Computational Materials Science 107 (2015) 48–53

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Computational Materials Science

journal homepage: www.elsevier.com/locate/commatsci

Screening of factors influencing the photocatalytic activity of TiO2:Ln

(Ln = La, Ce, Pr, Nd, Sm, Eu and Gd) in the degradation of dyes
E.G. Villabona-Leal a,1, J.P. López-Neira a,1, J.A. Pedraza-Avella b, Elías Pérez c, Octavio Meza d,⇑
a
Posgrado en Ciencias Aplicadas, Facultad de Ciencias, Universidad Autónoma de San Luis Potosí, Av. Salvador Nava, 078290 San Luis Potosí, Mexico
b
Universidad Industria de Santander – UIS, Grupo de Investigaciones en Minerales, Biohidrometalurgia y Ambiente – GIMBA, Sede Guatiguará, Km. 2 vía El Refugio,
Piedecuesta, Santander, Colombia
c
Instituto de Física, Universidad Autónoma de San Luis Potosí, Álvaro Obregón #64, 78000 San Luis Potosí, Mexico
d
Instituto de Física, Ing. Luís Rivera Terrazas, Benemérita Universidad Autónoma de Puebla, Apartado Postal J-48, Puebla 72570, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we analyzed the photocatalytic activity of TiO2:Ln (Ln = La, Ce, Pr, Nd, Sm, Eu and Gd) sys-
Received 7 October 2014 tems in the degradation of two organic dyes by means of a probabilistic approach to screen the factors
Received in revised form 6 May 2015 influencing their photocatalytic activity. The photocatalytic properties were described by six responses
Accepted 15 May 2015
(crystallite size, band gap energy, visible light absorption, specific surface area, zeta potential and photo-
catalytic conversion) as a function of lanthanide type (seven elements), lanthanide concentration (two),
pH level (two) and dye type (methyl orange and crystal violet). We analyzed 140 experiments using the
Keywords:
analysis of variance (ANOVA) method. The results show that band gap energy and specific surface area
Photocatalysis
Analysis of variance
exhibited behavior that depended on the atomic number of the element used. However, visible light
Crystal violet absorption was not modified by the type of lanthanide element or its concentration in the range studied
Methyl orange (0.1 and 0.3 wt.% lanthanides/TiO2 ratio), and the zeta potential depended mainly on pH. Photocatalytic
Lanthanides conversion depended on pH, dye type and doping element. The experimental factorial design of the pho-
TiO2 tocatalytic system allowed us to find the best conditions for enhancing the degradation of these two dyes.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction
The discharge of dye-contaminated wastewater by different
types of industry seriously damages microorganisms, aquatic life
and humans [1]. Due to their complexity, a variety of
non-biodegradable and highly water-soluble dyes are difficult to
remove from wastewater by conventional methods [2].
TiO2-based photocatalysts are commonly used agents for the
decomposition of organic pollutants present in wastewaters from
various industries, factories, laboratories, etc., which represent a
serious problem for the environment [3–5]. More recently, hybrid
materials, such as doped or decorated TiO2 particles, have become
available to improve this photocatalysis process.
The photocatalytic oxidation process consists of the activation
of particles of semiconducting materials, such as the abovemen-
tioned titanium dioxide, which is excited with light having energy
greater than or equal to the difference between the valence band
⇑ Corresponding author. Tel.: +52 (222) 229 5610x2045; fax: +52 (222) 229 56
11.
E-mail address: omeza@ifuap.buap.mx (O. Meza).
1
Both authors contributed equally to this work.
and the conduction band (ht P Eg) [6,7]. This generates an exciton
or electron–hole pair within the semiconductor; these migrate to
the material’s surface and initiate a series of redox reactions. The
final outcome of these events is the oxidation of pollutants that
are present in the reaction medium. The mean lifetime of an elec-
tron–hole pair is short (30 ± 15 ns) [7]. The incorporation of lan-
thanide ions onto the TiO2 surface increases the lifetime of
charge carriers due to energy transfer phenomena between the
host and dopant ions in TiO2 [8,9].
Experimentation has been used to understand and/or improve
these catalytic systems; however, there may be a large number
of factors, but usually only a handful of them are important or sig-
nificant. A screening experiment is therefore important to identify
the influential factors. Once these factors are identified, the next
stage of the investigation focuses on the elucidation and optimiza-
tion of the relationship between the response and the factors. The
experiments to screen the factors are usually performed at the
early stages of a design project when many of the factors initially
considered have very little or no effect on the performance. To con-
duct the experiment, the control factors and noise factors should
be identified [10–12]. The effects of these factors are then investi-
gated at different levels. As the number of levels increases for each

