Study on the photocatalytic activities of ZnO powder

Phạm Thị Ngọc Mai, Lê Sỹ Hưng, Phan Trí Hoà

Faculty of Chemistry, University of Natural Sience, Vietnam National University,
19 Le Thanh Tong, Hanoi, Vietnam

Abstract

Photocatalysis is one of the most common research areas of the modern science which uses a lot of
special kinds of materials activated under the effect of the light to catalyze the reactions in the nature.
Our objective here is to synthesize ZnO powder modified with different elements (such as C, S, N,
FexOy...), which allows materials to work under the visible light (λ= 400 nm – 760 nm) and therefore
widen the applications in the daily life. The photocatalytic activities of the obtained materials have
been assessed through phenol and methylene blue degradation reaction. Several other factors
influencing to the photocatalytic degradation such as pH, catalyst loading, time, the presence of H 2O2
also have been investigated. The microstructure of the material has been studied by XED and SEM.

Xúc tác quang hóa là một trong những lĩnh vực nghiên cứu phổ biến sử dụng vật liệu đặc biệt
được hoạt hóa dưới tác dụng của ánh sáng để xúc tác cho các phản ứng trong tự nhiên. Mục
đích của bài báo này là tổng hợp bột ZnO biến tính với một số nguyên tố khác nhau như C, S, N, Fe,
cho phép vật liệu hoạt động được trong vùng ánh sáng nhìn thấy thay vì vùng tử ngoại để từ đó có thể
mở rộng phạm vi ứng dụng trong đời sống hàng ngày. Hoạt tính xúc tác được đánh giá qua phản ứng
phân hủy phenol và metylen xanh. Một số yếu tố ảnh hưởng đến sự phân hủy quang hóa như pH,
lượng ZnO xúc tác, lượng xúc tác sử dụng, thời gian xúc tác, sự có mặt H 2O2, ... cũng được nghiên
cứu. Các đặc trưng cấu trúc của vật liệu được khảo sát bằng phương pháp nhiễu xạ tia X (XRD) và
hiển vi quét điện tử (SEM).

I. Introduction
Photocatalyst has been used in wastewater treatment processes to modify the rate of chemical reactions
using light irradiation [1].The advantage of this method is to convert contaminant materials to a large
extent into stable inorganic compounds such as water, carbon dioxide and salts, i.e. they undergo
mineralization. A lot of studies have been reported on the photocatalytic degradation (PCD) of refractory
organics. Bhatkhande et al. [2] reviewed recent works in this area and listed the compounds degraded by
photocatalysis by various researchers. Degussa P-25 TiO 2 has been used for many systems either in
suspended or in supported forms. In few studies, other semiconductors, such as ZnO, CdS, FeO and WO 3
have been used [2-4]. Although, TiO 2 in the anatase form has been used for many environmental
applications, ZnO is a suitable alternative to TiO 2 so far as band gap energy (~3.2 eV) is concerned. The
quantum efficiency of ZnO powder is also significant larger than that of TiO 2 powder, and higher catalytic
efficiencies have been reported for ZnO [4].
However these semiconductors mostly can only work under UV irradiation because of large band gap.
It is a disadvantage because UV is only about 5% in sunlight. Recently, a new trend of PCD study is
modifying the band gap of semiconductors to shift the working region from UV to VIS [5-7]. To make
visible-light driven photocatalysts, transition metal dopants have been widely used to extend
semiconductor’s light absorption into the visible-light region. Iron is frequently employed owing to its
unique half-filled electronic configuration, which might narrow the energy gap through the formation of
new intermediate energy levels. Fe-doped TiO 2 also exhibited enhanced activity under visible-light
irradiation for the degradation of MB, MO, methanol, and toluene. It is generally accepted that the Fe 3+
dopant formed shallow charge traps within the TiO 2 crystal lattice through the substitution of Ti4+, which
reduced the electron–hole recombination and improved the photocatalytic efficiency. Another way to
modify the band gap is doping nonmetal atoms, such as C, N, and S... Theoretical calculations showed that
the p-orbitals of these dopants significantly overlapped with the valence band O 2p-orbitals, which
facilitated the transport of photo-generated charge carriers to the surface of the catalyst.
The objective of our research is to synthesize and investigate the photocatalytic activity of a zinc oxide
(ZnO)-based material for a degradation of two model organic pollutants: methylene blue and phenol under
visible light. The influence of radiation time, catalyst loading, pH of the suspensions on the photocatalytic
degradation will be investigated.

