Journal of Colloid and Interface Science 299 (2006) 125–135

[Link]/locate/jcis

Photooxidation of dibenzothiophene on TiO2/hectorite thin films

layered catalyst
Jamie Robertson, Teresa J. Bandosz ∗
Department of Chemistry, The City College of New York, 138th Street and Convent Avenue, New York, NY 10031, USA
Received 11 December 2005; accepted 7 February 2006
Available online 5 April 2006

Abstract
A new titanium(IV) oxide–hectorite nanofilm photocatalyst was prepared on quartz slides. It was evaluated in the photooxidation of dibenzoth-
iophene (DBT) in nonpolar organic solution (tetradecane), as a model for diesel fuel. A removal regimen was developed consisting of catalytic
photooxidation followed by adsorption of products on silica gel. Photooxidation of DBT was performed with and without catalyst, at 254 and
300 nm. Comparison was made with a commercially available TiO2 catalyst, Degussa P25. The catalyst was analyzed by nitrogen adsorption,
XRD, SEM, and TGA-DTA. DBT concentrations were measured by HPLC and UV spectrophotometry. Preliminary qualititative analysis of
products was performed by UV and HPLC. Results indicated that the outlined process was effective in reducing sulfur levels to below 10 ppm
sulfur.
© 2006 Elsevier Inc. All rights reserved.

Keywords: Titanium oxide; Dibenzothiophene; Photooxidation; Desulfurization

1. Introduction move DBT and other heterocyclic sulfur compounds from both
aqueous and organic solutions [4–11]. Most of these investiga-
U.S. Environmental Protection Agency regulations slated to tions have taken place in the presence of water. Some have been
take effect in 2006 require deep desulfurization of both gasoline performed with the aid of catalysts, such as titanium(IV) oxide.
and diesel fuels. Specifically, new fuel standards call for even- The use of titanium(IV) oxide as a photocatalyst has re-
tual reduction in sulfur content to below 30 ppm sulfur by mass ceived extensive coverage in Ref. [12]. TiO2 can absorb light
for gasoline and 15 ppm for diesel [1]. Sulfur in fuel leads to the throughout the UV range and has been demonstrated to be an
release of SO2 upon combustion. High sulfur content is also as- effective photocatalyst for a number of reactions [12]. Recently,
sociated with the poisoning of catalysts in catalytic converters Dekany and co-workers have demonstrated the synthesis of
[2] and fuel cells. multilayer photocatalysts containing metal oxides layered with
Dibenzothiophene (DBT) and its derivatives occur naturally clays [13,14]. The multilayer photocatalyst is affixed to a solid
in coal and oil deposits. It is one of the most difficult sul- substrate. This prevents some common problems associated
fur compounds to remove from liquid fuels. The conventional with heterogeneous catalysts in some other systems.
desulfurization method involves reduction with hydrogen gas at Titanium(IV) oxide has been investigated as a catalyst for
the oxidation of dibenzothiophene [11,15]. It has been found
high pressures. Unfortunately, this method is not very effective
to greatly enhance the rate of photooxidation, particularly at
at removing DBT and its alkylated derivatives [3]. This neces-
higher wavelengths. At wavelengths above 300 nm, the extinc-
sitates the development of improved techniques for the removal
tion coefficient for DBT is much lower, so that photooxidation
of DBT from gasoline and diesel fuels. Recently, a number of
at these wavelengths is more likely due to indirect (catalyzed)
researchers have investigated the use of photooxidation to re-
photolysis than to direct photolysis.
Much of the research with TiO2 photocatalysts has involved
* Corresponding author. Fax: +1 212 650 6107. suspensions of the catalysts in either aqueous or polar organic
E-mail address: tbandosz@[Link] (T.J. Bandosz). solution. This method can pose a few logistical problems. Cat-
0021-9797/$ – see front matter © 2006 Elsevier Inc. All rights reserved.
doi:10.1016/[Link].2006.02.011
126 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135

