In summary, flower-like ZnO architecture was
successfully prepared by hydrothermal method. Assynthesized ZnO was mesoporous structure and
composed from many nanosheets, it showed the large
surface area (24.4 m2/g) and high pore volume (0.280
cm3/g). The degradation of caffeine on ZnO was fast
and archived 97.6% under UV light at 120 min,
particularly it was higher (100%) under solar light at
60 min. In addition, the flower-like ZnO exhibited a
good cycling stability. Therefore, as-prepared sample
was expected that could be potential material for
cleaning industrial wastewater.
Acknowledgments
This work was supported by Vietnamese
Ministry of Education and Training by the Grant
number of B2017-BKA-53
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Journal of Science & Technology 126 (2018) 016-020
16
Preparation of Flower-like ZnO Architecture for Photodegradation of
Caffeine in Aqueous Solution
Le Thi Mai, Nguyen Thi Men, Vu Anh Tuan*
Hanoi University of Science and Technology – No. 1, Dai Co Viet Str., Hai Ba Trung, Ha Noi, Viet Nam
Received: August 10, 2017; Accepted: May 25, 2018
Abstract
The flower-like ZnO architecture was prepared by hydrothermal method. As-synthesized samples were
characterized by XRD, SEM, and N2 adsorption/desorption isotherm. The composition of samples before
and after calcination was analyzed by XRD, the precursor was completely transformed to ZnO at 400 °C.
The catalytic performance of ZnO was evaluated by the degradation of caffeine in aqueous solution under
different irradiation of lights. The degradation efficiency was 97.6% under UV light in 120 min and it was
100% under solar light in 60 min. The reaction kinetic of photodegradation of caffeine was studied by first-
order kinetic model and the reusability of the ZnO sample was investigated through five cyclic tests.
Keywords: ZnO, Caffeine, Photocatalyst, Flower-like structure, First-order kinetic
1.Introduction1
Pharmaceutical and personal care products
(PPCPs) are increasingly important to our lives.
However, they are classified as the most serious
pollutants when discharged into the environment.
Their presence in surface water pollutes the water
environment and adversely effects on human health.
Therefore, the treatment of PPCPs before emitting
into environment has attracted the attention of many
scientific researchers in the Global [1,2].
Caffeine, C8H10N4O2, an alkaloid belonging to
the methylzanthine family [3], is an example of
PPCPs that often appears in surface water. Caffeine
present in beverages such as coffees, teas, soft drinks,
chocolate, some drugs, which makes it a widely
consumed substance in the world. The World Bank
reported that with its potential, Vietnam’s market
may consume 70,000 tons of coffees per year [4].
The presence of caffeine in surface water is due
to sewage spills, leaky sewer pipes, poorly
maintained septic systems, and other means of
sanitary sewer flows. In addition, it may be due to
attributable to storm water runoff containing
wastewater influences, food waste or beverage
containers from trash receptacles, recycled water
over-irrigation, human waste at homeless
encampments, or other anthropogenic activities [5].
Caffeine alone does not seem to be toxic to domestic
organisms. However, the presence of too much of it
in surface water, along with other organic pollutants
such as pesticides, pharmaceuticals and other
*Corresponding author: Tel.: (+84) 912.911.902
Email: tuan.vuanh@hust.edu.vn
chemicals, has serious implications for organisms and
humans [5]. Therefore, removal of caffeine from
effluents is very necessary.
Photocatalysis is an environmentally friendly
method for water and wastewater treatment. The main
advantage of advance oxidation process by
photocatalyst is the mineralization of organic
pollutants into CO2, H2O and simple inorganic acids
[3,6]. There are many types of semiconductor oxides
such as TiO2, ZnO, Bi2O3, and Nb2O5 were used as
photocatalysts for the decomposition of organic
pollutants. TiO2 has been widely used because of the
large band gap (>3.2 eV). However, ZnO presented a
relative lower cost, easier to synthesize, greater
thermodynamic stability than TiO2. In addition, ZnO
exhibited the great interest because of its excellent
performance in photocatalyst, solar cell, paint
manufacture and food additives [7].
