Research Article

Received: 4 November 2015 Revised: 15 February 2016 Accepted article published: 4 March 2016 Published online in Wiley Online Library: 5 April 2016

(wileyonlinelibrary.com) DOI 10.1002/jctb.4943

Enhanced photocatalytic degradation

of 4-chlorophenol and 2,4-dichlorophenol on
in situ phosphated sol-gel TiO2
Claudia Castañeda,a* Francisco Tzompantzi,a Ricardo Gómeza
and Hugo Rojasb

Abstract
BACKGROUND: Phosphated TiO2 photocatalysts with different phosphate content were synthesized by in situ phosphatation of
sol-gel TiO2 . H3 PO4 was used as a hydrolysis catalyst and as an anionic precursor. The solids were analyzed by several techniques
to determine the structural, textural and optical characteristics. The photoactivity of the materials was tested in the degradation
of 4-chlorophenol and 2,4-dichlorophenol, under UV irradiation.

RESULTS: XRD patterns showed that the presence of phosphate anions decreases the crystallite size without modification
of the anatase phase. Specific surface areas higher than the pristine TiO2 were obtained on the phosphated samples. The
presence of bidentate phosphates attached to the surface was identified by FTIR. The photoactivity of the materials tested in the
degradation of 4-chloropehol and 2,4-dichlorophenol showed notable improvement on phosphated TiO2 . The degradation rate
of the chlorophenolic compounds increases with the degree of substitution in the aromatic ring. Thus, the degradation rate of
2,4-dichlorophenol is higher than that of 4-chlorophenol. High efficiency in the degradation of the molecules after the recycling
of the photocatalysts was observed.

CONCLUSION: The modification in situ of TiO2 with low phosphate content promotes higher photocatalytic activity than that of
unmodified TiO2 and Degussa P-25 in the photodegradation of the chlorophenolic compounds.
© 2016 Society of Chemical Industry

Keywords: phosphated TiO2 ; sol-gel method; 4-chlorophenol photo-oxidation; 2,4-dichlorophenol photo- oxidation; photocatalysis

INTRODUCTION the characteristics of this oxide. Ortiz-Islas et al.17 reported that

Chlorophenols are widely used in several industrial processes, such
as fabrication of pesticides, insecticides and wood preservatives.
Since they have half-life times in water from 0.6 to 550 h and in
sediments up to 1700 h, they can be found in wastewater, ground-
water or soils.1,2 Advanced oxidation processes, among them pho-
tocatalysis, have been used in recent decades for the degrada-
tion of highly persistent and non-biodegradable pollutants in the
treatment of wastewater.
Titanium dioxide (TiO2 ) is considered a promising semiconduc-
tor in heterogeneous catalysis due to its interesting chemical
and physical properties. Its applications include use as catalytic
supports,3 photocatalysts,4,5 in the production of hydrogen,6,7 in
solar cell electrodes8,9 and gas sensors.10,11 As a photocatalyst, its
catalytic behavior depends on the particle size, surface area, poros-
ity, the presence of surface acid or basic groups, light intensity and
the nature of materials to be degraded.12,13
Modifications of TiO2 with anions have been reported to dimin-
ish the electron–hole recombination on the surface of titanium
dioxide.14 Thus, it has been reported that surface modification
of TiO2 by SO4 2− changes the band gap energy, increases the
surface area, decreases the crystallite size and improves the pho-
tocatalytic activity.15,16 On the other hand, the phosphatation of
2170
phosphate anions stabilize the titania in the anatase phase and
favor the development of Lewis acid sites. Connor et al.18 found
that the phosphates bind strongly on TiO2 as bidentate surface
species. Two species of orthophosphates adsorbed on titania
were reported by Gong:19 bridging bidentate surface complex
(TiO)2 PO2 with C2v symmetry and electrostatically adsorbed PO4 −3
ion with Td symmetry. Goswami et al.20 synthesized nanocrys-
talline phosphate doped TiO2 by the hydrothermal method and
they report that the incorporation of phosphates stabilized the
crystalline phase and caused a significant change in the TiO2 parti-
cle size and in its textural properties, which resulted in an increase
∗ Correspondence to: C Castañeda, Universidad Autónoma Metropolitana-
Iztapalapa, Depto. de Química, Área de Catálisis, Grupo ECOCATAL, Av. San
Rafael Atlixco No 186, México 09340, D.F. México.
Email: claudia.castaneda.mar@gmail.com
a Universidad Autónoma Metropolitana-Iztapalapa, Depto. de Química, Área de
Catálisis, Grupo ECOCATAL, Av. San Rafael Atlixco No 186, México 09340, D.F.
México
b Universidad Pedagógica y Tecnológica de Colombia, Escuela de Ciencias
Química, Grupo de Catálisis-UPTC, Avenida Central de Norte, Vía Paipa, Tunja,