http://dx.doi.org/10.1016/j.commatsci.2015.05.014
0927-0256/Ó 2015 Elsevier B.V. All rights reserved.
 E.G. Villabona-Leal et al. / Computational Materials Science 107 (2015) 48–53 49

control and noise factor, the number of combinations becomes
large and unmanageable. Therefore, running experiments with all
these combinations becomes uneconomical and time consuming.
In this work, we present a screening of factors that may influ-
ence the photocatalytic properties of TiO2–Ln systems. We ana-
lyzed six responses: crystalline size, band gap energy, visible
light absorption, surface area, zeta potential and photocatalytic
conversion. These responses were studied as a function of four fac-
tors: (A) seven lanthanide elements, (B) two lanthanide concentra-
tions, (C) two pH levels and (D) two dye types. We used dyes with
opposite electrical natures, i.e. crystal violet is a cation at both
reaction pH levels, while methyl orange is an anion under natural
conditions. These dyes also possess different electrical characteris-
tics than the TiO2–Ln system, as well as chemical stability and
minor discoloration when exposed to light for a long period of
time. As a result we find that photocatalytic activity of all doped
samples does not depend on the type of Ln, nor on its concentra-
tion, nevertheless if we compare the doped and the undoped sam-
ples, the doped samples have better photocatalytic activity (for any
Ln). This is because the addition of lanthanides inhibits crystal
growth, and this increases SSA. We are confident that our statisti-
cal analysis will help the understanding of the role of each factor
studied in the photocatalytic activity.
2. Experimental
TiO2–Ln powders were synthesized and characterized as previ-
ously reported [13]. Briefly, these systems were obtained by the
sol–gel method using titanium n-butoxide as the precursor. The
materials were doped with lanthanides (Ln = La, Ce, Pr, Nd, Sm,
Eu and Gd) by the addition of lanthanide nitrate as a precursor salt.
Lanthanide aqueous solutions were prepared by stoichiometric
addition to obtain 0.1 and 0.3 wt.% Ln on the TiO2. The obtained
gel was dried in an oven at 120 °C for 12 h and finally annealed
at 500 °C for 4 h using a heating rate of 2 °C/min.
Photocatalytic tests were carried out in a microscale photoreac-
tor equipped with a 5.5 W low-pressure cold-cathode mercury
lamp (UVP Pen-Ray 90-0012-01). In a typical experiment [13–
15], 10 mg of the photocatalyst was added to 10 mL of a solution
containing 35 ppm of methyl orange (mo) or crystal violet (cv);
the pH was adjusted to 5.6 or 3.1 with HCl. The suspension was
kept in the dark under magnetic stirring for 30 min. After 60 min
under UV–vis light, the suspension was filtered and the dye con-
centration was determined by UV–vis absorption spectroscopy
using a Hewlett Packard 8453 spectrophotometer.
X-ray diffraction patterns were collected using a Siemens D500
diffractometer with a Cu tube with Ka radiation at 1.5405 Å, scan-
ning in the 20–70° 2h range with increments of 0.021 and as wept
time of 1 s. Nitrogen adsorption isotherms were measured at liquid
nitrogen temperature (77 K) using a Micromeritics ASAP 2020
spectrometer in order to determine the specific surface area
(SSA) of the photocatalysts by BET. Before the measurements, the
samples were outgassed at 350 °C for 2 h [16]. Electrophoretic
measurements of zeta potential (Zp) at different pH values were
performed using a Zeta-Meter 3.0+ unit equipped with a molybde-
num anode and a platinum cathode [17,18]. All the experiments
(or measurements) are summarized in Table 1.
3. Results and discussions
Analysis of variance (ANOVA) is an effective analysis tool that
allows the simultaneous comparison of factors to determine if they
are identical or significantly different. ANOVA tell us if the variance
in our data is significant and measures that significance [19,20].
The experimental results are organized in three ANOVA designs
(see Table 1). In the first ANOVA, we analyzed four responses: crys-
tallite size, band gap energy, visible light absorption and surface
area as a function of two factors: (A) seven lanthanide elements
and (B) two concentrations, i.e. 0.1 or 0.3 wt.% Ln. The number of
experiments (or measurements) in this first ANOVA was
4  7  2 = 56. The average crystallite size d was estimated using
the Scherrer equation and diffraction spectra (see Fig. 1): d = K
k/b cos h, where b is the full width at half maximum (FWHM) of
the anatase peak (28.17°). The band gap energy (Eg) was estimated
from the spectra in percent reflectance mode by means of the
Kubelka–Munk function: F(R) = (1R)2/2R, where R is the diffuse
reflectance, through the corresponding Tauc plots: (F(R)  E)1/2
and E is the energy of absorbed light, by extrapolation of the
straight line to the abscissa [21–23]. The visible light absorption
(VLA) was calculated from the spectra of absorbance mode by
numerical integration in the range of 400–700 nm [24,25]. All