alyst suspensions limit the amount of TiO2 that can be used, The titanium oxide sol was prepared as in Lakshmi et al.
since agitation can only suspend a limited amount of catalyst. [18]. Briefly, 5 ml of titanium(IV) isopropoxide was added to
Also, suspended catalyst particles may actually block out ultra- 25 ml ethanol. The solution was stirred in an ice bath. To an-
violet light. This is particularly problematic for any scale-up of other 25-ml aliquot of ethanol, 0.5 ml of deionized water and
the process. Finally, suspended catalysts are costly and prob- 0.5 ml of 0.1 M hydrochloric acid were added. The solution
lematic to remove. Thus various methods and substrates have was removed from the ice bath and placed in a 15 ◦ C water bath
been used to make nanoscale TiO2 catalysts [13,16,17] with Then the acid solution was slowly added to it. A milky white
mixed effects. suspension formed within 1 min.
While some papers focus primarily on benzothiophenes in The hectorite suspension was prepared as in Kotov et al. [13].
the natural environment [6,8,10], others describe the removal One gram of synthetic hectorite (Na0.3 (Mg,Li)3 Si4 O10 (OH)2 )
of these species from petroleum feedstocks [5,7,9]. When a was added to 100 ml of deionized water. The mixture was
300-W high-pressure mercury lamp (unfiltered) was used to placed in a sonication bath (Branson 1510) for 40 min. The mix-
photoirradiate solutions of DBT in tetradecane (100 ml) or ture was centrifuged (Fisher Centrific, 3000 rpm) for 35 min.
water (300 ml), DBT and its derivatives were completely re- The supernatant was reserved for use in catalyst synthesis.
moved over the course of less than 10 h. The rate of pho- The multilayer assembly process was a variation of that per-
tolysis was highest for the most substituted DBT and lowest formed in Szabo et al. [14]. Substrate slides were immersed
for the least substituted, which is the reverse of the reaction into the titanium sol for 60 s. Slides were immediately rinsed
rate for hydrodesulfurization. Hirai et al. reported that when with running deionized water and air-dried. They were then im-
the tetradecane–DBT solution was irradiated without aqueous mersed into the hectorite suspension for 60 s and again rinsed
phase, yellow discoloration and increased viscosity occurred in with deionized water and air-dried. Hectorite, as a light trans-
the organic phase [5]. They also found that the absence of air or parent mineral with high surface area, was chosen to spatially
oxygen dramatically reduced the rate of photolysis. After irradi- separate layers of titania oxide and thus increase the efficiency
ation, only residual DBT was present in the organic phase, with- of the catalytic process. The layers of film were built via elec-
out other sulfur compounds. Less than 1% of tetradecane was trostatic adsorption. The experimental steps were repeated a
decomposed in the process. In the aqueous phase, the presence total of 10 times. The mass of the dry, uncalcinated slides was
of sulfate ion (SO2−4 ) was detected. Its concentration increased recorded. The hectorite/titania oxide film was stable in tetrade-
with a decrease in concentration of DBT, with 80% of the sulfur cane solution. In layering experiments, considerable variation
converted to SO2− 4 . In commercial light oil, the desulfuriza- was seen for the first four or five multilayers. By the time eight
tion was found to be 22% after 30 h, far less than predicted, multilayers had been deposited, slide coatings were found to
which was attributed to presence of naphthalene in the oil. The be quite consistent. Increase in mass was generally found to be
acidic minor products of the DBT oxidations were investigated proportional to surface area.
by Shiraishi et al. [9]. The formation of 2-sulfobenzoic acid The dry multilayered slides were heated in a horizontal tube
anhydride and benzothiophene-2,3-dicarboxylic acid was re- furnace in an air atmosphere to 400 ◦ C with 1 ◦ C/min heating
ported. rate. Temperature was maintained at 400 ◦ C for 6 h and then it
The objective of this research is to evaluate a two-stage was reduced over 6 h to room temperature. The mass of calci-
process for removal of dibenzothiophene from nonpolar organic nated slides was recorded. The material is hereafter referred to
solvent. The project requires the synthesis of a multilayer TiO2 – as CAT.
hectorite photocatalyst and the study of this catalyst for the The catalyst slides, as prepared, were analyzed by XRD
photooxidation of dibenzothiophene in organic solution. In de- and SEM. Due to space limitations, it was not possible to per-
termining the efficiency of the catalyst, studies are performed form TGA-DTA or nitrogen adsorption analysis on the catalyst
using light at different wavelengths, in the presence or absence slides. Characterization for these analyses was performed us-
of the catalyst. Comparative studies are also carried out between ing TiO2 powder obtained from the titanium sol. These samples
photooxidation of dibenzothiophene with the synthesized cata- were prepared by evaporating the ethanol at room temperature
lyst and with a commercially available TiO2 catalyst. and then calcinating the resulting powder in the tube furnace
using the program outlined above. The powder is referred to
2. Experimental throughout this paper as TiO2 .

2.1. Synthesis of the catalyst 2.2. Methods

Quartz slides (1 mm thick) were cut to a size of 1.25 by 2.2.1. Photooxidation

7.5 cm. Two small holes (about 2 mm in diameter) were drilled Photooxidation trials were performed in a Rayonet Cham-
in each slide to facilitate mounting. The slides were cleaned by ber reactor (RMR-600) using 253.7- and 300.0-nm UV lamps.
sonification (Branson 1510) for 20 min in detergent solution. Eight lamps were used in each photoirradiation. The nominal
As a next step they were rinsed with copious amounts of deion- power of the 253.7-nm lamps was approximately 8 W each at
ized water and dried in air. The slides were then immersed in that wavelength. The nominal power of the 300.0-nm lamps was
chromic acid for 1 h, rinsed and dried again. The mass of each 3.9 W each [19]. The sample tubes were mounted on a station-
slide was recorded prior to multilayer assembly. ary carousel, with each tube aligned with one of the lamps at a
 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135 127