TiO2 has been reported as an effective method for enhancing Boyacá, Colombia

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Enhanced photodegradation of 4-CP and 2,4-DCP on in situ phosphated sol-gel TiO2
in the photodegradation of fluorescein dye. Yu et al.21 reported
that phosphated mesoporous TiO2 presents higher photoactivity
than pure TiO2 and commercial P-25 in the oxidation of n-pentane.
They attributed the improvement in activity to the extended band
gap energy, increased surface area and the presence of Ti ions in
tetrahedral coordination. In contrast, Colón et al.22 modified TiO2
with different acid pre-treatments (nitric, sulfuric and phosphoric
acid). They found that the photoactivity in the degradation of phe-
nol decreased after treatment with phosphoric acid. This behavior
was attributed to the formation of pyrophosphate species on the
surface of the material.
With this in mind, to study the effect of phosphates on the pho-
tocatalytic properties of TiO2 , in the present work, phosphated
TiO2 semiconductors were prepared by in situ phosphatation
of sol–gel TiO2 and they were tested in the photodegradation
of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP), two
well-known pollutants. The phosphate anion was chosen because
of its strong adsorption on the TiO2 surface, its large negative
charge and its propensity to form hydrogen bonds. The photocat-
alysts were prepared varying the phosphate content (0.5, 1, 3 and
5 wt%). In addition, recycling of the best photocatalysts was per-
formed after each test to assess the stability of the phosphates on
the semiconductor surface.
EXPERIMENTAL
Photocatalysts synthesis
Phosphated titanium dioxide (PTi) was synthesized in situ via
the conventional sol–gel route. Titanium butoxide (Aldrich 98%)
and butyl alcohol (Aldrich 99.4%) were mixed in a glass flask.
Phosphoric acid (H3 PO4 , Baker Analyzed 84.8%) was used as a
hydrolysis catalyst and as an anionic precursor. H3 PO4 was added
in different amounts to the above mixture in order to obtain
TiO2 with different phosphate content (0.5, 1, 3 and 5% wt). The
mixture was maintained at 40∘ C under vigorous stirring for 2 h.
Distilled water was added to 50 mL of ethanol and the solution was
added dropwise to the reaction mixture to initiate the hydrolysis
process. The molar ratio of titanium butoxide:water:butyl alcohol
was 1:8:35, respectively. The resulting mixture was refluxed at 75∘ C
for 24 h under vigorous stirring. After, the gel obtained was rinsed
with distilled water and dried at 85∘ C for 24 h (Xerogel). Finally,
the powder was calcined at 400∘ C for 12 h with a heating ramp
of 0.5∘ C per min. The calcination temperature was chosen from
previous study of the optimal calcination conditions. The solids
were denoted as PTi0.5, PTi1, PTi3 and PTi5 corresponding the digit
with the phosphates percentages. For comparison, pure TiO2 was
synthesized using the same procedure with the addition of nitric
acid instead of H3 PO4 as hydrolysis catalyst. In addition, in some
cases, a commercial TiO2 (Degussa P-25) was used for comparative
behavior.
Characterization of photocatalysts
The semi-quantitative analysis of the phosphorus content in the
calcined photocatalysts was performed in a scanning electron
microscope JEOL 7600F, equipped with an energy dispersion X-ray
(EDX) spectrometer from Oxford instruments. From this informa-
tion, determination of the phosphate content in the materials was
obtained. XRD patterns and phase identification of the samples
were collected on a Bruker D2 Phaser diffractometer using Cu
K𝛼 radiation. The samples were scanned in the 2𝜃 range 20–80∘
with a step size of 0.02∘ and a counting time of 0.6∘ sec−1 . The
J Chem Technol Biotechnol 2016; 91: 2170–2178 © 2016 Society of Chemical Industry