Table 1
It shows the experimental design with related factors and responses. Four factors: (A) lanthanide type, (B) concentration, with – and + equal to 0.1 and 0.3 wt.%, (C) two pH
conditions, with – and + equal to 3.1 and 5.6 and (D) two dyes, with – and + equal to crystal violet and methyl orange, respectively. Five responses: energy gap, UV–visible
absorption, surface area, zeta potential and photocatalytic conversion.

D
 +
C
 +  +  +
A B Size (nm) Eg (eV) VLA SSA (cm2/g) Pz Conversion%
La  8.4 3.23 33.99 90 9.5 18.7 34.1 34.9 29.5 14
Ce  8.4 3.18 32.06 98 9.5 23.9 28.5 38.5 35.9 13,5
Pr  8.4 3.25 29.45 99 7.8 27.3 20.8 41.3 51.9 8,2
Nd  8.4 3.22 27.99 99 7.8 24.2 22.3 38.5 57.1 11,1
Sm  8.4 3.18 25.59 106 7.8 25.0 27.5 38.4 46.7 12
Eu  8.3 3.18 31.16 102 9.5 20.4 26.2 43.5 45.9 15,4
Gd  9.9 3.17 32.62 111 7.7 16.3 35.2 45.0 39.2 17,6
La + 7.2 3.15 31.70 119 25.8 25.8 30.3 40.9 40.2 13,5
Ce + 9.0 3.13 53.96 109 14.5 18.2 19.7 40.1 50.2 17,3
Pr + 8.4 3.19 38.87 112 8.7 17.0 32.3 41.7 38.2 11,9
Nd + 8.4 3.22 33.96 112 9.4 31.2 25.4 54.0 30.3 6,7
Sm + 7.1 3.18 32.15 110 15.5 22.5 24.0 35.6 52 15,2
Eu + 8.3 3.20 30.55 101 16.4 13.6 21.7 40.9 42.5 12,4
Gd + 8.3 3.22 29.37 94 10.4 20.9 27.6 58.3 43.4 8,5
Undoped 9.9 3.18 33.99 86 6.3 33.1 25.8 35.1 31.5 13.4
Designs (1) (2) (3)
50 E.G. Villabona-Leal et al. / Computational Materials Science 107 (2015) 48–53

energy, visible light absorption and surface area responses. In this

case, some effects had P-values less than 0.05, indicating that they
were significantly different from zero at the 95% confidence level,
i.e. they were statistically significant to the response [19,20].
As shown in Table 2, the crystallite size between doped materi-
Intensity (a.u.)

TiO2 : Ln (0.3%) als did not depend on the type of Ln, nor on its concentration,
because in all cases the P-values were greater than 0.05. Thereby,
the mean value of crystallite size for all doped samples was
8.4 ± 0.7 nm, while the undoped sample had crystallites 9.9 nm
TiO2 : La (0.1%)
in diameter, i.e. the experimental results show that the size was
reduced (16%) when the material was doped. Table 2 also shows
that the energy band gap depended on the interaction of factors
TiO2 (AB) and not in the individual factors A and B. This is further illus-
trated in Fig. 2, where Eg is plotted against the type of Ln (factor A)
at the two lanthanide concentrations (factor B). In order to obtain a
20 30 40 50 60 70 relationship between Eg and the individual effects of the type Ln
2θ (factor A) and the concentration of lanthanide (factor B), including
the interaction factor (AB) (suggested by P-value, see Table 2), a fit
Fig. 1. Diffraction patterns of TiO2, TiO2:La (0.1 wt.%) and TiO2:La (0.3 wt.%). For of the experimental values of Eg with these factors was done and
studied cases, the crystal structure did not change with the type of dopant or the fit is given by Eq. (1). As result, it is worth noting that the con-
dopant concentration.
tribution of the individual effects of A and B are weak compared to
the combined effect AB.

