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Correlation of Surface Area with Photocatalytic Activity of TiO2

Article  in  Journal of Advanced Oxidation Technologies · January 2018

DOI: 10.26802/jaots.2017.0063

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Article:

Correlation of Surface Area with

Photocatalytic Activity of TiO2
A. V. Vorontsov1,2,3*, E. N. Kabachkov4,5, I. L. Balikhin4, E. N. Kurkin4,5, V. N. Troitskii5, and P. G.
Smirniotis6
1 N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, pr. ak. Lavrentyeva 9, Novosibirsk 630090, Russia
2 Boreskov Institute of Catalysis, pr. ak. Lavrentyeva 5, Novosibirsk 630090, Russia
3 Altai State University, pr. Lenina 61a, Barnaul 656049, Russia
4 Institute of Problems of Chemical Physics, Chernogolovka, Moscow Region, 142432, Russia
5Scientific Center of the Russian Academy of Sciences in Chernogolovka, Chernogolovka, Moscow Region, 142432,
Russia
6Biomedical, Chemical & Environmental Engineering Department, College of Engineering and Applied Sciences,
University of Cincinnati, Cincinnati, OH 45221-0012, USA
*a-voronts@yandex.ru

Abstract

Experimental investigation has been undertaken with the goal to determine the effect of specific surface area, extent of
hydroxylation, surface acidity properties on TiO2 photocatalytic activity in deep oxidation of gas phase acetone. pH of aging,
calcination temperature and calcination time were varied in TiO2 preparation using TiCl4 hydrolysis. The photocatalytic activity
attains its maximal values at aging pH close to 4 and calcination temperature different for different calcination time and
hydrolysis conditions. Specific surface area continuously decreases with an increase in calcination temperature. Maximal
photocatalytic activity corresponds to very different surface area for different series of TiO2 samples. These data mean that TiO2
particles size and surface area does not have a direct influence on photocatalytic activity but it is rather surface properties such
as surface acidity and hydroxyl groups content, which are different for samples prepared at different pH and calcination
temperature, that determine the photocatalytic activity.

Keywords

Particles Size Effect; Surface Acidity; Acetone Oxidation; Gas-Phase Heterogeneous Photocatalysis

Received: June 22, 2017; Revised: July 20, 2017; Accepted: August 24, 2017

Introduction

Gas phase photocatalytic oxidation is an economical method for air purification from trace concentrations of
organic compounds [1]. TiO2 is the most often used photocatalyst due to its high activity, stability and low price [2,
3]. The research on the gas phase heterogeneous photocatalytic oxidation over TiO2 was started in the early 1960-
ths [4]. Since then, it has been demonstrated that almost any organic compound can be oxidized into inorganic
products over UV irradiated TiO2. The reaction of oxidation proceeds with participation of lattice and surface
oxygen through formation of oxygen vacancies that are cured via photoadsorption or dark reactions with gaseous
O2 [5, 6]. The activity of TiO2 in gas phase heterogeneous photocatalytic oxidation varies widely depending on TiO2
preparation conditions [7-27], the key parameters in sol-gel synthesis being hydrolysis media compositon,
calcination or solvothermal treatment temperature and time [28-30].

Journal of Advanced Oxidation Technologies 2018; 21(1) www.jaots.net

DOI: 10.26802/jaots.2017.0063
Journal of Advanced Oxidation Technologies 2018; 21(1)

The effect of preparation conditions on photocatalytic activity of TiO2 formed depends on the type of test reaction
and reagents. In gas phase heterogeneous photocatalytic oxidation, a variety of classes of reagents are used and
intermediate gas phase products are formed in significant concentrations for many of them. Simple short-chain
aldehyde acetaldehyde and ketone acetone usually does not produce intermediate gaseous products. In the present
study, acetone is selected as the reagent. A large number of publications is devoted to gas phase heterogeneous
photocatalytic oxidation of acetone [31-33]. The effect of the reagents and water vapor concentration on the reaction
rate is described by a single or two-site Langmuir-Hinshelwood (LH) kinetic model [28]. At water vapor
concentration below 1000 ppm, the rate of oxidation increases with an increase in water concentration, a fact not
fitting into the competitive adsorption LH model but is related to the participation of water molecules in the
oxidation reaction [40].
The major precursors for TiO2 synthesis available at large scale are TiOSO4 and TiCl4. Titanium alkoxides such as
ethoxide, isopropoxide or butoxide are often used for TiO2 preparation at smaller scale [2]. The traditionally used
sol-gel process for TiO2 preparaton involves hydrolysis at definite conditions with subsequent aging, drying and
calcination or hydrothermal treatment. The major parameters controlling the preparation are composition of the
reaction mixture during hydrolysis, calcination time and temperature. The influence of calcination parameters has
been studied in detail previously [8, 13]. Surface area monotonically decreases, particle size increases and
photocatalytic activity reaches a maximum value and then decreases when the calcination temperature rises [14,
18]. This widely observed dependence of photocatalytic activity on calcination temperature finds contradictory
explanations. Commonly accepted understanding is that an increase of particles size decreases activity due to the
higher probability of charges recombination [24]. However, the increase in activity with the growth of particles size
meets difficulties in understanding. The effect of the aging media pH on TiO2 properties and activity is studied
seldom and has not been comprehended [27]. Despite long time studies with the influence of preparation
conditions on TiO2 properties, the conclusive theory of the phenomena observed is unavailable.