www.soci.org
average crystallite size of powders (D) was determined from the
XRD patterns, according to the Scherrer equation (D = K 𝜆 / 𝛽
cos 𝜃), where K is a constant (shape factor, about 0.9), 𝜆 the
X-ray wavelength (1.5405 nm), 𝛽 the full width at half maximum
of the diffraction peak and 𝜃 the diffraction angle.23 The values
of 𝛽 and 𝜃 of anatase phase were taken from (1 0 1) diffrac-
tion planes. N2 adsorption-desorption isotherms at –196∘ C were
measured in a Quantachrome Autosorb 3B. Samples were previ-
ously evacuated at 250∘ C for 6 h. The Brunauer–Emmett–Teller
(BET) method was used to calculate the total surface areas of
the samples and the pore size distribution was determined using
the Brunauer–Joyner–Hallenda (BJH) method applied to the des-
orption branch. Diffuse reflectance spectra were obtained with a
Cary 100 UV–Vis spectrophotometer equipped with an integrating
sphere. The band gap energy values were calculated considering
the indirect allowed transitions of the TiO2 semiconductor from
the plot of the modified Kubelka–Munk function [F(R) × h𝜈]1/2 ver-
sus energy of absorbed light.24 The FTIR absorption spectra of the
samples were obtained with a Shimadzu IRAffinity-1 FTIR spec-
trometer in the wavenumber range 4000–350 cm−1 .
Photocatalytic degradation
To determine the optimum quantity of photocatalyst to per-
form the photocatalytic tests, degradations of 4-chloropenol (0.31
mmol L−1 ) using PTi1 sample were studied employing different
masses of semiconductor (25, 50, 100 and 200 mg). Study at three
calcination temperatures (300∘ C, 400∘ C and 500∘ C, 0.5∘ C min−1 , 12
h) was performed with the optimum quantity of catalyst.
Different solutions were prepared with molar concentra-
tions of 0.31 mmol L−1 4-chlorophenol (Sigma 99%) and
2,4-dichlorophenol (Aldrich 99%), respectively. For each test,
50 mg of the calcined photocatalyst were added to 200 mL
of aqueous solution in a glass reactor. The suspension was
stirred at 700 rpm in the dark for 30 min with air flow, to ensure
adsorption–desorption equilibrium of the test molecule. Subse-
quently, the solution was irradiated with UV light using a Pen Ray
Power Supply lamp, 𝜆 = 254 nm, 4.4 mW protected by a quartz
tube, immersed in the solution. Degradation of the pollutants
was monitored by analyzing an aliquot sample every 30 min and
following the absorption band of the test molecule (278 nm for
4-chlorophenol and 283 nm for 2,4-dichlorophenol) using a UV-Vis
spectrophotometer Cary 100. Total organic carbon (TOC) was also
quantified (Shimadzu TOC-V CSN).
RESULTS AND DISCUSSION
Characterization of the photocatalysts
Energy dispersion X-ray spectroscopy
Semi-quantitative analysis of the phosphorus content using EDX
was made for the PTi1 and PTi5 photocatalysts. For comparison,
EDX analysis for TiO2 was performed. The spectra of the samples
studied are presented in Fig. 1, where the characteristic signals for
titanium (Ti) and oxygen (O) at 4.50 and 0.52 keV, respectively, can
be observed. The distinctive signal for phosphorus (2.01 keV) is
present for both phosphated samples and its intensity is greater
for PTi5.
From these results, the phosphate content was estimated at
1.65% and 6.45% for the PTi1 and the PTi5 samples, respectively.
The anion percentages are higher in the calcined material due to
the loss of water and alcohol during activation at 400∘ C. Similar
results were reported by Pattnayak and Parida25 and Samantaray
2171
and Parida.26
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 www.soci.org C Castañeda et al.

Figure 1. EDX spectra of the TiO2 , PTi1 and PTi5 samples, calcined at 400∘ C.

(101)
(004) (200) (105) (204) Table 1. Textural and structural parameters of the calcined photo-
PTi5 catalysts at 400∘ C
Intensity (a.u.)