Eg ¼ 3:29  0:02 A  0:51 B þ 0:11 AB ð1Þ

factors and responses of the experimental designs are summarized
in Table 1. In this case, A takes values of 1–7, which correspond to La, Ce,
In the second ANOVA, we added one factor: (C) pH level Pr, Nd, Sm, Eu and Gd, respectively, and B takes values of 0.1 or
adjusted to 5.6 or 3.1, and we analyzed the zeta potential 0.3 wt.% Ln. Fig. 3 shows the experimental values and ANOVA pre-
(one response with three factors); here, we analyzed diction (Eq. (1)) of Eg for the Ln elements and concentrations. As
1  7  2  2 = 28 experiments. In the third ANOVA, we assessed observed, the dependence on the atomic number of the Ln element
photocatalytic conversion as a function of (A) type of lanthanide can be appreciated in the slope of the fitting. This property is seen
element, (B) concentration, (C) pH and (D) two dye types (one more clearly if we plot the slope (DEg/DB) vs. atomic number for
response with four factors), i.e. 1  7  2  2  2 = 56 experiments. the experimental data; see Fig. 4. An increase in the atomic number
The ANOVA table partitions the variability of responses into (N) increased the slope, going from a negative to a positive slope;
separate items for each of the effects. It then tests the statistical this behavior is described by a straight line, given by
significance of each effect, estimated by comparing the mean
square against an estimate of the experimental error. Table 2 sum- DEg =DB ¼ 0:09N  5:24 ð2Þ
marizes the ANOVA analysis for the crystallite size, band gap 2
Eq. (2) fits the experimental data with R = 91%, which means
that Eg is effectively sensitive to concentration changes, DB.
Visible light absorption was not affected by the type of lan-
Table 2
Analysis of variance tables for the first experimental design, in which four responses
thanide element or concentration (see Table 2 and Fig. 5), as indi-
were analyzed: crystallite size, band gap, UV–visible absorption and surface area as a cated by the P-values that are greater than 0.05. This result can be
function of two factors: (A) lanthanide type and (B) concentration. Statistically attributed to the conservation of the internal structure of the mate-
significant factors are denoted with ⁄. rial. This suggests that dopants are located on the TiO2 surface and
Source Sum of squares Df Mean square F-ratio P-value
Crystallite size
3.25
A:A 0.42875 1 0.42875 1.02 0.3354
B = 0.1 wt%
B:B 0.875 1 0.875 2.09 0.1789
B = 0.3 wt%
AB 0.244464 1 0.244464 0.58 0.4624
Total error 4.18679 10 0.418679
Total (corr.) 5.735 13
Energy gap
3.2
A 0.000144643 1 0.000144643 0.22 0.6472
B 0.00102857 1 0.00102857 1.58 0.2369
Eg (eV)

AB 0.00621607 1 0.00621607 9.57 0.0114⁄

Total error 0.00649643 10 0.000649643
Total (corr.) 0.0138857 13
UV–visible absorption
3.15
A 88.2516 1 88.2516 2.46 0.1477
B 101.521 1 101.521 2.83 0.1233
AB 46.0103 1 46.0103 1.28 0.2836
Total error 358.37 10 35.837
Total (corr.) 594.152 13
Surface area
3.1
A 4.34571 1 4.34571 0.31 0.5903 57 58 59 60 61 62 63 64
B 194.631 1 194.631 13.85 0.0040⁄
Atomic Number
AB 525.831 1 525.831 37.43 0.0001⁄
Total error 140.486 10 14.0486
Fig. 2. Relationship between the type and concentration (B) of lanthanide on Eg
Total (corr.) 865.294 13
(band gap energy).
 E.G. Villabona-Leal et al. / Computational Materials Science 107 (2015) 48–53 51

3.25 3.25 3.25 3.25

La−57 Ce−58 Pr−59 Nd−60
Eg (eV)

Eg (eV)

Eg (eV)

Eg (eV)
3.2 3.2 3.2 3.2

3.15 3.15 3.15 3.15

0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3
B B B B

3.25 3.25 3.25

Sm−62 Eu−63 Gd−64
Eg (eV)

Eg (eV)

Eg (eV)
3.2 3.2 3.2

3.15 3.15 3.15

0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3

B B B

Fig. 3. Experimental and ANOVA prediction for the Eg as a function of lanthanide type and concentration.

