Accepted Manuscript

Conversion of toluene into benzyl radical on anatase TiO2 (001) surface

Murugaiyan Sowmiya, Kittusamy Senthilkumar

PII: S2210-271X(17)30289-X
DOI: http://dx.doi.org/10.1016/j.comptc.2017.06.002
Reference: COMPTC 2538

To appear in: Computational & Theoretical Chemistry

Received Date: 14 April 2017

Revised Date: 1 June 2017
Accepted Date: 1 June 2017

Please cite this article as: M. Sowmiya, K. Senthilkumar, Conversion of toluene into benzyl radical on anatase
TiO2 (001) surface, Computational & Theoretical Chemistry (2017), doi: http://dx.doi.org/10.1016/j.comptc.
2017.06.002

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 Conversion of toluene into benzyl radical on anatase TiO2 (001) surface

Murugaiyan Sowmiya and Kittusamy Senthilkumar *

Department of Physics, Bharathiar University, Coimbatore, India-641 046.
*Corresponding author: Fax No: +91-422-2422387, E-Mail: ksenthil@buc.edu.in
Abstract
In this study, the initial step of toluene dissociation, that is, the formation of benzyl

radical through the reaction with hydroxyl group on anatase (001) surface is investigated

using density functional theory calculations. The calculated results show that the toluene is

physisorbed on the pristine TiO2 surface, and it is converted into benzyl radical when it

interactiing with surface hydroxyl groups through methyl group of toluene. It has been found

that the interaction between toluene and TiO2 surface through OH group is enhanced by the

presence of Ag tetramer. The calculated reaction energy profile shows that the reaction

associated with conversion of toluene into benzyl radical on TiO2-OH and TiO2-OH-Ag

surfaces is highly exothermic with an activation energy barrier of 0.56 and 0.53 eV,

respectively. The results obtained from this work reveal that the toluene dissociation on TiO2

surface is possible only through the surface hydroxyl groups and the presence of Ag tetramer

augments the dissociative reaction.

Keywords: Toluene, Hydroxyl group, Anatase (001) surface, Ag cluster, Interaction

1
1. Introduction

Volatile organic compounds are major components of indoor air pollution[1, 2].

Photocatalytic oxidation process is an economical and environmentally friendly approach

used to remove the pollutant by transforming the hazardous compounds into harmless

compound. Among the semiconductor photocatalysts, titanium dioxide (TiO2) is the most

appropriate candidate for photocatalytic processes due to its powerful oxidation properties,

superior charge transport properties and corrosion resistance [3-9]. In particular, anatase TiO2

is preferred over rutile because of its higher photocatalytic activity[10-13] and electron

mobility,[14, 15] thus allowing charge diffusion pathways of photogenerated carriers and

increased quantum efficiency. The type of crystal structure is one of the crucial aspects that

responsible for the reactivity of the catalyst. The crystal structure of anatase TiO2 is a

truncated square bipyramid and consisting majority (101) and minority (001) facets. A

number of studies have reported that the anatase (001) facet is chemically more reactive than

(101) surface [16-21]. Chen et al. have synthesized the anatase crystals with nearly 100 %

exposed (001) facet [22]. Therefore, in the present work we have studied the dissociation of

toluene on anatase (001) surface.

A number of studies have reported that the hydroxyl group on anatase TiO2 will act as

an active site for the dissociation of air pollutants[23-29]. Based on the results obtained from

X-ray photoelectron spectroscopy technique, Bianchi et al.[24] reported that the high OH

concentration on the TiO2 surface will enhance the degradation of toluene. Zhang et al.[27]

studied the photocatalytic degradation of gaseous toluene on TiO2 surface using experimental

techniques, and reported that the surface hydroxyl group is essential for the degradation of

toluene. Recently, Wang et al.[30] studied the adsorption of toluene on anatase TiO2 (101)

and (001) surfaces using experimental and theoretical methods, and concluded that the

degradation efficiency of anatase (001) facet is higher than that of anatase (101) surface. In
2
the same study, Wang et al.[30] reported that the anatase TiO2 (001) surface has high

capability to generate more number of surface OH groups due to the presence of fully

unsaturated five coordinated titanium atoms. However, the photocatalytic degradation of

toluene by TiO2 has some limitations, such as the low utilization efficiency of solar energy

and rapid recombination of photo generated charge carriers. Numerous studies have reported

that the deposition of noble metals on TiO2 will enhance the photocatalytic activity due to

their ability to act as both an electron donor and acceptor to increase the electron-hole pair

separation efficiency of TiO2[31-33]. A previous study shows that the degradation efficiency of

Ag doped TiO2 is higher than pure TiO2 for toluene degradation[34]. Based on the

experimental techniques, Pham et al.[35] found that the Ag–TiO2/PU has good photocatalytic

efficiency for toluene degradation under visible light.