PTi3
Surface Pore
PTi1
Eg area volume Crystallite
Sample (eV) (m2 g−1 ) Pore size (Å) (cm3 g−1 ) size (nm)
PTi0.5

TiO2 TiO2 3.01 126 56 0.23 10.1

PTi 0.5% 3.08 185 34 0.23 7.3
20 30 40 50 60 70 80 PTi 1% 3.11 198 34 0.22 7.1
2 (degrees) PTi 3% 3.09 269 34 0.24 5.6
PTi 5% 3.10 285 34 0.26 5.8
Figure 2. X-ray diffraction patterns for the TiO2 and phosphated TiO2
samples, calcined at 400∘ C.

Powder X-ray diffraction
The diffraction patterns of the phosphated TiO2 and unmodified
TiO2 are shown in Fig. 2. The materials calcined at 400∘ C exhibit
peaks located at 2𝜃 angles of 25.4∘ (101), 37.9∘ (004), 48.1∘ (200),
54.5∘ (105), 62.8∘ (204) and 75.2∘ (215), which correspond to the
anatase phase (JCPDS 84-1286). The rutile phase was not observed
in any of the phosphated and reference sol–gel TiO2 samples. This
indicates that the phosphate does not modify the TiO2 crystalline
phase.
Upon increasing the phosphate content, the peak intensity for
anatase (2𝜃 = 25.4∘ ) gradually decreases and the half-width of
the diffraction peak is broadened, indicating the formation of
smaller TiO2 crystallites. The average crystallite size was calculated
using the Scherrer equation from the broadening of this peak,
corresponding to the plane (101) (Table 1). As can be observed,
the crystallite size became smaller as the phosphate content
increased. This result suggests that the phosphatation inhibits the
2172
Nitrogen adsorption
Figure 3(A) shows the adsorption–desorption isotherms for the
modified samples and reference TiO2 calcined at 400∘ C. All the
samples exhibited the type IV nitrogen isotherm, which is char-
acteristic of mesoporous materials.27 The H2 type hysteresis was
observed in the four samples which are often referred to as
an ‘ink-bottle’ pore. The existence of the hysteresis loop in the
isotherm is due to the capillary condensation of nitrogen gas
occurring in the mesoporous cavity.28 The phosphatation in situ
of the TiO2 semiconductor induces a displacement toward lower
relative pressures in the desorption process, suggesting a change
in the mesoporosity of the material. The BET specific surface area,
pore size and pore volume of the phosphated samples and the
unmodified TiO2 are listed in Table 1. The modification of TiO2
with phosphates is beneficial to obtain solids with larger sur-
face areas, which could be related with the hydroxylation extent
of the material generated during the gelification of the titanium
butoxide in presence of phosphoric acid. The monomodal pore

growth of the TiO2 crystallites. size distribution (Fig. 3(B)), derived from the desorption branch of

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(A) (B)
3.5

Desorption Dv (logd)/(cm3/g)
PTi5 TiO2

Adsorbed Quantity (a.u.)

PTi3 3.0
PTi0.5
2.5 PTi1
PTi1
PTi3
2.0 PTi5
PTi0.5
1.5
TiO2
1.0
0.5
0.0
0.0 0.2 0.4 0.6 0.8 1.0 20 30 40 50 60 70 80
P/Po Pore Size (Å)

Figure 3. (A) Nitrogen adsorption–desorption isotherms, and (B) pore size distribution for the TiO2 and phosphated TiO2 samples, calcined at 400∘ C.

the isotherms indicates a decrease in the pore size of the phos- (A)
phated materials in relation to TiO2 ; however this property does 1.6 269 330 TiO2
not change with the increase of the anion content. Thus, the 225
1.4 PTi0.5
phosphatation process probably promotes a pore blocking, which 1.2 PTi1
PTi3
causes a change in the mesoporosity of the TiO2 semiconductor. 1.0 PTi5