In relation to structure, ZnO could be prepared
with different morphologies and it strongly affected
to the catalytic ability [8]. The architecture structure
with the large surface area and high pore volume will
give advantage for the adsorption, diffusion, and
reaction of organic compounds on the surface of
ZnO. Therefore, the objective of this research was to
preparation of flower-like ZnO architecture for
photodegradation of caffeine in water.
2. Experimental
2.1. Materials
Zinc nitrate hexahydrate (Zn(NO3)2.6H2O,
99.5%) and urea (NH2)2CO, 99.5%) were purchased
from China, caffeine was obtained from Sigma-
Aldrich (99.0%). All the chemicals were used without
any purification and distilled water was used
Journal of Science & Technology 126 (2018) 016-020
17
throughout the experiments.
2.2. Synthesis of flower-like ZnO
The hierarchical ZnO was fabricated by a simple
hydrothermal process. In a first stage, 30 mL of zinc
nitrate hexahydrate 0.5M, 0.03 mole urea, and 70 mL
of distilled water were put in a bearker 250 mL. The
mixed solution was stirred at 240 prm for 30 min.
Then, the mixed solution was transferred into teflon-
lined autoclave and heated at 90 °C for 24 h.
Subsequently, the autoclave was cooled to room
temperature, the precipitation was detached by
vacuum pumping filtration, washed with distilled
water for 4-5 times and dried at 90 °C for 24 h.
Finally, the flower-like hierarchical ZnO were
obtained by calcining the precipitate at 400 °C for 2 h
with a heating rate of 2 °C/min.
2.3. Characterization
The crystalline phase of samples was
investigated by X-ray power diffraction. XRD
patterns were obtained by using Bruker D8 Ax XRD-
diffractometer (Germany) with Cu Kα irradiation
(40kV, 40 mA). The 2θ ranging from 10° to 80° was
selected to analyse the crystal structure. The
morphology of the samples was observed by field
emission scanning electron microscopy (FE-SEM,
JEOL-7600F). The textural properties were measured
via N2 adsorption/desorption isotherms using a
Micromeritics (Gemini VII analyzer). The specific
surface area, pore volume and pore diameter were
obtained by using the Brunauer-Emmett-Teller (BET)
method.
Fig. 1. (a-c) SEM images of hierarchical flower-like
ZnO with different scale bars and (d) the digital photo
of the Persian rose.
3. Results and discussion
3.1. SEM analysis
The SEM images of as-synthesized ZnO are
depicted in Fig. 1. ZnO was observed with uniformly
hierarchical flower and 1 μm in size, as seen in Fig.
1(a). The micro flower-like ZnO was composed of
many nano sheets formed by many zinc oxide
nanoparticles, as seen in Fig.s 1(b) and (c). In
addition, as-synthesized sample showed a beautiful
rose-like ZnO, as seen in Fig. 1(d). Thus, exception
of the ZnO particles are shaped like nanorods,
nanoneedles, nanowires, nanobelts, nanosheet, etc.,
the flower-like shape is expected as a great
morphology for photocatalytic application process.
3.2. XRD analysis
The crystal phase of the samples was
characterized by XRD analysis and the result is
shown in Fig. 2. The diffraction peaks of precursor
before calcination were in good agreement with with
zinc hydroxide carbonate, Zn4(CO3)(OH)6.H2O
(JCPDS:11-0287). While, the diffraction peaks of
precursor after calcination were attributed to zinc
oxide, ZnO (JCPDS:19-1458) and no other
characteristic peaks for impurities were detected,
indicating precursor had completely transformed into
the pure ZnO crystal at 400 °C in 2 h [9,10].