In the present work, we investigate the influence of TiO2 preparation conditions from TiCl4 on TiO2 specific surface
area and photocatalytic activity in gas phase acetone oxidation. The influence of media pH during TiO2 aging,
calcination temperature and calcination time are investigated. During this research, procedures for preparation of
relatively large batches of photocatalytic TiO2 have been developed.

Experimental

Chemicals

The following chemicals were used in catalysts preparation: NaCl (chemically pure, KhimCo), NaOH (chemically
pure, Khimproductsiya), TiCl4 (chemically pure, Khimprom), NH4Cl (chemically pure, Khimprom), NH3 (25%,
SigmaTek), hexane (pure for analysis, Kriokhrom). Acetone (very high purity, Reakhim) was used for carrying out
photocatalytic oxidation tests. The tests utilized oxygen of compressed air purified by passing through silica gel
and activated carbon as well as sodium hydroxide in order to remove all impurities and CO2. Distilled water was
used for catalysts synthesis and humidification of air for catalytic tests.

Catalysts Preparation
All TiO2 samples of the present study were prepared via hydrolysis of TiCl4 in liquid aqueous media. Different
procedures were used for preparation of different series of the samples and they have different designations
expressed by the first one or two capital letters and number. Samples designations are inherited from our previous
studies discussed in the next sections.

E18. 500 cm3 of TiCl4 was added at the rate of 10 cm3/min into 4000 cm3 of aqueous solution of 1.07 kg NaCl under
continuous stirring with a home-made mechanical mixer and thermostating at 35 – 38 °C. The slurry formed was
neutralized with 2500 cm3 of aqueous solution of 1.17 kg of NaOH and 0.66 kg of NaCl added gradually at the rate
of 5000 cm3/h till the pH of the slurry became 6.0. pH was measured with a pH-meter Expert-001-1 (Econiks-
Expert). The neutralized slurry was dried using spray drying with the rate of spraying 5 L/h. The dried powder
Journal of Advanced Oxidation Technologies 2018; 21(1)

was calcined in a crucible in air in a home-made rotating oven during 75 min at a temperature of 350, 420, 500 and
600 °C. The calcined powder was washed with distilled water thoroughly in a funnel in order to remove NaCl and
dried.
E21. Hydrolysis and neutralization were carried out exactly as for samples E18. The neutralized slurry was
evaporated in a pan under boiling. Calcination was done in a rotating oven during 75 min at temperatures of 350,
400, 450, 500 and 550 °C.
F1. 10 cm3 of TiCl4 was added to 50 cm3 of liquid hexane. 3.3 cm3 of distilled water was added to the organic
solution and the mixture was stirred for 30 min. The resultant slurry was dried in a drying oven at 130 °C and
calcined in air atmosphere in the rotating oven during 30 min at temperature of 300, 330, 350, 400, 500, 600, 700, or
800 °C.
H19. 50 cm3 of TiCl4 was added to 400 cm3 of aqueous solution of 100 g of NH4Cl. The resultant slurry was
neutralized by adding aqueous ammonia till obtaining the desired pH 4.0, 4.5, 5.8, 7.0, or 8.6. The aqueous slurry
was then dried in a drying oven at 60 °C and calcined during 180 min at temperature of 400 °C. Previously, we
reported the preparation and properties of H19 samples obtained at pH 7.0 and different calcination temperatures
in the range of 320 to 500 °C [41].

H34. Hydrolysis and neutralization were carried out as for samples H19. The final pH of the neutralization was 1.2,
2.3 or 3.7. Drying and calcination were carried out during 70 min at a temperature of 450 °C.