F(R)
0.8
UV-Vis absorption and diffuse reflectance spectroscopy 0.6
411
To observe the optical response of the phosphated TiO2 , the UV-Vis 0.4
absorption spectra were recorded in a wavelength range between 0.2
190 and 500 nm (Fig. 4(A)). A strong absorption band between 300
0.0
and 400 nm was observed. This absorption band is characteristic 200 300 400 500
of O2p → Ti3d transitions in the tetrahedral symmetry. The two
Wavelength (nm)
shoulders that appear from approximately 190–240 and 250–300
nm, present in both the unmodified TiO2 as well as the phosphate (B)
3.0
TiO2 , may be associated with bulk crystals.24
Unmodified TiO2 and phosphated materials show clear ultra- 2.5
violet absorption. The unmodified TiO2 powder exhibits an 2.0
1/2

absorption band edge at 411 nm. However, phosphated samples

[F(R) x hv]

present a blue-shifted in comparison with the optical response of 1.5

unmodified TiO2 . This behavior is attributed to the well-known 1.0 TiO2
quantum-size effect for semiconductors. UV-visible absorption PTi0.5
band edge is a direct function of the crystallite size for diameters 0.5 PTi1
PTi3
less than 10 nm.12 The increase in the phosphate content causes 0.0 PTi5
a decrease in the crystallite size and hence an absorption toward
2 3 4 5 6
lower wavelengths. The band gap energy values (Eg) calculated
from the modified Kubelka–Munk plot (Fig. 4(B)) were obtained Energy (eV)
considering indirect transitions of the semiconductors (reported Figure 4. (A) UV-Vis spectra for the TiO2 and phosphated TiO2 sam-
in Table 1). The estimated band gap energy for TiO2 is 3.01 eV ples, calcined at 400∘ C, and (B) Kubelka–Munk modified spectra for the
and a slight increase between 3.08 and 3.11 eV was observed as a photocatalysts.
result of the phosphatation of the material.
was detected at 1670 cm−1 .30 In the modified photocatalysts, these
Fourier transform infrared spectroscopy latter signals are broader, indicating that the phosphatation of
FTIR spectra of the phosphated TiO2 photocatalysts were used to TiO2 increases the amount of surface-adsorbed water and hydroxyl
analyze the structure of the materials (Fig. 5(A)–(C)). In the region groups. This behavior is in agreement with the larger surface
of low energy 500–722 cm−1 the stretching vibrations of Ti–O areas observed for the phosphated samples. A band at 1050 cm−1
and Ti–O–Ti bonds, typical of titanium dioxide,29 can be seen in appears in the phosphated TiO2 materials and is attributed to the
Fig. 5(A). phosphate in a bidentate state of ligation; 31 the band at 2329
An amplification of the infrared spectrum was performed in cm−1 is assigned to vibration of the P–OH bond which increase
order to elucidate better the vibration bands (Fig. 5(B)). As can be proportionally with the phosphate content.32 A signal at 1125
observed, a wide band at 3243 cm−1 corresponding to adsorbed cm−1 associated with a Ti–O–P bond, with P replacing Ti4+ in the
water (Ti-OH2 ) is observed in all samples. The signal at 1510 cm−1 TiO2 lattice, was not observed.33
is assigned to the combination of the symmetric and asymmetric The infrared spectra of the photocatalysts after use in the
stretching modes of water molecules adsorbed on the TiO2 surface degradation reactions can be observed in Fig 5(C). The vibration
2173

and the band related with the flexion vibration of H–O groups bands at 1050 cm−1 attributed to the phosphates are still present;

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 www.soci.org C Castañeda et al.

(A) (B)
1050
PTi5 3243 2329 1670
PTi5 1510
PTi3

Absorbance
Absorbance
PTi1 PTi3
PTi1
PhTi0.5
TiO 2 PTi0.5
TiO
2

3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) Wavenumber (cm-1)

(C)
1050
2329
PTi5
Absorbance PTi3

PTi1

PTi0.5

TiO 2

3500 3000 2500 2000 1500 1000

Wavenumber (cm-1)

Figure 5. (A) FTIR spectra for the TiO2 and phosphated TiO2 samples, calcined at 400∘ C, (B) enlargement of the infrared spectrum, and (C) FTIR spectra for
used photocatalysts in the degradation reactions.