The ZnO formation mechanism was explained
following: The mixing process was performed at
room temperature. When urea was added to the Zn2⁺
solution, the urea molecules hydrolysis in aqueous
slolution to form amonniac and carbon dioxit, and
then form OH⁻ and CO32⁻ anions:
(NH2)2CO+3H2O→2NH3.H2O+CO2 (1)
NH3.H2O→NH4⁺+OH⁻ (2)
CO2 + OH⁻ → CO32⁻ + H2O (3)
Then the OH⁻ and CO32⁻ was continue to react
with Zn2⁺ ion to generate zinc carbonate hydroxide
4Zn2⁺+CO32⁻+6OH⁻+H2O →Zn4(CO3)(OH)6.H2O (4)
The precipitate was filted, washed with distilled
water several times, dried at 90 °C over night, and
then calcined at 400 °C for 2 h with ramping rate 2
°C/min to obtain ZnO powder:
Zn4(CO3)(OH)6.H2O→4ZnO+CO2+4H2O (5)
3.3. N2 adsorption/desorption isotherm analysis
The N2 adsorption/desorption isotherm was
conducted to investigate the porosity of the material,
including its specific surface area and pore sizes. The
isotherm and pore size distribution curves flower-like
ZnO sample are presented in Fig. 3. The isotherm
curve was identified as type IV. When the relative
pressure (P/Po) increased from 0.91 to 0.98, a sharp
hysteresis loop was observed, indicating the presence
of mesoporous material. In addition, when the
Journal of Science & Technology 126 (2018) 016-020
18
relative pressure was higher than 0.98, an abrupt
increase in the amount of adsorbed nitrogen was
observed. The pore size distribution was relatively
wide and most of pores in range from 15 to 100 nm.
As a result, ability to diffuse and efficiently transport
hydroxyl radicals in photochemical reactions
enhances the catalytic activity of the ZnO material
[9,11]. The surface area and average pore size of as-
prepared ZnO were 24.4 m2/g and 0.280 cm3/g,
respectively.
Fig. 2. XRD patterns of the precursor before
calcination and as-synthesized ZnO
Fig. 3. N2 adsorption/desorption isotherm (inset: pore
size distribution) of as-synthesized ZnO.
3.4. Photocatalytic degradation mechanism of
caffeine on ZnO
The degradation of caffeine was conducted with
0.3 g ZnO, 100 mL caffeine solution with a
concentration of 5 mg/L under subdued light,
tungsten lamp (100 W), UV light (15 W) and solar
light (at 11 h-13 h in summer). The results are shown
in Fig. 4(a). It was clearly seen that the degradation
efficiency of caffeine was strongly affected by light
irradiation. Under subdued light, the degradation
efficiency in 60 min was negligible. Under tungsten
lamp, the degradation of caffeine was 18.8% in 120
min, whereas the degradation efficiencies of caffeine
significantly increased under UV light and solar light,
these values were 97.6 and 100%, respectively.
Particularly, the caffeine was completely degraded in
60 min, it could be attributed to simultaneous existent
of visible and UV in solar light, this was agreed with
previous report [12].
Fig. 4. (a) Effect of irradiation light on degradation of
caffeine and (b) first-order curves.
The photodegradation rate of caffeine by flower-
like ZnO can be evaluated by using the pseudo-first-
order model called Langmuir–Hinshelwood model as
follow:
ln
C0
Ct
= kt (6)
Where C0 and Ct are the concentration of
caffeine at initial (t =0) and time t (min), respectively.
k is the pseudo first-order rate constant. The k value
was calculated from the slope of the ln (C0/Ct) − t
plots.
It is obviously seen that in Fig. 4(b), the
degradation rate of caffeine under subdued light was
low with a small rate constant 0.001 min-1), the rate
constant slightly increased to 0.003 min-1 with
irradiation of tungsten lamp. Howerer, it was strongly
increased to 0.017 to 0.041 min-1 for UV light and
solar light, respectively.
The directed comparison as-prepared ZnO with
Journal of Science & Technology 126 (2018) 016-020
19
other samples in literature is a challenge since ZnO
have been prepared by different methods for many
applications such as cosmetic, paint, sensor,
adsorption, and photocatalyst. However, it was clear
showed that as-prepared ZnO had the hierarchical
structure with the high reaction performance, the
degradation efficiency was higher than that of other
ZnO samples that had been reported, as seen in Fig. 1
and Table 1.
Table 1. Comparison as-prepared ZnO with other
samples.