HE28. The calcination temperature of the samples was tried to be fine tuned in this series of TiO2 samples. The
preparation procedure was the same as for samples of series E18. Final pH after the neutralization was 6.0.
Calcination was performed for 75 min at temperatures 430, 440, 450, 460 or 470 °C.
HE47. Hydrolysis and neutralization were carried out following the same procedure as for samples series E18, E21
or HE28. Final pH of the neutralization was tried to be fine tuned at the values of 3.0, 3.3, 4.0 or 4.2. Drying and
calcination was carried out during 75 min in a rotating oven at 440 °C.
Characterization
Phase composition of the prepared samples was studied with XRD using DRON ADP-2-02 diffractometer
2 samples are very similar to

those obtained in previous publications for anatase photocatalysts [9- 19] and are not shown. All samples contained
anatase phase only. Specific surface area was measured using low temperature nitrogen adsorption in a
Quantasorb apparatus (Quantachrome).
Measurements of Photocatalytic Activity
Photocatalytic activity of TiO2 samples was measured in the reaction of complete oxidation into inorganic
compounds (mineralization) of acetone vapors with oxygen of air. Acetone is a convenient reagent for testing
photocatalytic activity since no intermediate gaseous products are formed and the photocatalytic activity can be
calculated from the rate of CO2 formation. The procedure of the carrying out the reaction and measurement of
activity has been proven dependable and reported in detail previously [42-48]. In brief, 5 mg of TiO2 sample was
wet loaded onto the center round spot of 3 x 3 cm glass plate. The plate was placed into a glass reactor with an
optical quartz window that was included into a flow-circulation system. The installation scheme that includes the
flow-circulation reaction system is given in Fig. 1. Air from an air line is purified and passed through saturators
filled with liquid acetone and water. The flows saturated with acetone and water vapors are diluted with pure air
and supplied as feed for the flow-circulation reaction block. The circulation pump provides circulation of air with a
rate much higher (over 10 times) than the feed rate. Under this condition the mixing of the reagents and products is
very efficient and concentration gradients are absent.

The system allows keeping uniform concentrations and temperature. Standard testing conditions were acetone
concentration 400 - 600 ppm, water vapor concentration 4400 ppm, temperature 40 °C, flow rate 40 - 60 ccm. Errors
Journal of Advanced Oxidation Technologies 2018; 21(1)

of the measurement of concentration and flow rate did not exceed 10 %. The external appearance of the
photocatalytic installation with the flow-circulation reaction block is shown in Fig. 2.
Air discharge
Air input

FIG. 1. SCHEME OF INSTALLATION USED FOR THE STUDIES ON PHOTOCATALYTIC ACTIVITY IN A FLOW-CIRCULATION REACTOR.
1 – PRESSURE REGULATOR, 2 – AIR PURIFICATION UNIT, 3 – FLOW CONTROLLER, 4 – BUBBLER WITH ACETONE, 5 – BUBBLER WITH
WATER, 6 – FLOW MIXING BLOCK, 7 – FLOW CONTROLLER, 8 – SAMPLING PORTS, 9 – QUARTZ PHOTOCATALYTIC REACTOR, 10 –
CIRCULATION PUMP, 11 – XE LAMP LIGHT SOURCE, 12 – FLOW METER, 13 – MIRROR, 14 – THERMOSTATED CHAMBER

FIG. 2 EXTERNAL VIEW OF THE INSTALLATION WITH A FLOW-CIRCULATION PHOTOCATALYTIC REACTION BLOCK
Journal of Advanced Oxidation Technologies 2018; 21(1)

Irradiation was provided by a 1000 W Xe lamp light transmitted through a filter. Fig. 3 demonstrates transmission
spectrum of the light filter used. The filter removes visible part of the emission spectrum of the Xe lamp.

30

25

20
橡 铒篑赅龛 ? %

15

10

200 250 300 350 400 450

碾Wavelength,
桧 ? 忸腠nm ? 盱
FIG. 3 TRANSMISSION SPECTRUM OF THE FILTER USED FOR IRRADIATION OF PHOTOCATALYSTS WITH A XE LAMP LIGHT

The incident irradiance was 7 mW/cm2. The irradiance was measured with ferrioxalate actinometry. Quantum
efficiency was calculated using the rate of CO2 production and the flux of UV radiation incident onto the
photocatalyst surface. The exact procedure and formulas are given in the referenced papers.

Results and Discussion

Aging media composition, calcination temperature and time were the parameters varied during the sol-gel TiO2
preparation and their effects are discussed in this section.

