Photocatalytic Degradation of Phenol using

Copper-doped Titanium Dioxide

Khrizelle Angelique L. Sablan
College of Engineering, University of the Philippines Diliman, Quezon City, Philippines
khayesablan@yahoo.com

ABSTRACT

The photocatalytic degradation of phenol was investigated using the copper-doped titanium dioxide as a catalyst
under visible light. An initial concentration of 20 ppm was used for the phenol. The concentration of the solution was
checked every 15 minutes for an hour and was analyzed using a high performance liquid chromatograph (HPLC). The
removal efficiency of the catalyst after an hour was 88.569 %.

Introduction
Titanium dioxide photocatalysis was first
discovered by Akira Fujishima in 1972 as a way to split
water into its constituent elements- hydrogen and
oxygen. Originally, photocatalysis was intended for
energy production purposes but it was discovered that
photocatalysis is also useful for water treatment. Since
then, most of the studies are focused on degrading
pollutants found in water particularly organics.
Photocatalysis works by the excitation of electrons by
light causing them to jump from the valence band to
the conduction band leaving behind a positive hole.
The hole then becomes a hydroxyl radical, a powerful
oxidizing agent. The electron then combines with the
oxygen from the water to produce a superoxide ion, a
reducing agent. The hydroxyl radical and the

superoxide ion react with the organic pollutants to

degrade them into less harmful compounds.
In Fujishimas experiment, he used the
anatase phase of titania as a photocatalyst. Anatase is
one of the three mineral forms of titania, the two others
being brookite and rutile, and is primarily the preferred
phase for photocatalysis due to its better charge carrier
mobility explained by the larger band gap but smaller
indirect band gap and the surface characteristics of the
phase.

Titanium dioxide has proven to be a good photocatalyst

but the activity is limited to the ultraviolet region. To
fully harness the light provided by the light source, it is
often wanted to extend the photocatalytic activity of the
catalyst to the visible light region. There are various
ways of achieving this but the usual way is to dope
titania with a metal. The metal lowers the band gap and
allows photocatalysis even in the visible spectra.
For this particular experiment, anatase titania
is doped with coppers to induce catalytic activity in the
visible light region. The material to be degraded is
phenol which is common in the environment as it is
found in most dyes and drugs. Furthermore phenol has
a lot of derivatives lead by chlorophenols which also
pose hazards to the environment and people.
The level of degradation will be measured
using an HPLC or high performance liquid
chromatography.
Chromatrography is a separation technique for
quantifying the amount of a component in a sample.
There are two important phases in the chromatograph
namely the stationary phase and the mobile phase.
The stationary phase is either a liquid or solid which is
usually nonpolar. The mobile phase varies for GC (gas
chromatrograph) and HPLC. Gas is used for GC and
liquid is used for HPLC. The separation of the phases
happens due to the difference in affinity of the
components to the mobile phase and stationary phase.
The more attracted the component is to the mobile
phase, the longer the distance it will travel in the

column. On the other hand if the component is more

attracted to the stationary phase, the distance would
be shorter. The mobile phase is chosen according to
the analyte and need not to be a single compound.
The main difference between a regular
chromatrograph and the HPLC is that the HPLC
applies a strong pressure unto the solvent pushing it
through the column at a faster rate.
Now, since we are with a solution of phenol
and water, HPLC is the best option for concentration
determination.

Materials and Methods

analysis and mobile phase setting should have been

set prior to analysis and during stabilization time which
is around 30 minutes. The pre-set parameters for
phenol testing were loaded and the samples were
automatically analyzed by the machine.

Results and Discussion

Calibration curves were generated using
different concentrations of standard solutions of phenol.
The area under the curve was used as a basis for the
calibration but the r-squared value was 0.9799.

Generation of a Calibration Curve

Concentration (ppm)

25

A calibration curve was determined by preparing

standard solutions of phenol in water with
concentrations of 1, 5, 12, 18, and 25 ppm. All the
solutions were prepared from a 10000 ppm stock
solution using micropipettors for measuring the amount
of phenol needed for each standard. After which, these
standards are mixed with deionized water in a
magnetic stirrer at a speed of 3000 rpm for a few
minutes. When
the
solutions
are
already
homogeneously mixed, samples are drawn for HPLC
measurements.

20

15

10

-4

y = 1.28502 x10 x - 0.11407

0
0

50000

100000

150000

200000

Area

Photocatalytic Activity Testing

Figure 1. Calibration curve based on the area under the curve
generated by the HPLC

A 20 ppm solution of phenol was prepared and an

HPLC analysis sample is taken from the initial sample.
The catalyst, which is Cu-doped TiO2, is weighed and
added to the phenol solution at a dosage of 3g/L and
the solution is illuminated using an LED lamp. A sample
for HPLC analysis is taken every 15 minutes for an
hour.

HPLC Analysis
The HPLCs mobile phase should be set and allowed
to stabilize for 30 minutes before use.
For each sample, 2 mL should be taken and filtered
using a syringe filter. The filtrate is directly stored in a
microvial and is subjected to HPLC analysis.
For the analysis, the microvials are placed inside the
designated area for samples and the parameters such
as the temperature and the proper time for HPLC

The photocatalyst is fast-acting as seen on the curves

in figures 2 and 3. After just fifteen minutes, the
removal efficiency is already around 50%. After an
hour, the concentration of phenol decreased to 2.411
ppm.

Conclusions
Percentage Removal of Phenol

100

80

60

40

20

0
0

10

20

30

40

50

60

70

Irradiation Time (min)

Figure 2. Phenol Percentage Removal vs. Irradiation Time (as calculated

based on the area)

The behavior of the system is comparable to the study

done by Chiou et. al in which they degraded phenol
with TiO2 doped with praseodymium which showed the
same results of degrading phenol within an hour at
concentrations lower than 25mg/L. This proves that the
catalyst used is competent for phenol degradation.

The photocatalytic activity of copper-doped titanium

dioxide was investigated for phenol degradation and it
showed excellent results for the concentration 20ppm
both in removal efficiency and time. The HPLC
measurements were used to determine the
concentration and it was found that the calibration
using the height of the peak is more linear therefore
more fit. It was used to determine the concentrations
of the solutions and the resulting efficiency is
99.044% which is comparable to other catalysts used
before.

References:
1)

Percentage Removal of Phenol

2)
100

80

3)

60

4)

40

20

0
0

10

20

30

40

50

60

70

Irradiation Time (min)

5)

Figure 2. Phenol Percentage Removal vs. Irradiation Time (as calculated

based on the area)

A possible mechanism for the photocatalytic

degradation of phenol is:

6 5 6 4 ()2 2 +
2
(1)
Upon calculation, the removal efficiency of the
photocatalyst based on the equation generated from
the area under the curve is 88.569% as shown in
figure 3. But from figure 4 removal efficiency of the
photocatalyst increased to 99.044% upon using the
equation generated from the height. The phenol is
almost completely removed from the system with just
an hour.

Chiou, C.H., Juang, R.S. (2007) Photocatalytic

degradation of phenol in aqueous solutions by
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Hazardous Materials 149 pp. 1-7
Fujishima, A., Rao, T.N., & Tryk, D. A.
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of Photochemistry & Photobiology C:
Photochemistry Reviews I pp. 1-21
Fujishima, A., Zhang, X. (2006) Titanium Dioxide
Photocatalysis: present situation & future
approaches C.R. Chimie 9 pp. 750-760
Kandiel, T.A., Robben, L., Alkaim A., &
Bahnemann, D. (2013) Brookite versus anatase
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