ZnO
samples
Particles
Size
Applicati
-on
Performance Ref.
Flower 1 µm - - [13]
Flower 1-2 µm Bromop-
enol dye
removal
96% within 120 min,
concentration of 10 ppm
[14]
Rod 80-100
nm
RhB
removal
97 % within 120 min,
concentration of 10 ppm
[15]
Nano-
spheres
15-60 nm RR141
removal
78% within 240 min,
concentration of 10 mg/L
[16]
Nano
disks
~ 200 nm RhB
removal
90 % within 90 min,
concentration of 10 ppm.
[17]
Flower 1 µm Caffeine 100 %, within 60 min,
concentration of 5 mg/L
This
study
Fig. 5. UV-Vis spectra of caffeine aqueous solution
as function of reaction time with ZnO as catalyst.
Fig. 6. Mechanism of caffeine photodegradation
using flower-like ZnO under UV light and solar light.
Fig. 5 shows the absorption spectrum of the
caffeine solution at the concentration of 5 mg/L with
0.3 g of ZnO under UV irradiation at different
reaction times. The maximum absorption peak of the
caffeine at 274 nm diminished gradually and even
disappeared at 120 min. This result suggests that the
caffeine molecules and intermediates are degraded
almost completely by oxidation, hydroxylation and
mineralization processes. It is therefore beneficial for
water treatment to help protect the environment. The
mechanism for photocatalyst activity of flower-like
was proposed, as shown in Fig. 6.
Upon the UV or solar light irradiation, the
electrons in the valence band of ZnO can be excited
to the conduct band, leaving holes in the valence
band. The electrons can active molecular oxygen to
form superoxide ion (O2-) and the photogenerated
holes react with either water (H2O) or hydroxyl ions
(OH⁻). The formation of •OH, •O2⁻ radicals water
have created hydroxylation, oxidation and
mineralization processes, as described by equations
7-12 [1,18-20]. Which are able to degrade caffeine to
intermediated products, CO2 and H2O.
Water is dissociated into ions
H2O → H⁺ + OH⁻ (7)
ZnO can absorb UV light (or solar light) and
generate electron-hole pairs (Fig. 6)
ZnO + hν → e⁻ + h⁺ (8)
The electrons move to the surface of the catalyst
and adsorbed O2 on the surface to form •O2⁻
e⁻ + O2 → •O2⁻ (9)
The •O2⁻ can react with surface adsorbed H2O to
form H2O2:
•O2⁻ + H2O → H2O2 (10)
Photoconversion of H2O2 gives OH radicals:
H2O2 + hν → 2•OH (11)
The holes react with OH⁻ ions in the water form
OH radicals:
h⁺ + OH⁻ → •OH (12)
Fig. 7. Cycling stability of ZnO catalyst
3.5. Reusability of the catalyst
In the practical application, the reusability of the
catalyst is also the critical parameter. In this study,
as-synthesized ZnO was reused for four times at the
Journal of Science & Technology 126 (2018) 016-020
20
same condition, caffeine concentration of 5 mg/L and
ZnO 0.3 g under UV light. Fig. 7 shows the
degradation efficiency caffeine of ZnO at each cycle.
The performance of catalyst only presented a little
drop. At the first run, the degradation efficiency was
97.6%, and this value was remained over 80.0% after
four cycles. This revealed that flower-like ZnO
architecture had a good cycling stability and potential
application in industry.
4. Conclusion
In summary, flower-like ZnO architecture was
successfully prepared by hydrothermal method. As-
synthesized ZnO was mesoporous structure and
composed from many nanosheets, it showed the large
surface area (24.4 m2/g) and high pore volume (0.280
cm3/g). The degradation of caffeine on ZnO was fast
and archived 97.6% under UV light at 120 min,
particularly it was higher (100%) under solar light at
60 min. In addition, the flower-like ZnO exhibited a
good cycling stability. Therefore, as-prepared sample
was expected that could be potential material for
cleaning industrial wastewater.
Acknowledgments
This work was supported by Vietnamese
Ministry of Education and Training by the Grant
number of B2017-BKA-53.
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