The primary step in the toluene degradation on TiO2 with hydroxyl group is formation

of benzyl radical by breaking of C-H bond in the methyl group. In the present work, we have

studied the conversion of toluene into benzyl radical on anatase TiO2 (001) surface using

density functional theory calculations. First, we quantify the interaction of toluene with

pristine TiO2, TiO2-OH and TiO2-OH-Ag surfaces and then second, we have studied the

reaction pathway for conversion of toluene into benzyl radical by identifying the transition

state and calculating the activation energy barrier by using climbing image nudged elastic

band (CI-NEB).

2. Computational details

The density functional theory calculations are performed using the projector

augmented wave (PAW) method as implemented in the Vienna ab initio simulation package

(VASP) [36-38]. The exchange-correlation interactions are treated by generalized gradient

approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) [39, 40] functional. The valence

orbitals are calculated as linear combinations of plane waves, and the size of the basis set is
3
determined by a cutoff energy of 400 eV. In all the DFT calculations, a 5x5x1 Monkhorst-

Pack [41] k-point grid is used for sampling the Brillouin zone. To accelerate the convergence,

a Methfessel-Paxton smearing of the Fermi surface is employed with a smearing width of

0.2 eV. The constructed TiO2 (001) surface is composed of five-fold Ti (Ti5+), two-fold

O (O2-) and three-fold O (O3-) atoms. In the present study, we utilized a 3x3 surface supercell

containing four O-Ti-O layers, which is allowed to relax until the total energy difference

between the loops is less than 1 meV and force is less than 0.02 eV/Å. A vacuum region of

10 Å is used to avoid periodic image interactions between the slabs of TiO2 surface. The

interacting stable configurations of TiO2 surface with OH group, Ag tetramer and toluene

were obtained by using the following procedure, initially we have optimized the isolated OH,

Ag tetramer, and toluene, and then the most interacting configuration for toluene and Ag

tetramer on anatase (001) surface with and without OH group is obtained through geometry

optimization. During the geometry optimization of interacting configurations, the bottom two

layers of the TiO2 surface is kept fixed, and the top two layers of the TiO2 surface and

adsorbate are allowed to relax. The interaction energy, E int is calculated as the energy

difference between total energy of the interacting system and sum of the energy of the

individual systems. The PBE functional with Grimme's [49] D2 correction is also used to

calculate the adsorption energy. In this method a semiempirical dispersion potential is added

with the conventional Kohn-Sham DFT energy obtained with PBE functional.

3. Results and discussion

3.1. Toluene interaction on pristine TiO2 surface

The optimized structure of toluene molecule and clean anatase (001) is shown in

Figure 1. Initially, we have studied three different interacting configurations, Tol1, Tol2 and

Tol3 for the interaction of toluene with anatase (001) surface, and then optimized structure is

shown in Figure 2. The interaction energy of studied configurations is in the range of 0.96 to
4
1.15 eV, indicating a very weak interaction between toluene and pristine TiO2. Bader charge

analysis show that a negligible amount of charge is transferred between toluene and TiO2,

and there is no significant structural change on the adsorbed toluene molecule due to the

interaction with TiO2. The above results clearly show that the toluene molecule will not

dissociate on the pristine TiO2 surface.

Ortho ( o )

Meta ( m )

Para ( p )
(a) (b)

Figure 1. Optimized structure of (a) toluene and (b) anatase TiO2 (001) surface. The blue,
red, green and yellow colors represent Ti,O, C and H atoms, respectively.

Table 1. Interaction energy of different configurations of adsorbates on anatase TiO2 (001)

surface calculated using PBE method.
Configuration Interaction Energy ( Eint ) in eV
Tol1 1.04
Tol2 1.15
Tol3 0.96
TolOH1 -0.73
TolOH2 -0.57
TolOH3 -3.3
Ben -7.92
TolOHAg1 -0.91
TolOHAg2 -0.66
TolOHAg3 -3.92
BenAg -8.47

5
 Tol1 Tol2

Tol3

Figure 2. Optimized structure of interacting configurations of toluene on pristine anatase

TiO2 (001) surface.

Further, we have studied the flat orientation of toluene on TiO2 and TiO2-OH surfaces

and the calculated results show that the interacting configurations are found to be unstable

with the interaction energy in the range of 2.25 to 2.96 eV, and the distance between toluene

and TiO2 surface is around 3.6 Å.