distance of approximately 1 cm, to ensure equal UV intensity from 50 to 1000 ppm weight in tetradecane. Ten milliliters of
for the eight sample tubes mounted in the chamber. each solution was placed in a 12-ml glass vial, along with 0.50 g
Sample tubes were composed of quartz silica, with a total of silica gel. The tubes were capped, shaken, and stored in the
tube volume of 15 ml. Ambient air was supplied at a rate of dark overnight. Samples were filtered using a syringe equipped
0.2 L/min for the duration of the photooxidation. To increase with a 0.2-µm filter. Concentration of DBT was determined for
the concentration of active radicals [15], the air was humidified each sample using UV spectrophotometry at 313 and 326 nm.
by passing it through a water bubbler prior to its entering the
reactor tubes. 2.2.3. UV spectroscopy
Stock solutions were made of DBT (98% purity) at a con- DBT concentrations were determined by UV spectropho-
centration of 200 ppm weight in n-tetradecane (purity  99%). tometry on a Cary 100 Bio. For DBT, absorbances at 313 and
DBT was supplied by Sigma–Aldrich. Tetradecane was ob- 326 nm were compared with calibration curves generated pre-
tained from VWR. Ten milliliters of solution were added to viously on the same instrument. To eliminate interference from
each sample tube. oxidation products of DBT, 10.0 ml of each sample was placed
Trials without the catalyst were performed with 254-nm in a closed vial with 0.50 g of silica gel for at least 12 h, prior
lamps. After 2-h of irradiation, two tubes of solution were re- to spectrum measurement. Adsorption experiments showed that
moved and diluted back to their original volume with tetrade- this amount of silica would lead to a reduction in DBT con-
cane. (Samples were found to lose less than 3% of their original centration by no more than 5 ppm, indicating that DBT is not
volume over the course of 8 h of photoirradiation). Samples strongly adsorbed on its surface. The oxidation products, on the
were placed in taped vials and stored in the dark prior to be- other hand, are strongly adsorbed on silica, allowing their re-
ing analyzed by UV spectrophotometry. The sample tubes were moval from sample solutions.
replaced by fresh sample solutions. Additional sample tubes
were removed at varying time intervals. In this way, two to four 2.2.4. HPLC
replicate samples at each interval were obtained with irradiation DBT concentrations for trial 1-300 were obtained by reverse
times of 2, 4, 6, and 8 h for each solution. Trials were numbered phase HPLC on a Agilent 1100 with a Merck SP-18 column
for record-keeping purposes (e.g., 1-254, 2-254, etc.). with Lichrospher C-18 bonded packing and a UV detector at
Trials at 300 nm without a catalyst were performed in a fash- 245 nm. In preparation for HPLC, 1 ml of sample was diluted to
ion identical to the 254-nm trials, except that 300-nm lamps 10 ml with ethanol. The mobile phase was a mix (75/25) of ace-
were used. The 300-nm lamp produces a broader wavelength tonitrile and water, with a flow rate of 0.8 ml/min. This solution
pattern centered on 300 nm, with the intensity dropping to near was injected using an injection loop with an injection volume
zero around 250 and 350 nm. The total photon intensity was of 20 µl. An external standard of DBT was found to elute un-
approximately half that of the 254-nm trials. These trials were der these conditions at 3.9 min. DBT sulfone (97%, Aldrich)
numbered 1-300 and 2-300. was found to elute around 1.4 min. Separate peaks were un-
In a third trial, 1-DARK, everything was as in the above resolved for other photooxidation products, with the exception
described experiments, but the tubes were wrapped in foil, to of a peak that appeared consistently at 2.1 min for all of the
prevent any ambient light from entering the tubes. These trials oxidized samples. DBT concentrations were quantified using a
were otherwise identical to the previous trials. calibration curve.
Each photooxidation trial was repeated in the presence of During the course of these experiments, it became apparent
the photocatalyst. One catalyst slide was placed in each sam- that the tetradecane solvent, as supplied, contained aromatic im-
ple tube, oriented so that one side of the slide would receive purities, possibly including DBT. This was evidenced by a peak
maximum irradiance from the lamps. These trials were labeled with the same retention time as DBT that was present even
1-254-CAT and 1-300-CAT, respectively. The trials were other- during blank injections. This is hardly surprising, considering
wise identical to the noncatalyzed trials. An additional sample, the presence of DBT in most hydrocarbon feedstocks. In order
consisting of a foil-wrapped tube with a catalyst slide, was sub- to determine the actual concentration of the solutions, rather
jected to air bubbling for 8 h. than simply the amount of DBT added, the HPLC calibration
An 8-h oxidation trial was performed using Degussa P25 as was performed using only ethanol as a solvent, without tetrade-
photocatalyst. This trial was labeled 1-254-P25. Three samples cane.
were prepared using 10.0 mg of P25. Three more were prepared Qualitative determination of photooxidation products was
using 20.0 mg. The samples were subjected to the same air bub- performed by reverse phase HPLC on a Waters 2695 with a
bling and irradiation conditions as in trial 1-254. At the end of Waters 996 photodiode array detector and an RP-18 column
irradiation, samples were filtered to remove suspended TiO2 , (LiChrospher 100 packing, 5-µm diameter, 150-mm length).
and placed in taped vials. The mobile phase was a mix (75/25) of acetonitrile and water,
with a flow rate of 0.6 ml/min. Solutions were injected using an
2.2.2. Adsorption of DBT and products of its oxidation autoinjector with an injection volume of 10.0 µl. Catalyst slides
on silica and spent silica gel were rinsed with HPLC grade acetonitrile,
An adsorption isotherm for DBT on silica was measured to remove adsorbed products. These solutions were injected
at room temperature. Silica gel (40 mesh) was obtained from onto the HPLC column. Retention times were compared with
Baker. Solutions were made with DBT concentration varying standards of DBT and DBT sulfone, also in acetonitrile.
128 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135