confirming the stability of the phosphates bonded to the surface were calcined at three temperatures (300∘ C, 400∘ C and 500∘ C)
of TiO2 during the photodegradation reactions. As expected, the and tested in the photoreaction during 3 h. As can be seen in
bands at 1510 and 1670 cm−1 were more intense due to the hydra- Fig. 6(B), degradation of the contaminant using the PTi1 sample
tion suffered by the solid in contact with the reactant aqueous calcined at 300∘ C is not efficient; however, when the reaction is
solutions. carried out with the semiconductor calcined at 400∘ C, the photo-
catalytic activity dramatically improves and a degradation of 68%
was attained after 210 min. Increasing further the calcination tem-
Photocatalytic degradation
perature to 500∘ C notably the photoactivity was suppressed and
Optimization of the photocatalyst quantity and of the calcination
temperature for the photocatalytic test only 29% of the molecules were oxidized.
Further photoactivity tests of the samples were performed using
In order to determine the optimal mass of solid to perform the
50 mg of the semiconductor calcined at 400∘ C in the degradation
photocatalytic test, the degradation of 200 mL of a solution of
of 4-clorophenol and 2,4-diclorophenol.
4-clorophenol was performed using different quantities of PTi1
(25, 50, 100 and 200 mg). In Fig. 6(A) it can be seen that 50 mg
of semiconductor were sufficient to degrade the contaminant; at Degradation of 4-cholophenol
higher solid contents the reaction remains constant and diffusion The photodegradation capacities of the phosphated titania
effects, such as the light intensity and mass transfer diffusion are were tested with two important pollutants, 4-chlorophenol
evident. and 2,4-dichlorophenol (2,4-DCP). The contaminant concen-
On the other hand, to determinate the most favorable calcina- tration was monitored by UV-Vis spectroscopy applying the
tion temperature for the photodegradation of 4-CP, 50 mg of PTi1 Beer–Lambert law.

(A) (B)
70
4-CP photodegradation (%)

1.8
1.7 60
K x 10-6 (M min-1)

1.6 50
1.5 40
1.4 30
1.3 20
1.2 10
1.1 0
25 50 75 100 125 150 175 200 300 400 500
Mass Photocatalyst (mg) Calcination temperature (°C)
2174

Figure 6. (A) Effect of the mass, and (B) effect of the calcination temperature of the PTI1 photocatalyst in the photodegradation of 4-CP after 3 h reaction.

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3.5 0min
Adsorption
30min
3.0 60min
90min
2.5

Absorbance
120min
150min
2.0 180min

1.5
1.0 283
0.5
0.0

200 250 300 350

Figure 7. UV absorption spectra of the degradation of 4-CP using the PTi1 Wavelength (nm)
sample.
Figure 9. UV absorption spectra of the degradation of 2,4-DCP using the
PTi1sample.
70
4-CP photodegradation (%)

60
50 90

2,4-DCP photodegradation (%)

40
80
70
30
60
20
50
10
40
0% 0%
0 30
TiO2 PTi0.5 PTi1 PTi3 PTi5 P-25
20
Figure 8. Photocatalytic degradation of 4-CP for the studied photocatalysts
after 3 h reaction. 10
0
TiO2 PTi0.5 PTi1 PTi3 PTi5 P-25

Figure 7 illustrates the changes in the UV absorption spectra of Figure 10. Photocatalytic degradation of 2,4-DCP for the studied photo-
4-CP at different irradiation times. 4-chlorophenol presents strong catalysts after 3 h reaction.
absorption bands in the ultraviolet region with wavelengths at
195, 223 and 278 nm. As the reaction progresses, the characteristic
peaks of 4-CP at 𝜆 = 278 nm and 𝜆 = 223 nm decreased in height.
An increase in the absorbance is observed near 250 nm and
can be attributed to the formation of intermediates, especially O
benzoquinones. 34 In addition, the absorption spectrum displays O
a bathochromic shift towards 285 nm, indicating the formation of P
O
intermediary species with a different cromophore group, such as O
hydroquinone.35 This last peak (285 nm), assigned to the n → 𝜋*
transitions of C–Cl bond, decreases rapidly because this bond
is the most reactive. Finally, the absorption bands located near
190 and 230 nm are assigned to the 𝜋 → 𝜋* transitions of the
aromatic group.36 These bands present a significant decrease with
Ti