6
3.2. Toluene interaction on TiO2 surface with OH groups

To study the interaction of toluene with OH groups on TiO2 (TiO2-OH) surface, we

have studied four configurations, TolOH1, TolOH2, TolOH3 and Ben. The optimized

geometry of studied configurations are shown in Figure 3 and the interaction energies are

presented in Table 1. The selected structural parameters and Bader atomic charges are

summarized in Tables S1 and S2, respectively. As shown Figure 3, the two OH groups are

interacting with Ti atoms of TiO2 with the Ti-OOH distance of 1.93 Å. In the TolOH1

configuration, the hydrogen atom attached with ortho ( o ) and meta ( m ) carbon atoms of

toluene are interacting with the surface hydroxyl group. In the TolOH2 configuration, the

hydrogen atom attached with the para ( p ) carbon atom is interacting with the surface

hydroxyl group. In these two adsorption configurations, there is no significant change in

structural parameters of the toluene molecule on TiO2-OH surface. The calculated interaction

energy for TolOH1 and TolOH2 adsorption configurations is -0.73 and -0.57 eV. Further, it

has been found that there is no significant charge transfer between toluene and TiO2-OH

surface in the TolOH1 and TolOH2 adsorption configurations, which indicates that in these

configurations toluene is very weakly interacting with TiO2-OH surface through hydrogen

atom of the o , m and p carbon atoms. In TolOH3 configuration, the methyl group of

toluene is pointing towards the hydroxyl groups on the TiO2 surface. The calculated structural

parameters show that the C7-H7 bond distance slightly increased by about 0.02 Å with

respect to the isolated molecule and there is no significant amount of charge is transferred

from toluene to TiO2-OH surface. It has been found that the TolOH3 configuration is the

most interacting configuration for the toluene molecule on TiO2-OH surface with the

interaction energy of -3.3 eV.

In Ben configuration, the methyl group of toluene molecule is interacting with the

surface hydroxyl group. In this configuration, the hydrogen atom of methyl group is cleaved
7
and binds with the hydroxyl group, which results the formation of benzyl radical and water

molecule on the TiO2 surface. The calculated interaction energy for this configuration is

-7.92 eV. It is noted that the C1-C7 bond distance of toluene is contracted by about 0.1 Å,

and the C1-C6 bond distance is elongated by about 0.03 Å with respect to the isolated toluene

molecule (see Table S1). The distance between C7 and H7 atoms of toluene molecule in the

Ben adsorption configuration is 1.83 Å, which is higher by about 0.7 Å with respect to the

isolated toluene.

(a) (b)

(c) (d)
8
 (e)

Figure 3. Optimized structure of (a) TolOH1, (b) TolOH2 (c) TolOH3 and (d) Ben
(e) Electron density difference plot of Ben configuration. Blue isosurface represent the
decrease in electron density and red isosurface represent the increase in electron density.

Upon the interaction of toluene with TiO2-OH surface the distance between titanium

and oxygen atom of OH group increases by 0.32 Å. Electron density difference plot shown in

Figure 3e indicates that a significant amount of charge depletion on the toluene and charge

accumulation around newly formed water molecule. Similarly, from the Bader charge

analysis, it has been found that the oxygen atom of hydroxyl group gains the charge by about

~0.2 e from the methyl group and titanium atom. The above results show that the hydroxyl

group on TiO2 is acting as effective Lewis acid adsorption site and toluene molecule is

converted into benzyl radical and water when the methyl group of toluene is interacting with

hydroxyl group on the TiO2 surface and is in agreement with the previous experimental

findings [27].

We have also studied the interaction of toluene with pristine TiO2 and TiO2-OH

surfaces using PBE-D2 method and the optimized geometry of the interacting configurations

are shown in Figures S1 and S2. The calculated interaction energies are summarized in Table

S3. The optimized structure of the interacting configurations of toluene on TiO2 and TiO2-OH

9
surfaces at PBE-D2 method is similar to the structure obtained with pure PBE, however, the

distance between the interacting atoms is decreased by about 0.05 to 0.26 Å with the PBE-D2

functional. As given in Table S3, the interaction energy calculated with PBE-D2 method is

increased by about 0.5 to 0.7 eV with respect to the values calculated from pure PBE

functional. In agreement with the PBE results, the PBE-D2 results show that the toluene

molecule is converted into benzyl radical and water when the methyl group of toluene is

interacting with hydroxyl group on the TiO2 surface. That is, the trend of the interaction is

similar in both pure PBE and PBE-D2 methods.