2.2.5. Adsorption of nitrogen The structural parameters calculated from the isotherms are
On the catalysts, sorption of nitrogen at its boiling point was listed in Table 1. The total pore volume of the Degussa P25 sam-
carried out using ASAP 2010 (Micromeritics). Before the ex- ple is twice that of TiO2 . In spite of this, the micropore volume
periments, the samples were outgassed at 120 ◦ C to constant and total surface area of TiO2 are about 20 and 37% greater,
vacuum (10−4 Torr). From the isotherms, the surface areas respectively. This is the result of 20% higher volume of micro-
(BET method), total pore volumes, Vt (from the last point of pores in the synthesized sample than in P25. The surface area
isotherm at relative pressure equal to 0.99), volumes of micro- and volume of pores are critical components of a photocatalyst,
pores, Vmic , mesopore volumes, and Vmes , along with pore size since catalysis is assumed to take place only for molecules on
distributions, were calculated. The last three quantities were or near the surface. Pore diameter is also important, since mole-
calculated using density functional theory, DFT [20,21]. cules are expected to accommodate more effectively in pores
whose diameter is close to that of the molecule. As expected
2.2.6. Thermal analysis based on the shape of isotherms, the hectorite sample has a
Thermal analysis was carried out using TA Instrument high surface area, reaching 377 m2 /g, and a very high volume
Thermal Analyzer. The instrument settings were heating rate of micropores with small average diameter. The data indicate
10 ◦ C/min and an air or nitrogen atmosphere with 100 ml/min that the interlayer space of hectorite is accessible for the ni-
flow rate. For each measurement about 25 mg of a ground cat- trogen molecule and the significant volume of pores is formed
alyst sample were used. between the small hectorite particles. The mineral significantly
differs from montmorillonite in its primary and secondary pore
2.2.7. SEM structure [22].
Scanning electron microscopy was performed on a Hitachi Fig. 2 shows the distribution of pore sizes in the two cat-
S-4700 cold field emission instrument. The accelerating volt- alysts and the hectorite calculated using the DFT method. As
age was 2000 V. Scanning was performed in situ on a section expected, a majority of the pore volume of P25 is composed of
of a catalyst slide (CAT), as well as on TiO2 powder and hec- large pores, with an average diameter of around 30 nm. Con-
torite. versely, a large portion of the TiO2 pore volume consists of
pores in a size range around 3–10 nm. These micropores ac-
3. Results and discussion count for the larger surface area of the catalyst, even while
the material seems to be more dense than P25. In the case of
Nitrogen adsorption isotherms are presented in Fig. 1. Their hectorite the PSD indicates a high degree of heterogeneity for
the pore structure of this materials. Besides micropores smaller
shape indicates that significant differences in surface texture
than 2 nm, a significant volume exits in pores between 3 and
exist. Although the isotherms for titania samples are type II
10 nm.
of the IUPAC classification, the Degussa P25 titania adsorbs
much more nitrogen at higher pressure, indicating that its pores Table 1
are much larger than those in TiO2 . Nitrogen uptake of the lat- Structural parameters of the catalysts calculated from nitrogen adsorption
ter sample is greater at low pressure, which is related to the isotherms
presence of larger pore volumes and surface area. The nitrogen Sample SBET Vt Vmic Vmes L
adsorption isotherm on hectorite also represents type II but the (m2 /g) (cm3 /g) (cm3 /g) (cm3 /g) (Å)
volume of pores is much higher than for titanium oxide materi- Degussa P25 64 0.167 0.019 0.148 104
als. Hectorite 377 0.262 0.163 0.099 30
TiO2 catalyst 89 0.082 0.023 0.059 37

Fig. 1. Nitrogen adsorption isotherms. Fig. 2. Pore size distributions.

 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135 129

Fig. 3. SEM images: CAT (A–D), P25 (E), and hectorite (F). Magnification bars: A—200 nm; B—100 µm; C—1 µm; D—200 nm; E—4.44 µm; F—2.22 µm.

