONACYT-CB-183196, FOMIX-Yucatán 2008-108160, and
band of ZrO2 can be easily transferred to the conduction CONACYT LAB-2009-01 (No. 123913). In addition, we
band of ZnO, and thus, the band gap may be decreased, indi- would like to thank CONACYT for the fellowship given to
cating that ZnO-ZrO2 nanoparticles have a suitable band gap M. Uribe, and to ICMS-CSIC, LANNBIO CINVESTAV-
to generate excited electron/hole pairs [17] allowing the use Mérida, UAM-I, and UJAT for the facilities.
of simulated solar radiation.
Both oxides, ZnO and ZrO2, are well known for their
photocatalytic properties, but one of their limitations is the Supplementary Materials
need of UV light for its activation, especially ZrO2 that usu-
ally requires UV radiation due to its wide band gap. Here, In the supplementary information, the authors provided
we investigated the effect of ZnO in the photocatalytic perfor- the details on the mechanism of formation for ZnO-ZrO2
mance of ZrO2 under simulated solar light. Since the use of materials, as well as the crystalline data obtained through
pure ZnO leads to the formation of several compounds dur- the Rietveld refinement and HRTEM of the 13ZnOZrO2.
ing the photoreaction, it is remarkable that 75ZnO-ZrO2 (Supplementary Materials)
nanocomposite conducted to a reaction without formation
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