3.3. Toluene interaction on TiO2-OH-Ag surface

In order to investigate the effect of Ag cluster on toluene dissociation on TiO2-OH

surface, we have studied the interaction of toluene on TiO2-OH surface with Ag tetramer. It

has been found that the Ag tetramer is strongly interacting with the TiO2 surface with the

interaction energy of -2.98 eV. Here, the bond is formed between Ag and surface O and Ti

atoms of TiO2 with the Ag-O bond distance of 2.3 to 2.7 Å, which is close to the

experimental bond distance of 2.32 Å[42], and the Ag-Ti bond distance of 2.8 to 3 Å. Four

configurations TolOHAg1, TolOHAg2, TolOHAg3 and BenAg are studied for the toluene

interaction on TiO2-OH surface with Ag tetramer (TiO2-OH-Ag). The optimized geometry of

the studied configurations are shown in Figure 4. In the TolOHAg1 configuration, the o and

m carbon atoms of toluene are interacting with the silver atom with C-Ag distance of 2.3 Å.

The interaction energy of TolOHAg1 configuration is -0.91 eV. From Table S2, it has been

found that the C1-C6, C6-C4 and C6-H2 bond distance of toluene in the TolOHAg1

configuration is elongated by about 0.02 Å with respect to the isolated toluene molecule. The

results from the Table S3 show that the charge by about 0.13 e is transferred from silver atom

to the bonded o and m carbon atoms of toluene in the TolOHAg1 configuration. In

TolOHAg2 configuration, the hydrogen atom attached with the p -carbon atom of toluene is
10
interacting with TiO2-OH-Ag surface. The calculated interaction energy of TolOHAg2

configuration is -0.66 eV. It has been observed that the structural parameters of toluene is not

significantly altered upon the interaction with TiO2-OH-Ag surface through the hydrogen

atom of p -carbon. The calculated Bader atomic charges show that only a negligible amount

of charge is transferred between toluene and TiO2-OH-Ag surface in the TolOHAg2

configuration. The above results show that the toluene molecule is not converted into benzyl

radical through the interaction of o , m and p carbon atoms of toluene with OH group on

TiO2-Ag surface. Similar to TolOH3 configuration, in TolOHAg3 configuration, the methyl

group of toluene is pointing towards the hydroxyl groups on the TiO2-OH-Ag surface. It has

been observed that there is a slight change in structural parameters of toluene while

adsorption on TiO2 surface and a very small amount of charge by about 0.01 to 0.04 e is

transferred between the toluene and TiO2-OH-Ag surface. The interaction energy for

TolOHAg3 configuration is -3.92 eV which is higher by 3 eV than the TolOHAg1 and

TolOHAg2 configurations.

In BenAg configuration, the C7-H7 bond of methyl group of toluene is dissociated

and the detached hydrogen atom is attached with the OH group, forming a benzyl radical and

water molecule on the TiO2 surface. The calculated interaction energy for BenAg

configuration is -8.47 eV. It has been found that the oxygen atom of OH group gains charge

by about ~ 0.23 e from methyl group and titanium atom. The electron density difference plot

of BenAg configuration show that the electron density is decreasing on the methyl group of

toluene, and is increasing on the H-OOH-HOH bonding region (see Figure 4e). The above

results clearly show that the conversion of toluene into benzyl radical takes place only

through the interaction of methyl group of toluene with OH group on TiO2 surface and the

presence of Ag tetramer enhances the interaction between toluene and TiO2-OH surface.

11
(a) (b)

(c) (d)

12
 (e)
Figure 4. Optimized structure of (a) TolOHAg1, (b) TolOHAg2, (c) TolOHAg3 (d) BenAg
(e) Electron density difference plot of BenAg configuration.

3.4. Reaction path associated with conversion of toluene into benzyl radical

The above results show that the toluene molecule is converted into benzyl radical and

water molecule on TiO2-OH and TiO2-OH-Ag surfaces through the interaction of methyl

group of toluene with surface hydroxyl group. Now, it is interesting to study the reaction

pathway associated with the conversion of toluene into benzyl radical and water molecule on

TiO2-OH and TiO2-OH-Ag surfaces by calculating transition state and energy barrier. In

order to determine the transition state and to calculate the energy barrier for toluene

conversion into benzyl radical, we have performed climbing image nudged elastic band

(CI-NEB) on a series of configurations connecting the initial and final states. Here, the initial

state (reactant) is the TolOH3 and TolOHAg3 configurations, and the final state (product) is

converted benzyl radical and water molecule on TiO2 surface. In the initial state, the distance

between methyl group of toluene and OH group on TiO2-OH and TiO2-OH-Ag surfaces is

around 2.5 Å. The minimum energy pathway for conversion of toluene into benzyl radical on