Fig. 3 presents SEM images of the materials studied. As can for the large surface area of the catalyst, while the small size of
be clearly seen, the surface of CAT cannot be described as a the individual crystals leads to greater microporosity.
homogeneous layer of material (Figs. 3A and 3B). Rather, it The phase composition of TiO2 on the catalyst slides was
is made up of agglomerations of nanoscale particles of hec- determined by X-ray diffraction. Because the catalyst was
torite (outer layer), stuck together into features, which are in mounted on quartz, it was possible to insert it directly into the
some cases nearly a micrometer across. The individual crystals XRD instrument. Fig. 4 shows the X-ray diffraction spectrum
appear to span a range of about 15–40 nm. The micrographs of a catalyst slide over a 2Θ range from 3◦ to 49◦ . This range
presented in Fig. 3 are in marked contrast to the results of Ko- covers three of the most intense anatase peaks, as well as two
tov et al. [13]. One reason for this is in the use of hectorite of the most intense rutile peaks. As Fig. 4 shows, the catalyst
instead of montmorillonite. As mentioned above, based on the reveals well-defined peaks corresponding to the anatase crystal
high volume of large pores, the hectorite tends to form agglom- structure, with no significant corresponding rutile peaks. The
erates of particles (Fig. 3F). This process hinders the formation absence of the most intense rutile peak suggests that the cat-
of monolayers of TiO2 . Another reason is likely variation in alyst material is essentially entirely anatase. The broad hump
the layering process itself. Even in the case of pure titania cat- from about 16◦ to 30◦ indicates that at least some of the mate-
alysts, Degussa P25 (Fig. 3E), the micrograph suggests crystal rial is still in an amorphous state and may be related to the thin
growth by progressive agglomeration. The resulting structures layer of hectorite. for which diffraction peaks are rather broad.
show treelike complexity, rather than the smooth layering ob- In the case of Degussa P25 the mixture of anatase and rutile is
served by Kotov et al. When the film layer is broken (Fig. 3C), detected.
the spheres of TiO2 is revealed with sizes between 30 nm and X-ray diffraction can also be used to estimate average crys-
1 mm. They are located between the layers of hectorite, forming tallite size using the Scherer equation [23]. When the most in-
a sandwich structure. These complex structures are responsible tense peak for our catalysts at 25.4◦ , is used for calculation, the
130 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135

Fig. 4. XRD patterns for the samples studied.

calculated particle size is about 32 nm. This is in good agree- Fig. 5. DTG curves in air.
ment with the range of particle sizes seen in the SEM images
(Fig. 3). In the case of P25 and hectorite the particle sizes are
found to be about 12 and 30 nm, respectively, which is also in
agreement with the SEM analysis.
To get a better picture of the phase changes of the catalyst,
differential thermal analysis was performed. Uncalcined TiO2
powder, P25 and hectorite were analyzed. Figs. 5 and 6 show
the resulting DTG and DTA graphs, respectively. The DTG
curve for TiO2 shows an initial decrease in mass represented
by the peak at about 120 ◦ C, which represents the loss of ad-
sorbed water from the surface of the powder. The final weight
of the powder was consistently between 70 and 75% of the orig-
inal weight. The typical weight loss of the coated catalysts was
around 20 to 25%. Some of this difference is likely caused by
the presence of hectorite on the slides, which contributes to the
total mass but does not account for the mass change to the same
degree. TG analysis of dry hectorite powder showed a 17% Fig. 6. DTA curves in air.
decrease in mass up to 400 ◦ C. In addition, it is possible that
the coated slides do not recrystallize completely during calci- decline in mass may be a result of these groups being released
nation. suddenly as the material recrystallizes.
The DTA curve for TiO2 shows two large exothermic peaks The results of TA analysis for P25 show a weight loss due
around 270 and 425 ◦ C, with a smaller peak at 350 ◦ C (Fig. 6). to loss of adsorbed moisture, as well as a second loss around
The 425◦ peak is accompanied by a sharp decrease in mass. 270 ◦ C. This DTG peak, unlike the corresponding one for our
This would normally indicate some sort of outside interference catalyst, is related to an endothermic effect (Figs. 5 and 6). The
with the instrument. Repetition of the experiment showed the mass leveled off near the minimum just above 400 ◦ C, though
same results. The drop in mass is therefore believed to be char- there is an increase in the intensity of the endothermic effects
acteristic of the material. Temperature spikes such as these may around 800 ◦ C. As XRD indicated (Fig. 4), Degussa P25 is a
be caused either by changes of state or by chemical reactions mixture of anatase and rutile phases of TiO2 . Unlike our cata-
occurring in the sample. The amorphous titania is known to lyst, which forms as an amorphous powder, P25 is purchased
undergo a reorganization of crystal structure to form the pre- as an essentially crystalline material. Hence, it did not exhibit
dominately anatase phase during calcination. The experiment the more complex behavior of the amorphous powder when ex-
was repeated using nitrogen, rather than air. Three tempera- posed to heat treatment.
ture peaks were still apparent, though at slightly higher furnace To properly account for the effect of radiation on DBT re-
temperatures. The relative intensity of the peaks changed, with moval, the dark trial, 1-DARK, was performed. In this trial, a
the 375 ◦ C peak being the most prominent. The 450 ◦ C peak 200 ppm solution of DBT was subjected to gas bubbling (air
was considerably smaller, and there was no corresponding steep and moisture) in the absence of light and catalysts. No signifi-
change in mass. This seems to indicate that the change in mass cant loss of DBT was found. Therefore, it is concluded that any
is linked to an oxidation reaction. The amorphous titania should decrease in DBT concentration in subsequent trials is the result
include ethano, aqua, hydroxo, and isopropoxo ligands, which of photooxidation reaction.
are removed during the calcination process. It is reasonable that The results of the photolysis experiments are summarized
such groups could be burned in the presence of air. The steep in Fig. 7 and Table 2. Final concentrations of DBT under trial
 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135 131

(A)

Fig. 7. Changes in DBT concentration with time for various trials.