55
0.3 B = 0.1 wt%
B = 0.3 wt%
0.2 50

0.1
Δ Eg / Δ B (eV/Wt.%)

45
0
VLA (a.u.)

40
−0.1

−0.2 35

−0.3
30
−0.4

−0.5 25
57 58 59 60 61 62 63 64 57 58 59 60 61 62 63 64

Atomic Number Atomic Number

Fig. 4. Slope of Eg vs. atomic number from the experimental data. An increase in the Fig. 5. Experimental VLA as a function of atomic number and Ln concentration (B).
atomic number (N) increases the slope, going from a negative to a positive slope. VLA was not affected by the type of lanthanide element or concentration.
Where B is the Ln concentration.

SSA ¼ 73:59 þ 5:85 A þ 159:86 B  30:64 AB ð3Þ

not in the TiO2 volume; the internal structure is thereby conserved.
This is expected given that lanthanide elements are around 54%
larger than Ti4+ ions, which makes impairs isomorphic substitution
of dopants inside the host material.
Fig. 6 shows the specific surface area (SSA) as a function of
atomic number, where it can be observed that the SSA was larger
at low dopant concentrations (0.1 wt.%) and high atomic numbers.
Considering dopant ions as spheres around TiO2, and since it is well
known that small spheres (lanthanides) have greater SSA, then for
low dopant concentration (0.1 wt.%), the SSA increases with the
atomic number due to the fact that the atomic radius is inversely
proportional to the atomic number (this is called lanthanide con-
traction). For the higher dopant concentration (0.3 wt.%), the
behavior was different, that can be attributed to the atoms ten-
dency to agglomerate at higher dopant concentration. When
spheres are agglomerated the total volume is increased, and there-
fore the SSA decreases. Taking into account these observations, the
specific surface area (SSA) was modeled by the following equation:
2
The equation fits the experimental values with R = 83%. Fig. 7
shows the experimental values and ANOVA prediction (Eq. (3))
for the SSA as a function of the type of Ln (A) and its concentration
(B). It shows a dependence on the atomic number and the Ln con-
centration, confirming that doping effectively modifies the specific
surface area of these systems.
An interesting surface property for applications in solution is
the zeta potential, which is shown as a function of A and B for these
systems in Fig. 8. We observed no relationship between the type of
Ln element and its concentration. The second experimental design
(see Table 3) shows that the zeta potential only depended on the
pH level. The zeta potential follows the following empirical
equation:
ZP ¼ 49:33  12:70C ð4Þ
where C is the pH level (3.1 or 5.6). Eq. (4) fits the experimental data
with R2 = 87%. As observed here, the zeta potential decreases with
pH, given that surface charge of the particle depends on the ionic
52 E.G. Villabona-Leal et al. / Computational Materials Science 107 (2015) 48–53

120 B=0.1wt%,pH=3.1
B = 0.1 wt% 30 B=0.3wt%,pH=3.1
B = 0.3 wt%
B=0.1wt%,pH=5.6
115
20 B=0.3wt%,pH=5.6

110
10
pH
SSA (cm 2/g)

105 0

Pz
−10
100

−20
95

−30
90
57 58 59 60 61 62 63 64
−40
Atomic Number 57 58 59 60 61 62 63 64
Atomic Number
Fig. 6. Experimental SSA as a function of atomic number and Ln concentration (B).
Fig. 8. Zeta potential as a function of all the studied factors. No relationship was
observed between the type of lanthanide and its concentration (B).
strength and pH. Fig. 8 shows photocatalytic conversion as a func-
tion of all the factors; see also Table 4. We can see that no relation-
ship was found between the type of Ln and its concentration on
Table 3
photocatalytic conversion. Photocatalytic conversion was modeled Analysis of variance tables for the second experimental design. Zeta potential as a
by the following equation: function of three factors: (A) lanthanide type, (B) concentration and (C) pH.
Statistically significant factors are denoted with ⁄.
Pcon ¼ 44:24  2:99 C þ 36:54 D  9:17 CD ð5Þ
Zeta potential