II. Experimental
II.1 Synthesis of ZnO-based powder
ZnO-based powder were prepared by wet chemical method using zinc nitrate and sodium hydroxide as
precursors and soluble starch as stabilizing agent. The starch was dissolved in 300 mL of distilled water,
followed by adding zinc nitrate. Iron (II) sulfate, cadimium nitrate, and sodium sulfide were added as
source of Fe, Cd, and S respectively. Zinc nitrate solution and solution that contains desired elements are
added drop by drop in to the sodium hydroxide solution under constant stirring.
The reaction was allowed to proceed for 2h after complete addition of sodium hydroxide. The solution
was then allowed to settle for overnight and the supernatant solution was discarded carefully. Thus
obtained particles were washed several times using distilled water to remove the by-products and the
excessive starch that were bound with the particles. After washing, the particles were dried at 120°C to
completely convert Zn(OH)2 to ZnO.
II.2 Investigate the photocatalytic degradation of methylene blue and phenol
The reactor for the photocatalytic degradation of methylene blue and phenol was wrapped around by an
aluminum foil for reflection of UV light back into the reactor. The UV lamp was kept on for a certain
periods between 2 to 4 hours. Samples of approximately 10 mL aliquots were withdrawn after certain
periods of time, centrifuged to remove any suspended solid and analyzed by a Shimadzu UV visible
spectrophotometer to determine % methylene blue removals in the sample. The percentage of dye removal

was calculated by the formula: % removal = ,where A is the absorbance of solution at

time t, A0 is the absorbance of solution at initial (t=0).

III. Results and discussions

III.2 Photocatalytic activity of ZnO based materials

In this experiment, the photocatalytic activity of ZnO based materials was studied carefully on the
basis of the % methylene blue removals. Each material was tested with a weighted amount of powder (1.0
gram) and stirred in 400ml of 10 ppm methylene blue solution at pH = 6.0. The reactions were carried out
in 1 hour with vis-lamp source.

Figure 17. Photocatalytic activity of ZnO based materials

 From the data, ZnO doped with ZnS shows the greatest photocatalytic activity. According to [59],
the existence of S in ZnO lattice may introduce new impurity level between the conduction and valence
bands of ZnO, and hence narrow the band gap of ZnO. We therefore will concentrate our study on the
ZnO modified with S (ZnO1-x Sx) to have further information about the properties and its photo-activity.

III.2 Microstructural characterization of ZnO1-x Sx photocatalyst

The powder X-ray diffraction was performed using X-ray Diffractometer with nickel filtered
CuKα (λ = 1.54 Å) radiation and analysed using APD (Automatic Powder Diffraction) software. The
diffracted intensities were recorded from 30–80° 2θ angles. The 2θ (31.7, 34.4, 36.2, 47.5, 56.6, 62.8,
67.9) as well as the d values coincide with those of the standard hexagonal ZnO. No ZnS peaks were
observed on X-ray diffraction. This can be explained by the very small amount of ZnS. The SEM image of
S-doped ZnO powder also reveals the particles with different particle shapes, but with the average value
smaller than that of ZnO powder, and also with a larger amount of small particles. The reason may be due
to the presence of S during synthesis, which prevents or inhibits the particle growth of ZnO.