Table 2
Summary of the photolysis experiments
Trial Order of Rate Final [DBT] Final [S] % DBT
reaction constanta (ppm) (8 h) (ppm) (8 h) removal
2-300 First 0.11 79 14 60
Zeroth 14.80
2-254 First 0.17 53 9 73
1-300-CAT Zeroth 16.25 69 12 66
First 0.12
1-254-CAT First 0.25 29 5 86
1-254-P25-10 Unknown Unknown 40 7 80 (B)
1-254-P25-20 Unknown Unknown 43 7 78
a First-order rate constants are in ppm−1 h−1 . Zero-order rate constants are
in h−1 .

1-300 averaged 80 ppm. This is the equivalent of about 14 ppm

sulfur and constitutes reaction of 60% of starting DBT. Data
presented in Fig. 7 suggest that the photooxidation of DBT in
1-300 is first order with respect to DBT, as expected for low
concentration for Langmuir–Hinshellwood kinetics at low con-
centrations. This is in apparent contrast with the results of Hirai
et al. [5], who used a starting concentration of DBT of 2–4 g/L
(2650–5300 ppm of sulfur) and found a zero-order rate. This
discrepancy is a result of the concentration differences. For
semiconductor-catalyzed photoreactions zero order is expected
at high concentrations. It is also significant that according to
the results of Hirai et al. [5], the pure tetradecane solution ap- (C)
pears to obey a first-order rate law. In fact, several of the figures
depicting the biphasic system also appear to tail off near the Fig. 8. UV spectra of the DBT solution before photooxidation (A), after pho-
end at very low concentrations. These low concentrations are tooxidation (B), and after photooxidation followed by adsorption onto sil-
more consistent with the conditions reported here. According to ica (C).
Salem [12], the mechanism of the reaction is likely the produc-
tion of conduction-band holes in the TiO2 photocatalyst, which HPLC results, in addition to being a tool for concentration
could then interact either with the organic substrate (in our case, determination, yield a hint to the products of photooxidation.
DBT) or with an inorganic oxidant, including O2 , to form radi- The peak that appeared at a retention time of about 2.1 min grew
cals. in height with the course of the reaction, reaching a maximum
132 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135

near 30 mAU. The primary quantitative results were obtained

using UV spectrophotometry. Fig. 8A shows a typical UV spec-
trum for DBT at a concentration of 200 ppm. Four main peaks
are visible. Of these four, the 313- and 326-nm peaks show
a linear dependence on DBT concentration over the range in-
vestigated. Following photooxidation, a number of changes are
observed in the spectrum of the sample solutions (Fig. 8B). An
increase in absorbance at 326 nm was recorded with increas-
ing irradiation, along with the emergence of maxima at 304 and
310 nm. Due to the intensity and closeness of the peaks, how-
ever, it was not possible to resolve them.
To test the separation method, the solution after irradiation
was mixed with silica gel powder, shaken, and left for 75 min
to allow adsorption of the oxidation products (DBT is not ad-
sorbed onto silica). Fig. 8C shows the spectrum of the same
solution as in Fig. 8B but after the adsorption process. The
remaining four peaks are the same four peaks that are character-
istic of DBT. It is important to note that it is not certain whether
there are any compounds other than DBT remaining in solution
after adsorption. In that event, the data presented here would
represent an overestimate of the amount of DBT remaining in
solution. However, the similarity of the spectra in Figs. 8A and
8C suggests that any contributions from other compounds are
minimal.
In addition to the evidence from UV spectroscopy, two other
observations support the hypothesis of nearly complete product
removal. During photooxidation, the sample solutions became
increasingly yellow, in accord with the observations of Hirai
et al. [5]. After adsorption onto silica, the solutions returned to a
nearly colorless state (Fig. 9A). Moreover, during the process of
photooxidation, some of the products adsorbed onto the catalyst
slides. This adsorption of the products resulted in a yellowing
(darkening in the photos) of the slides, as shown in Fig. 9B. Fig. 9. Changes in the color of the DBT solutions exposed to photooxidation
The slide on the left is unused, while that on the right was used and silica adsorption (A); changes in the color of the CAT after exposure to
for 8 h of photooxidation at 254 nm. Adsorption likely occurs photooxidation (B).
on hectorite owing to its high surface area and pore volume.
This phenomenon can be technologically advantageous from DBT from the original solution. As with the 300-nm trial, there
the point of view of removal of oxidation product but, on the is some variation in the calculated concentrations of DBT at
other hand, it may prevent the reuse of the catalyst. each irradiation time. Of note is the variation between the 4-h
The results of trial 2-300, plotted in Fig. 7, indicate that the samples. It is significant that the concentrations appear to come
photooxidation may either follow a zero- or first-order rate law in pairs, with samples 4A and 4B showing significantly differ-
with respect to DBT. A zero-order fit again results in a slightly ent concentrations than 4C and 4D. Samples 4A and 4B were
lower R 2 value (0.985). First-order dependence on the substrate present at the same time in the reaction chamber, while 4C and
is to be expected in the case of single-photon direct photolysis. 4D were present during a different 4-h period. This suggests
In this sort of mechanism, the rate-limiting step is presumed that some unknown variable may be responsible for this dis-
to be n–π ∗ excitation of the substrate, followed by rapid reac- crepancy. Unlike the 300-nm trials, the rate for 2-254 shows
tion of the excited intermediate to form a series of products. clear first-order dependence on DBT. A zero-order fit gives an
Because oxidant concentrations and irradiation intensity were R 2 of only 0.90. The rate constant for the 254-nm reaction is
kept essentially constant, a first-order rate is reasonable. From calculated to be 0.1690 ppm−1 h−1 .
a linear least-squares fit of the data in Fig. 7, the pseudo-first- For the 1-300-CAT, after 8 h of irradiation in the presence
order rate constant under these conditions was determined to of the catalyst, the average concentration of DBT decreased to
be 0.1149 ppm−1 h−1 . On the other hand, trial 2-254 shows 69 ppm DBT (Fig. 7). This is equivalent to 12 ppm sulfur, a
a clearer first-order rate dependence than the 300-nm trials removal of 66% of the original DBT. Like the uncatalyzed tri-
(Fig. 7). A greater decrease in the concentration of DBT over als, the catalyzed reaction could appear to follow either a zero-
time is observed. The 8-h irradiated samples showed an aver- or first-order rate law with respect to DBT. However, the first
age final concentration of 53 ppm DBT, which is equivalent to order regression fit is in this case worse than the zero-order
about 9 ppm sulfur. This represents a removal of 73% of the (R 2 = 0.977). The first-order rate constant is 16.25 ppm−1 h−1 .
 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135 133