where C is the pH level (3.1 or 5.6) and D is the dye type (1 for Source Sum of squares Df Mean square F-ratio P-value

crystal violet and +1 for methyl orange). Eq. (5) predicts (with A 41.8951 1 41.8951 1.15 0.2950
R2 = 82%) that the maximum photocatalytic conversion is around B 25.8432 1 25.8432 0.71 0.4084
C 7056.44 1 7056.44 194.33 0.0000⁄
42% for crystal violet (D = 1) at the high pH level (C = +1); see
AB 73.4508 1 73.4508 2.02 0.1696
Fig. 9. The opposite electrical nature of TiO2–Ln (negative) and crys- AC 170.776 1 170.776 4.70 0.0417
tal violet (positive) at pH 5.6 promotes dye adsorption onto the TiO2 BC 6.70321 1 6.70321 0.18 0.6718
surface. However, the maximum photocatalytic conversion (around Total error 762.561 21 36.3124
43%) for methyl orange (D = +1) occurred at the low pH level Total (corr.) 8137.67 27

(C = 1) because the methyl orange has a bipolar nature, and the
ionized groups are around 70% positive and 30% negative at pH
3.1 (calculated using the Henderson–Hasselbalch equation) [26]. Finally, Table 5 shows the average for the doped and undoped
Evidently, this dye is susceptible to preferential adsorption on the materials for crystallite size, specific surface area and photocat-
TiO2 surface by groups Ti–OH+2 (low pH) and Ti–O (high pH). alytic conversion. This table shows that the maximum

La−57 Ce−58 Pr−59 Nd−60

SSA (cm /g)

SSA (cm /g)

SSA (cm 2/g)

SSA (cm /g)

110 110 110 110

2

2
2

100 100 100 100

90 90 90 90
0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3
B B B B

Sm−62 Eu−63 Gd−64

SSA (cm /g)

SSA (cm /g)

SSA (cm 2/g)

110 110 110

2

100 100 100

90 90 90
0.1 0.2 0.3 0.1 0.2 0.3 0.1 0.2 0.3
B B B

Fig. 7. Experimental and ANOVA prediction for the SSA as a function of lanthanide type and concentration.
 E.G. Villabona-Leal et al. / Computational Materials Science 107 (2015) 48–53 53

Table 4
8.4 ± 0.7 nm; the undoped sample was 9.9 nm in diameter, so the
Analysis of variance tables for the third experimental design. Photocatalytic conver-
sion as a function of three factors: (A) lanthanide type, (B) concentration, (C) pH and experimental results show that the size was reduced by 15.7%
(D) dye type. Statistically significant factors are denoted with ⁄. when the material was doped. This size reduction increased
21.4% the SSA when the material was doped. The photocatalytic
Photocatalytic conversion
activity depended on the surface interactions between the catalyst
Source Sum of squares Df Mean square F-ratio P-value
and the dye. As expected, an increase in the specific surface area
A 71.8911 1 71.8911 1.90 0.1753 increased the conversion by around 20.4% and 31.5% for crystal
B 0.07875 1 0.07875 0.00 0.9639
violet and methyl orange, respectively.
C 785.252 1 785.252 20.71 0.0000⁄
D 623.779 1 623.779 16.45 0.0002⁄
AB 30.9772 1 30.9772 0.82 0.3709 4. Conclusions
AC 6.14469 1 6.14469 0.16 0.6892
AD 3.83254 1 3.83254 0.10 0.7520
This study screened factors influencing the photocatalytic activ-
BC 41.3145 1 41.3145 1.09 0.3021
BD 20.0402 1 20.0402 0.53 0.4710 ity of TiO2:Ln using the analysis of variance (ANOVA) method.
CD 7353.19 1 7353.19 193.93 0.0000⁄ Surface area and energy gap were found to depend on the interac-
Total error 1706.26 45 37.917 tion between the dopant Ln element and its concentration. In both
Total (corr.) 10642.8 55
cases, a clear dependence on the lanthanide atomic number was
observed. Visible light absorption did not depend on the type of
lanthanide or its concentration. This likely occurred since the
B=0.1wt%,pH=3.1 B=0.3wt%,Ph=3.1 dopants did not change the internal structure of the material.
B=0.1wt%,pH=5.6 B=0.3wt%,pH=5.6 Zeta potential was proportional to the pH level. Ln elements affect
60 the photocatalytic activity because doping inhibits the growth of
(a) cv
Conversion %