Figure 1. XRD patterns of ZnO1-x Sx powder Figure 2. SEM image of ZnO1-x Sx powder

III.3 Adsorption of methylene blue / phenol on ZnO1-x Sx photocatalyst

To find out if the material cans adsorb methylene blue, the dark experiment was carried out in the
absence of light for ZnO1-x Sx powder (1.0g) with 400ml of 10 ppm of methylene blue solution at pH = 6.0,
in 2 hour. The result points out that there is no adsorption of methylene on ZnO 1-x Sx photocatalyst. The
increase or decrease in absorbance value may be caused by error of instrument or suspended solid still
existing in samples.
III.4 Effect of radiation time
The effect of radiation time on percentage of methylene blue removal was described on Fig.3. One
gram of catalyst was used to degrade 400 ml of 10 ppm methylene blue solution at pH = 6.0, in 4 hours
and the dye removal was determined after every hour. As can be seen from Fig.3, after 1 hour % dye
removal of methylene blue was 46.9, and after 2 to 4 hours of irradation, the % of dye removal improved
just a little. The reactivity of ZnO1-x Sx is much higher in comparison with pure ZnO [8] (saturation after 2
hours), which may be resulted from the smaller particle surface. The nearly saturation after 1 hour is
possibly due to the chemical coverage of most of reaction sites on surface of material, which prevents
them from contact with the light source.
III.5 Effect of ZnO1-x Sx photocatalyst loading
Figure 4 describes the photocatalytic activity of various amounts of the catalyst loading, ranging
from 0.5 grams to 2.0 grams, in the same experiment conditions. The % dye removal increases with
increasing the catalyst loading, possibly because increasing the amount of catalyst will increase the
number of active sites on the photocatalyst surface. Consequently, this increases the number of hydroxyl,
and superoxide radicals. However, % dye removal of 2.0 gram loading is just slightly higher than that of
1.0 gram loading better. It can be explained due to the interception of the light by the suspension
especially at the high concentration of the suspension. For economic reason, 1 gram of catalyst loading
will be chosen for further experiments.
So lieu: Su dung so lieu nay de ve lai hinh.
Effect of Vis-radiation time on methylene blue degradation (Fig.3)
Time (hour) Dye removal, %
1.0
0 0.0
1 46.9
2 50.2
3 50.2
4 50.2

Table 13. Effect of ZnOxS1-x catalyst loading (Fig.4) ( Dye removal vs time, voi 4 catalyst
loading khac nhau)

Time (hour) Absorbance

Catalyst loading
0.5 1.0 1.5 2.0
(gram)
0 1.823 1.780 1.630 1.760
1 1.647 0.946 0.644 0.634
Dye removal, % 9.65 46.85 60.49 61.5

. Hinh Hinh

Figure 3. Effect of UV-radiation time on Figure 4. Effect of ZnO1-x Sx photocatalyst loading

photocatalytic of ZnO1-x Sx on % dye removal

III.5 Effect of pH on ZnO1-x Sx photocatalytic activity

pH of the dispersion may strongly influence the rate of reaction on semiconductor particle
surfaces since it relates to the surface-charge-properties of the photocatalyst. Experiments were carried out
at pH values of 4.0, 6.0, 8.0 and 10.0 using 1.0 gram of ZnO 1-xSx catalyst, and 10 ppm methylene blue
solution. The reaction took place in 1 hour, with Vis-lamp source. Results are shown in Table 1.

Table 1. Effect of pH on degradation of methylene blue

pH 4.0 6.0 8.0 10.0

% dye removal 29.4 40.8 47 37

As pH increased from 4.0 to 8.0, the removal percentage increased from 29.4 % to 47 %, while at
pH = 10.0 it drops down to 37 %. At too low or too high pH, ZnO may be dissolved as reactions: ZnO +
H+  Zn2+ + H2O; ZnO + 2OH- + H2O  Zn(OH)42- therefore % dye removals at pH 4.0 and 10 are lower.
At higher pH (6.0  8.0), there was an excess of OH− anions, which makes an easier photo-generation of
hydroxyl radicals. In addition, change in pH shifts the redox-potentials of valence and conduction bands,
which may affect interfacial-charge-transfer. The optimum pH range is therefore from 6.0 to 8.0.