Table 3
Results of photolysis on Degussa P25 titanium oxide
Sample Mass of catalyst Irradiation time Absorbance [DBT] Absorbance [DBT] [DBT] (Avg)
(mg) (h) at 326 nm (ppm) at 313 nm (ppm) (ppm)
Initial 0 0 199
1-254-P25-10A 10 8 0.4598 36 0.4427 47 42
1-254-P25-10B 10 8 0.4316 34 0.4009 43 38
1-254-P25-20A 20 8 0.4735 37 0.4711 50 44
1-254-P25-20B 20 8 0.4743 37 0.4496 48 43

If the rate of reaction is in fact independent of the concentra- of the two samples are essentially the same compounds and thus
tion of DBT, it would be consistent with the general mechanism supports the hypothesis that oxidation at 254 nm is primarily a
for TiO2 -catalyzed photooxidation given by Salem [12], as well result of direct photolysis.
as the mechanism proposed by Abdel-Wahab and Gaber [15]. Table 2 summarizes the results of the photooxidation trials.
Both of these mechanisms involve primary excitation of TiO2 Possible rate constants are listed for all fits yielding an R 2 value
electrons to produce photochemical holes and conduction-band better than 0.95, with the best fit listed first. As demonstrated in
electrons. DBT molecules adsorbed onto the surface of the cata- the table, all of the catalyzed trials showed an improved rate of
lyst then react with either holes or electrons to lead to oxidation reaction over the corresponding uncatalyzed trials. Between the
products. The rate of this reaction mechanism is dependent on catalysts tested, the layered catalyst showed somewhat higher
the light intensity and surface area of the catalyst, but not on efficiency than Degussa P25 at 254 nm. Although the percent-
the substrate concentration. Because DBT has a much lower age of DBT removed was relatively close, it is significant that
absorbance around 300 nm, the primary mechanism for pho- our catalyst slides contained no more than 9 mg of catalyst for
tooxidation at this wavelength appears to be indirect photoly- any trial. All of the 254-nm trials showed first-order rate de-
sis. pendence on the concentration of DBT, while the 300-nm trials
In the case of trial 1-254-CAT, after 8 h of photolysis (fol- may be either first or zero order in DBT.
lowed by adsorption onto silica) the average concentration of In all cases, removal of DBT was greater with the 254-nm
DBT was reduced to 29 ppm. This is 5 ppm sulfur, a removal of lamps than with the 300-nm ones. However, this result does
86% of the original DBT. This is a substantial reduction from not necessarily indicate the superiority of irradiation at 254 nm.
the 53 ppm result from trial 2-254. This trial also showed sig- The 254-nm lamps used in these experiments were estimated to
nificant variation between replicates, which can be attributed to have about twice the intensity of the 300-nm lamps. Assum-
both variation between the lamps and slight positioning varia- ing single-photon excitation of DBT, the rate would depend
tions for the catalyst slides. Interestingly, for this sample, the directly on the intensity of incident radiation, as well as on
data cannot be fitted to a zero-order curve like that used for the the absorptivity coefficient at the incident wavelength. The ab-
300-nm catalyzed data (R 2 = 0.847). A first-order rate expres- sorbance of DBT is somewhat higher at 254 nm than at either
sion, however, successfully explains the results. A first-order 313 or 325 nm. This would lead one to expect a rate constant for
rate constant of 0.2497 ppm−1 h−1 was calculated for the con- 254 nm at least double that of the 300 nm lamps. This was not
ditions in this experiment. the case in these experiments. The apparent first-order depen-
Table 3 collects the data from trial 1-254-P25, which was dence on DBT concentration for the 254-nm reaction suggests
performed using Degussa P25 photocatalyst. Over the course of a different mechanism than that proposed for the 300-nm reac-
8 h, the samples containing 10 mg of P25 reacted all but 40 ppm tion. The rate constant of the catalyzed reaction is 44% larger
of sulfur. The amount of DBT remaining in these solutions is than that for the uncatalyzed trial. Hence, it is reasonable to
less than the 53 ppm remaining in the uncatalyzed samples, but conclude that the catalyst did have an effect. The dark trial with
more than the 29 ppm remaining after 8 h of irradiation with the catalyst demonstrates that the catalyst did not simply ad-
the quartz-supported catalyst. It is important to mention here sorb the additional DBT, since that sample showed no decrease
that the maximum mass of the layered material present in any in DBT concentration in the absence of light.
of the catalyst trials was 8.4 mg, where titania makes up only One possible explanation of the result is that the reaction
a fraction of this mass. Interestingly, the samples with much proceeds by multiple pathways under irradiation at 254 nm.
more P25 catalyst did not remove more DBT than those with The dominant pathway is the first-order direct photooxidation
10 mg. This suggests that the surface area present in 10 mg was of DBT. In addition, the presence of the photocatalyst allows
sufficient to perform whatever catalysis occurred. Alternately, it for additional indirect photolysis to occur on the surface of the
may simply be due to a limitation of the use of suspended TiO2 . TiO2 . This results in a higher overall removal rate, with pre-
It is difficult to maintain large amounts of suspended catalyst for dominately first-order rate dependence.
long periods of time, even with constant agitation. To analyze these adsorbed products, spent catalyst slides and
Comparison of the UV spectra for a solution irradiated for silica were rinsed with three times 3 ml of acetonitrile. The
8 h at 254 nm, in the absence of catalyst, and 20 mg of P25 resulting solutions were analyzed by HPLC. This analysis con-
shows that peaks are nearly identical in shape, with only a slight firmed the presence of products significantly more polar than
difference in their height. This indicates that the major products the DBT starting material. The standards used were DBT and
134 J. Robertson, T.J. Bandosz / Journal of Colloid and Interface Science 299 (2006) 125–135