TiO2-OH and TiO2-OH-Ag surfaces is shown in Figures 5 and 6, respectively. As shown in

Figures 5 and 6, the reactions are highly exothermic and the calculated relative energy values

are -4.62 and -4.55 eV. The activation energy barrier for the conversion of toluene into
13
benzyl radical on the TiO2-OH and TiO2-OH-Ag surfaces is 0.56 and 0.53 eV. From the

Figure 5, it has been observed that the reaction begins with the elongation of the C7-H7 bond

in the methyl group of toluene. At the TS, the distance between abstracted hydrogen atom

and the carbon atom of methyl group increases to 1.79 Å from 1.1 Å in the reactant. Further,

in the TS structure, the distance between oxygen atom of surface hydroxyl group and

attached titanium atom increases to 2.40 Å from 1.95 Å in the reactant.

Figure 5. Relative energy profile for conversion of toluene into benzyl radical on anatase
(001) surface with OH group.

Similarly, it has been found that the elongation of C7-H7 bond is initiating the conversion of

toluene into benzyl radical on TiO2-OH-Ag surface. Here, in the TS configuration, the C7-H7

bond distance is increased by about 0.56 Å with respect to the initial state and the calculated

smaller energy barrier (0.03 eV) shows that the presence of Ag tetramer enhances the toluene

dissociation on TiO2-OH surface. Li et al.[43] recently studied the reaction between toluene

14
and OH radical using B3LYP/6-31G(d) level of theory and reported an energy barrier of

0.05 eV for the formation of benzyl radical and water molecule. It has been noted that the

energy barrier reported in the present work is higher by about 0.45 eV with respect to the

value reported by Li et al.[43] Note that, in the present work the oxygen atom of hydroxyl

group is binding with surface Ti atom and an amount of energy is utilized to break this bond,

which is the reason for higher barrier calculated in the present work.

Figure 6. Relative energy profile for conversion of toluene into benzyl radical on anatase
(001) surface with OH groups and Ag tetramer.

15
4. Conclusions

The primary step of toluene dissociation on anatase TiO2 (001) surface is investigated

by using density functional theory calculations. It has been found that the toluene is not

dissociated on the pristine TiO2 surface and it is converted into benzyl radical through the

interaction of methyl group of toluene with the OH group on the TiO2 surface. The reaction

profile calculation for conversion of toluene into benzyl radical on TiO2-OH and

TiO2-OH-Ag surfaces shows that the reactions are highly exothermic and the energy barrier

for the reaction is 0.56 and 0.53 eV, respectively. In agreement with previous studies, it has

been found that the toluene is dissociated only through interaction with OH group on the

anatase TiO2 (001) surface and the reaction is augmented by the presence of Ag cluster. Most

importantly, the converted benzyl radical is physisorbed on the anatase TiO2 (001) surface,

which clearly indicates the catalytic activity of anatase TiO2 (001) surface, and TiO2 is not

affected by the conversion of toluene into benzyl radical. Due to the presence of unsaturated

five coordinated titanium atoms in the anatase TiO2 (001) surface, it has an ability to generate

more number of surface OH groups, and hence it can easily regenerate the surface OH groups

after the conversion of toluene into benzyl radical and water molecule on TiO2-OH surface.

Therefore, it is expected that the anatase crystal with large number of (001) facets is a good

catalyst for the dissociation of toluene molecule.

Acknowledgement

One of the authors, M.S. is thankful to the University Grants Commission (UGC),

Govt. of India, for awarding Basic Scientific Research (BSR) Fellowship. The authors

thankful to department of science and technology (DST), India, for funding to establish the

high performance computing facility under the PURSE program.

16
Supplementary material

The selected bond lengths (in Å) in the isolated and adsorption configurations of

toluene on TiO2-OH and TiO2-OH-Ag surfaces are summarized in Table S1. The calculated

Bader atomic charge for selected atoms in the isolated toluene and surface OH groups is

summarized in Table S2. Interaction energy of different configurations of adsorbates on

anatase TiO2 (001) surface calculated using PBE method summarized Table S3. Optimized

structure of interacting configurations of toluene on pristine anatase TiO2 (001) surface at

PBE-D2 method is shown in Figures S1. Optimized structure of (a) TolOH1, (b) TolOH2 and

(c) TolOH3 (d) Ben at PBE-D2 method is shown in Figures S2.

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Highlights

• This study elucidates the conversion of toluene into benzyl radical on TiO2
• Toluene is converted into benzyl radical via OH group on TiO2 surface
• Presence of Ag cluster augments the conversion reaction

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Graphical Abstract

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