irradiation time.
As can be seen in Fig. 8, the TiO2 , PTi0.5, PTi1 photocatalysts and
Degussa P-25 degraded in nearly 45, 62, 68 and 46%, respectively.
It should be noted that the activity of the phosphated sample at
1% is higher than that of the reference sol–gel TiO2 and P-25 in
the degradation of 4-CP. Probably the small crystallite size present
in PTi1 facilitates surface charge transfer, which decreases the
recombination of electron–hole pairs and improves the pho-
tocatalytic activity.37 However, at high phosphate content the
photoactivity was inhibited. Although the PTi3 and PTi5 photo-
catalysts present larger surface areas and a smaller average crystal
size, the elevated PO4 3− content could block the active sites on Figure 11. Illustrative design explaining the role of phosphates in
the TiO2 surface diminishing the interaction of the pollutant with chlorophenols photodegradation.
2175

the semiconductor.

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 www.soci.org C Castañeda et al.

(A) (B)
80 40
70

Residual TOC (%)

Residual TOC (%)

60 30
50
40 20
30
20 10
10
0 0
TiO2 PTi1 P-25 TiO2 PTi1 P-25

Figure 12. Residual TOC in the photodegradation of (A) 4-CP and (B) 2,4-DCP using TiO2 , P-25 and PTi1 samples after 3 h reaction.

(A) (B)
0.0004
1.45 x 10-6 M min-1 0.0003
1.60 x 10-6 M min-1
Concentration [M]

Concentration [M]
1.27 x 10-6 M min-1
0.0003 1.59 x 10-6 M min-1
0.0002

0.0002
PTi1 PTi1
TiO2 0.0001
TiO2
0.0001 P-25 1.77 x 10-6 M min-1 P-25 1.87 x 10-6 M min-1

0 30 60 90 120 150 0 30 60 90 120 150

Time (min) Time (min)
Figure 13. Zero-order kinetics for the photodegradation of (A) 4-CP and (B) 2,4-DCP using the PTi1sample.

90 more slowly, which indicates that the breakage of C–Cl bonds is

Cycle 1
80 Cycle 2
preferred.
Photodegradation (%)

70 Figure 10 presents the 2,4-DCP photodegradation percentages

60
50
40
30
20
10
0
4-CP
Figure 14. Recycling of the PTi1 photocatalyst for the degradation of 4-CP
and 2,4-DCP.
Degradation of 2,4-dichlorophenol
The UV absorption spectra of 2,4-DCP degradation at different
irradiation times using PTi1 is shown in Fig. 9. The absorption
band at 283 nm is associated with the 2,4-DCP. When the pol-
lutant is placed in contact with the photocatalyst, without UV
irradiation, a decrease in the absorbance is observed. This behav-
ior implies strong adsorption of the organic compound on the
surface of the solid. When the suspension is irradiated, an increase
in the absorbance is evidenced. This could be indicating release
of the pollutant from the surface of the photocatalyst. As the
photocatalytic reaction progresses, the absorption band at 283
nm (n → 𝜋* transitions) gradually decreases, which is a result of
the photo-oxidation of the compound. The 203 nm band asso-
2176
obtained by the studied photocatalysts. In the presence of TiO2
and phosphated photocatalysts (0.5, 1, 3 and 5%), oxidations of
70, 77, 83, 62 and 39% were achieved, respectively, in the same
reaction time. When the test was performed with Degussa P-25,
nearly 71% of molecules were degraded.
Similar to that observed in 4-chlorophenol photodegradation,
a low level of phosphates, particularly the PTi1 solid shows the
higher photocatalytic activity than reference sol–gel TiO2 and
2,4-DCP Degussa P-25. On the other hand, an increase in the phos-
phate content above 3% negatively affects the activity. In a
similar manner to that proposed for 4-chlorophenol, the high
anion content on the surface could block the substrate adsorp-
tion and transfer between the hole and the substrate can be
hindered.
From the results obtained in this study, the phosphates anchored
to the surface of TiO2 could obstruct the recombination of holes
and electrons. The negative charge of the phosphates generates a
positive partial charge on titanium which attracts the photogener-
ated electrons to the surface. The electrons reduce the oxygen to
form superoxide radicals and the photogenerated holes migrate
toward the surface to oxidize the organic pollutant. An illustration
of the role of the phosphates on the surface of TiO2 is shown in
Fig. 11.
Determination of the mineralization of the organic compounds
was evaluated by measuring the total organic carbon (TOC) of the
irradiated solution. Figure 12(A) and (B), respectively, presents the
residual TOC results obtained after 3 h reaction, in the degradation

ciated with 𝜋 → 𝜋* transitions of the aromatic ring disappears of 4-CP and 2,4-DCP using TiO2 , PTi1 photocatalysts and Degussa