Effect of TiO2 Aging pH

After TiCl4 was added completely into the hydrolysis aqueous media, the second stage of the TiO2 deposition was
started that includes further hydrolysis of Ti-Cl bonds and condensation of the Ti-OH moieties into Ti-O-Ti bonds.
It turned out that pH of the aqueous media during this aging process plays a crucial role. It strongly changes
specific surface area and photocatalytic activity while keeping the dominant phase of anatase. No other phases in
significant quantity and amorphous material were detected in the samples prepared due to the application of
calcination at a high temperature of above 320 °C and aging pH above 1.

Fig. 4 shows the effects of pH of aging media onto specific surface area and photocatalytic activity of TiO2 formed
for three series of catalysts prepared at different conditions. The specific surface area (BET) and quantum efficiency
(QE) data of catalysts H34 prepared at pH below 4 show increasing tendencies with an increase in pH. The samples
of the series HE-47 were prepared at pH around 4. Their activity increases with an increase in pH when the initial
aging pH was below 4 and decreases when it is above 4. Finally, the catalysts of the series H19 were prepared at
initial aging pH 4 and higher. We can see that specific surface area of these samples continues to increase with an
increase in solution pH while photocatalytic activity steadily decreases. Thus, the starting pH of aging equal to
approximately 4 provides conditions for formation of the most active photocatalyst for the reaction of gas phase
acetone mineralization. The highest activity of the TiO2 sample sets prepared at pH around 4 is similar: 68 % for
Journal of Advanced Oxidation Technologies 2018; 21(1)

H34, 66 % for HE-47,and 61 % for H19. This QE is close to that for Hombikat UV 100 (Sachtleben Chemie GmbH)
anatase photocatalyst [42].

FIG. 4 INFLUENCE OF PH OF TIO2 PRECIPITATION ON ITS SPECIFIC SURFACE AREA AND QUANTUM EFFICIENCY IN ACETONE
OXIDATION

FIG. 5 CORRELATIONS OF SPECIFIC SURFACE AREA AND PHOTOCATALYTIC ACTIVITY FOR TIO2 SAMPLES PREPARED AT PH
BELOW 4 (INCREASING TREND) AND ABOVE 4 (DECREASING TREND)

TiO2 specific surface area always has direct correlation with the size of the primary particles. Correlations of the
specific surface area with photocatalytic activity of TiO2 samples prepared at different pH is demonstrated in Fig. 5.
There are two separate types of the correlation with increasing and decreasing tendency. At pH below 4,
photocatalytic activity increases with an increase in surface area while at pH above 4 the activity decreases. The
correlation coefficients for the ascending and descending branches are 0.88 and -0.38 with the meaning that the
correlations are really observed. The rising line slope is 1.58 while it for the descending line is -0.75 showing a
slower change after the maximum. The observed crossing of the lines arises from different conditions used for
preparation of different photocatalysts series so that the activity may be smaller or larger with the same surface
area depending on other than specific surface area properties. The observed two different kinds of correlation of
Journal of Advanced Oxidation Technologies 2018; 21(1)

specific surface area and photocatalytic activity mean that photocatalytic activity can be increasing or decreasing
with the TiO2 particles size.

Effect of TiO2 Calcination Temperature

The temperature and time of TiO2 calcination have a strong influence on both specific surface area and
photocatalytic activity in deep oxidation of acetone as Fig. 6 demonstrates.

FIG. 6 PHOTOCATALYTIC ACTIVITY AND SPECIFIC SURFACE AREA OF TIO2 SAMPLES AS A FUNCTION OF CALCINATION
TEMPERATURE

Properties of five different series of TiO2 catalysts are shown in Fig. 6 for diverse preparation conditions. All the
samples demonstrate the same tendency of the steady decrease of specific surface area with an increase in
calcination temperature. Only HE-28 samples show some inconsistent increase in the very narrow calcination
temperature range of 420 – 440 ⁰C that can be ascribed to scattering or errors in experimental points (the error in
the experimental values is around ±5 %). Quantum efficiency of deep acetone photocatalytic oxidation is always
maximal at some value of the calcination temperature, the position of the peak being dependent on catalysts
preparation conditions other than calcination temperature. The peak temperature is as follows: H19 – 450, HE-28 –
430, E-21 – 400, E-18 – 420, and F1 – 600 ⁰C. Thus, for the majority of samples, the photocatalytic activity peak
calcination temperature changes in the range of 400 – 450 ⁰C. The only sample that demonstrated very different
peak temperature is F1: the maximal value of photocatalytic activity for this sample corresponds to calcination
temperature 600 ⁰C. The cause for this behavior lies in completely different preparation scheme for this catalyst
series. The preparation was performed in reverse micellar system. The calcination time for these catalysts is only 30
min that also gave contribution to the high temperature needed for obtaining the highest activity.