4. Conclusions

The results presented here indicate that the applied proce-

dure produces an effective photocatalyst for the removal of
dibenzothiophene from nonpolar organic solvent. At 300 nm
in the presence of catalyst, photooxidation appears to proceed
primarily by indirect photolysis, according to a zero-order rate
law. At 254 nm the rate is determined primarily by first-order
direct photolysis, though the presence of the catalyst contributes
(A)
to a greater overall rate of removal. Coupled with adsorption of
oxidation products by silica adsorption, the process presented
here is capable of reducing sulfur concentrations below the tar-
get level of 10 ppm.
The catalyst synthesized was not, as previously expected, a
series of alternating monolayers. Rather, the results indicate a
complex structure of agglomerated nanoparticles. This struc-
ture leads to a high degree of microporosity, with a correspond-
ingly high surface area. These features suggest the synthesized
catalyst may perform with greater efficiency than the commer-
(B) cially available Degussa P25.
Under the conditions tested, irradiation at 254 nm appears
to be more effective than irradiation at 300 nm in removal of
DBT. However, due to the uncertain order of the rate of the
300 nm reaction, further experiments are warranted to deter-
mine if a change of conditions would improve the photolysis
yield of the 300 nm process. Specifically, higher intensity lamps
and a higher starting concentration of DBT, as well as the pres-
ence of naphthalene, may favor the 300 nm reaction.

(C) Acknowledgments

Fig. 10. Examples of the chromatograms used for qualitative determination of

The authors gratefully acknowledge the assistance of Dr.
the effects of photooxidation.
James T. Yardley and Dr. Richard Harniman of the Columbia
University Nanocenter in producing SEM images. We are also
DBT sulfone. These compounds eluted at 8.1 and 2.5 min, re-
indebted to Dr. Jeffrey Steiner and Karin Block of the City Col-
spectively. In HPLC analysis of the compounds extracted from
lege Earth and Atmospheric Sciences Department for assistance
silica, an array of compounds was eluted in rapid succession.
with XRD. The help of Dr. Stanislaus Wong (Brookhaven Na-
All of the compounds eluted before DBT, and some even earlier
tional Laboratory/SUNY), Tirandai Hemray-Benny of SUNY,
than DBT sulfone (Fig. 10). While the product peaks were not
and Dr. Jorge Morales of CCNY in obtaining the SEM images
resolved, some qualitative information was obtained. Clearly, a
of CAT, Degussa P25, and hectorite is appreciated.
number of compounds were produced as a result of photoox-
idation [9]. One peak corresponds well to the retention time
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