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Enhanced photodegradation of 4-CP and 2,4-DCP on in situ phosphated sol-gel TiO2
P-25. The TOC measurements confirm that the PTi1 sample is more
efficient than both TiO2 and Degussa P-25 for mineralization of the
organic pollutants. Comparing the behavior of the two molecules,
it can be seen that the oxidation of 2,4-DCP was greater than that
obtained for 4-CP. This result indicates that the total mineralization
of chlorophenols is greater with more chlorine substitution in the
aromatic ring.
From the photoactivity data as a function of time for the PTi1
sample, TiO2 and Degussa P-25, the kinetic behaviors of the pho-
todegradation reactions were analyzed. The photodegradations of
4-CP and 2,4-DCP follow zero-order kinetics, represented in Fig. 13.
The 4-CP and 2,4-DCP degradation rates were higher with the
phosphated photocatalyst PTi1 than with TiO2 and Degussa P-25.
The apparent rate constant for the degradation of chlorophenols
increases with the number of chlorides in the molecule. This obser-
vation is in agreement with the results reported by Hugül et al.38 in
the decomposition of 2-CP, 2,4-DCP and 2,4,6-TCP by UV/hydrogen
peroxide oxidation. A similar kinetic order was reported by
Sivalingam et al.39 in the photodegradation of substituted phenols
using solution combustion synthesized TiO2 (pentachlorophe-
nol > trichlorophenol > dichlorophenol > p-chlorophenol).
The behavior observed in this work can be explained by the
strong positive mesomeric effect (+M-effect) of the − OH group
of the aromatic ring, where it is expected that the major points
of attack by . OH radicals will be the positions of high electron
density. Thus, para- and ortho- positions are the most active in
photodegradation of chlorophenols.40 For this reason, 2,4-DCP
was more vulnerable to hydroxyl radical attack, evidenced by the
greater reactivity compared with that of 4-chlorophenol.
An important parameter to assess the application of photocat-
alysts in the degradation of organic pollutants is the recycling
experiment. Favorably, PTi1 was recycled after being recovered
from the solution and subjected to heat treatment at 400∘ C for 3 h.
This experiment was made three times to analyze the reproducibil-
ity and the statistical values obtained are reported as error bars in
Fig. 14. The photocatalytic behavior of the calcined and recycled
samples in the degradation of 4-CP and 2,4-DCP after 3 h reaction
is shown in Fig. 14. As can be observed, the photocatalytic degra-
dation of 4-CP decreased from 68% to 64% and the oxidation of
2,4-DCP decreased from 83% to 80%. The results confirm that PTi1
can be employed as a promising reusable material for removal of
chlorophenols.
CONCLUSIONS
The in situ modification of TiO2 with phosphate anions promotes
the formation of solids with high specific surface areas and small
crystallite size. PTi1 sample was more photoactive than reference
sol–gel TiO2 and Degussa P-25 in the degradations of 4-CP and
2,4-DCP. On samples with low phosphate content (PTi 1 wt%), a
favorable degradation of organic pollutants such as chlorophenols
was obtained, while for samples with phosphate content of 3
wt% or higher a possible blockage of the TiO2 surface by the
phosphate anions could cause a decrease in the photoactivity.
The degradation rate increases with substitution of chlorine into
the phenolic ring; therefore, the oxidation of 2,4-dichlorophenol
is greater than that of 4-chlorophenol. The photocatalysts can be
easily recycled and the phosphates bound to the surface of TiO2
are stable, resulting in an acceptable degree of activity retention
upon reuse.
J Chem Technol Biotechnol 2016; 91: 2170–2178 © 2016 Society of Chemical Industry
www.soci.org
ACKNOWLEDGEMENT
The authors are grateful to CONACYT for the scholarship num-
ber 287123 and for the financial support grants 194451 Materiales
nanoestructurados para fotocatálisis and FOINS/75/2012 Fotosín-
tesis artificial.
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