III.6 Rate equation for degradation of methylene blue

For engineering purposes, it is useful to find out a simple and easy-to-use rate equation that fits the
experimental rate data. Since adsorption was not observed in the photocatalytic oxidation process, the
pseudo-first-order reaction equation was used to describe the photo-oxidation kinetics of methylene blue.

The pseudo-first-order reaction equation was introduced as follows: where C is the

methylene blue concentration at time t and k is the reaction rate. This equation can be integrated to give

the following form:

Ve lai hinh:

Table 9. ZnO rate equation for degradation of methylene blue

Time (min) 0 10 20 30 40 50 60
Abs 0.834 0.808 0.802 0.795 0.744 0.704 0.675
Time (min) 70 80 90 100 110 120
Abs 0.641 0.622 0.595 0.570 0.543 0.514

Figure 5. The rate equation of methylene blue degradation

The plot of ln(C/C0) versus time for the degradation of 5 ppm solution of methylene blue is given
in Figure 5. The first order rate equation shows a pretty good straight line for the data, which supports for
the assumption that the rate-determining step of the reaction involves hydroxyl radical formation or attack
[5]. The hydroxyl radical formation was supposed to follow these reactions: ZnO(h +vb) + H2O  ZnO +
HO* + H*; ZnO(h+vb) + OH-  ZnO + OH*, wherein ZnO(h+vb) represents the hole formed under light
interaction and located on the surface of ZnO. If the concentration of H 2O and OH- can be considered as
constants, the rate of reaction depends only on the hole (ZnO(h +vb) concentration. According to the above
kinetic model, the rate constant k was found to be 0.009 (greater than rate constant of pure ZnO, 0.003
[8]). In order to explain the enhanced visible-light activity, several possible mechanisms were proposed.
One of them is that with S in crystal structure of ZnO, new impurity level is introduced between the
conduction band and valence band of ZnO, and then the electrons can be promoted to the conduction band
from this impurity level.

III. 7 Effect of H2O2 in the photocatalysis:

Hydrogen peroxide is one of the most versatile, dependable and environmentally compatible
oxidizing agents. It therefore may have effects on the photocatalysis process. Different volumes of H 2O2
6M solution were added into the photocatalysis process using ZnO1-xSx. Results are given in Fig. 6.

Fig 6. Effect of different amount of hydrogen peroxide on the absorbance of Methylene blue

According to the data, it can be seen that H2O2 significantly increases the dye removal of MB, and
the increasing levels depend on the amount of H2O2 added. The higher the amount of H2O2, the higher the
dye removal. However, the material is dissolved in the solution. This can be explained by the fact that
H2O2 is a really strong oxidizer which creates an environment of OH -. Then, OH- accelerate the
decomposition of MB during the photocatalytical process: ZnO(h+vb) + OH-  ZnO + OH*.
However, ZnO1-x Sx is not stable in the basic solution, which leads to the destruction of the
material in the too basic environment. In conclusion, H 2O2 is not a good choice as the support reagent
despite its high-efficiency of dye removal of MB.

IV. Conclusion
For ZnO based materials, ZnO doped with S showed a greatest PCD efficiency on methylene blue
degradation under visible irradation. The particle size was also smaller than pure ZnO particle size. The
photocatalytic degradation efficiency has been found to increase with increasing the catalyst loading up to
a limiting value of 2.0 g, and with increasing pH, but when pH is higher than 8 the efficiency dropped
down. The photocatalytic reaction seems to follow the first order rate equation. This also supports the
assumption that the rate-limiting step may be involved in the hydroxyl radical formation and attack.
Furthermore, ZnO1-x Sx material presented an amazing photocatalytic activity under the irradiation of
visible light. This success will offer a cheap, potential, and effective treatment method of waste-water in
Vietnam.

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