The highest photocatalytic activity in the present study was observed for the sample E-18 calcined at 420 ⁰C. The
quantum efficiency for this sample was 90 % which is significantly higher than that for widely known
commercially available samples P25 and Hombikat UV 100. The second highest was E21 calcined at 400 ⁰C with QE
81 %. The samples HE-28 and F1 possess similar activity 61 and 66 % which is close to activity of Hombikat UV 100
[42]. The least active sample series is H19 that has the highest activity of only 41 %.

In the section 3.1, it was reported that the peak photocatalytic activity was observed at some values of TiO2 specific
surface area, and this value is different for different series of TiO2 samples prepared at variable pH value. However,
the initial pH of the aging solution corresponding to the highest activity was always the same at 4. This means that
pH is the predominant factor for peak photocatalytic activity and specific surface area and particles size are
Journal of Advanced Oxidation Technologies 2018; 21(1)

influencing it much weaker. In the present section, the effect of calcination temperature is investigated on specific
surface area and photocatalytic activity.

FIG. 7 UNREFINED CORRELATION OF PHOTOCATALYTIC ACTIVITY AND SPECIFIC SURFACE AREA FOR TIO 2 SAMPLES PREPARED
AT DIFFERENT CALCINATION TEMPERATURE

Fig. 7 demonstrates the point chart of quantum efficiency of deep acetone photocatalytic oxidation versus specific
surface area. Data for all the samples in Fig. 6 were included into Fig. 7. Without any guidelines, the points in Fig. 7
looks very scattered and no one can deduce any correlations of activity and specific surface area. This plot explains
contradictory opinions on the effect of particles size and surface area onto photocatalytic activity. However, if some
guidelines are provided for the data, the character of the influence and correlation becomes evident as Fig. 8
reveals.

FIG. 8 SEPARATED CORRELATIONS OF PHOTOCATALYTIC ACTIVITY WITH SURFACE AREA OF THE CALCINATION TEMPERATURE
EFFECT FOR DIFFERENT SETS OF SAMPLES

The guidelines connect the data points corresponding to the same TiO2 samples sets obtained at different
calcination temperature while all other preparation conditions kept constant. The maximum values of the quantum
Journal of Advanced Oxidation Technologies 2018; 21(1)

efficiency correspond to different values of specific surface area for different sample sets. For the set F1, the peak
activity is observed at the lowest specific surface area 37 m2/g. This is due to the very specific reverse micellar
preparation method used. For TiO2 of E21 series, the peak quantum efficiency of 81 % corresponds to the highest
specific surface area 158 m2/g. The other series of TiO2 samples have peak activity at intermediate surface area but
different for each samples set. This result again confirms the hypothesis that specific surface area and particles size
are only secondary factors influencing photocatalytic activity.
The question arises what are the dominant factors influencing photocatalytic activity for TiO2 samples prepared
from TiCl4 in aqueous phase hydrolysis and calcination process. XRD characterization of the TiO2 samples having
maximal activity in each series revealed that anatase is the crystal phase. Rutile in small quantity is observed only
for samples prepared at initial aging pH below 4. Therefore, phase composition does not give contribution to the
different photocatalytic activity. Change in pH during TiO2 aging influences its surface acidity. Calcination at
different temperature and for different periods of time influences concentration of surface hydroxyl groups. Since
aging pH and calcination temperature and time influence photocatalytic activity strongly, surface acidity and
concentration of surface hydroxyl groups are the dominant factors determining photocatalytic activity in deep
oxidation of acetone.

Conclusions

The experimental research on the influence of TiO2 nanoparticles properties on their photocatalytic activity has led
to the following conclusions.
1. Increase in aging pH and calcination temperature during TiO2 preparation by hydrolysis of TiCl4 results in
increase and decrease of specific surface area of TiO2, respectively.

2. Photocatalytic activity of TiO2 is maximal at pH of aging equal to 4, while calcination temperature for obtaining
maximal activity depends on other preparation conditions. Therefore, TiO2 surface area and particle size are only
secondary factors influencing photocatalytic activity, while extent of surface hydroxylation and other surface
properties such as acidity and surface structure should play the key role in obtaining high photocatalytic activity.

ACKNOWLEDGMENT

This work was supported by Russian Foundation for Basic Research projects 13-08-01286 and 15-08-01936.

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