50 nanocrystals, thus increasing the specific surface area and thereby

40 increasing photocatalytic activity. The experimental factorial
30
design of this photocatalytic system allowed us to find the best
conditions for enhancing the degradation of the two dyes under
20 pH
investigation.
10
57 58 59 60 61 62 63 64
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40 [3] U.G. Akpan, B.H. Hameed, J. Hazard Mater. 170 (2009) 520–529.
[4] I. Oller, S. Malato, J.A. Sánchez-Pérez, Sci. Total Environ. 409 (2011) 4141–4166.
30
[5] Il-Hyoung Cho, Kyung-Duk Zoh, Dyes Pigm. 75 (2007) 533–543.
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57 58 59 60 61 62 63 64 1596–1604.
[8] An-Wu Xu, Yuan Gao, Han-Qin Liu, J. Catal. 207 (2002) 151–157.
Atomic Number
[9] Jingjing Xu, Yanhui Ao, Degang Fu, Chunwei Yuan, J. Hazard. Mater. 164 (2009)
762–768.
Fig. 9. Photocatalytic conversion for (a) crystal violet and (b) methyl orange as a [10] B.K. Rout, R.K. Mittal, Robot Comput. Integr. Manuf. 24 (2008) 239–248.
function of all factors. For crystal violet, maximum conversion occurred at high pH [11] B.K. Rout, R.K. Mittal, Robot Comput. Integr. Manuf. 25 (2009) 651–666.
and methyl orange occurred at low pH. [12] O. Meza, E. Vega, E. Pérez, Int. J. Adv. Manuf. Technol. 66 (2013) 455–460.
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[14] Zhanxia Shu, Xiuling Jiao, Dairong Chen, CrystEngComm 15 (2013) 4288–4294.
Table 5 [15] N. Couselo, F.S.G. Einschlag, R.J. Candal, M. Jobbágy, J. Phys. Chem. C 112 (2008)
Average for the doped and undoped materials regarding crystallite size, specific 1094–1100.
surface area and photocatalytic conversion. This shows only the maximum photo- [16] G. Leofanti, M. Padovan, G. Tozzola, B. Venturelli, Catal. Today 41 (1998) 207–
catalytic conversion conditions, i.e. high pH for crystal violet (C = +1, D = 1) and low 219.
pH for methyl orange (C = 1, D = +1). (C) Two pH conditions, with – and + equal to [17] Jun Lin, Jimmy C. Yu, J. Photochem. Photobiol. A 116 (1998) 63–67.
3.1 and 5.6 and (D) two dye types, with – and + equal to crystal violet and methyl [18] Mianxince Song, Liang Bian, Tianliang Zhou, Xiaoyong Zhao, J. Rare Earths 26
orange, respectively. (2008) 693–699.
[19] D.C. Montgomery, Design and Analysis of Experiments, Wiley, New York, 2001.
C = +1, D = 1 C = 1, D = +1 [20] N.L. Frigon, D. Mathews, Practical guide to experimental design, Wiley, New
Size (nm) SSA (cm2/g) Conversion (%) Conversion (%) York, 1996.
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Doped 8.4 ± 0.7 104.4 ± 8.1 42.3 ± 6.5 43.1 ± 8.2 [22] J. Tauc, R. Grigorovici, A. Vancu, Phys. Status Solidi B 15 (1966) 627–637.
Undoped 9.9 86.0 35.1 31.5 [23] A. Ibrahim, S.K.J. Al-Ani, Czech. J. Phys. 44 (1994) 785–797.
Increment 15.7% 21.4% 20.4% 36.7% [24] A.V. Vorontsov, A.A. Altynnikov, E.N. Savinov, E.N. Kurkin, J. Photochem.
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[25] J.A. Pedraza-Avella, R. López, F. Martínez-Ortega, E.A. Páez-Mozo, Ricardo
photocatalytic conversion occurred at high pH for crystal violet
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(C = +1, D = 1) and at low pH for methyl orange (C = 1, D = +1). [26] R.G. Sandberg, G.H. Henderson, R.D. White, E.M. Eyring, J. Phys. Chem. 76
The mean value of crystallite size for all doped samples was (1972) 4023–4025.