Journal of Science and Technology 55 (xx) (2017) 249–256

APPLICATION OF TiO2–P25 IN THE PHOTODEGRADATION

OF n–LAURYL DIETHANOLAMINE AND CINNAMIC ACID
IN PRESENCE OF OXYGEN

Loc L. C. 1, 2, *, Anh H. C. 2, Anh N. P. 2, Tot N. T. N. 2, Quy N. N. 2, Tri N. 1,

Cuong H. T. 1, Van N. T. T. 1

1
Institute of Chemical Technology, Vietnam Academy of Science and Technology
1 Mac Dinh Chi Street, Ward 1, District 1, Ho Chi Minh City, Vietnam
2
Faculty of Chemical Engineering, University of Technology–VNUHCM
268 Ly Thuong Kiet Street, Ward 14, District 10, Ho Chi Minh City, Vietnam

*
Email: camloc.luu@gmail.com

Received: 30 December 2017; Accepted for publication: 9 March 2017

ABSTRACT

In this paper, the activity of TiO2–P25 in the photodecomposition of recalcitrant organic

compounds such as n–lauryl diethanolamine (n–LDA) and cinnamic acid (CA) solution in UV +
BLED light in presence of oxygen was investigated and the optimum conditions of reaction were
determined. With physicochemical characteristics such as anatase/rutile ratio of 80/20, the
crystallite size of 23 nm, BET surface area of 43.6, the light absorption wavelength of 390 nm,
band gap energy of 3.17 eV, and point of zero charge of 6.3, TiO2–P25 catalyst is able to
photodecompose more than 95 % of LDA and CA after 90 minutes in presence of oxygen under
irradiation of UV–B light.

Keywords: cinnamic acid, n–lauryl diethanolamine, oxygen, TiO2–P25.

1. INTRODUCTION

Pollution of persistent organic compounds (POCs) is one of the primary concerns. In

wastewater, POCs are usually aromatic hydrocarbons, condensed polycyclic compounds,
organochlorines. These matters are highly toxic to organisms and humans and derived from
various sources [1]. Until now, photocatalysis is considered as a capable method to degrade
thoroughly POCs [2], reusable treated wastewater [3]. Currently, TiO2 – Degussa P25 (TiO2–
P25) is one of the commercial photocatalysts that is highly active and commonly used. TiO2–
P25 is used in treatment of phenolic compounds and pesticides in wastewater [4–6] such as
phosphamidon [7], dephenamid [8], indole–3–acetic and indole–3–butyric acid [9], dimethoate
[10], propham, propachlor and tebuthiron [11], 4–chlorophenol and 2,6–dicholorophenol [12];
substances in urban wastewater (acetaminophen, antipyrine, atrazine, carbamazepine, diclofenac,
flumequine, hydroxybiphenyl, ibuprofen, isoproturon, ketorolac, ofloxacin, progesterone,
Application of TiO2–P25 in the photodegradation of n–lauryl diethanolamine and cinnamic acid…

sulfamethoxazole and triclosan) [13, 14], textile wastewater (reactive red 4, methylene blue [15–
17], reactive red 222 [18], crystal violet [19], remazol black [16], methyl orange and congo red
[20]), herbicide (picloram [21] and imazethapyr [22]),...
Cinnamic acid (C9H8O2) of phenolic acids is a very persistent unsaturated carboxylic. It
usually presents in wastewater of processing plant of vegetables and vegetable oils, mostly in
wastewater of processing plant of palm oil and olive oil (105.3 mg/L) [23]. Cinnamic acid (CA)
is processed by advanced oxidation processes by H2O2 [24], Fenton reaction Cu2+/H2O2 [24]
Fe2+/H2O2 [24, 25] or Fe2+/H2O2 combining UV [25]. However, the photocatalytic reaction of
TiO2 using various oxidizing agents to degrade CA wasn’t studied.
Our survey is carried out within 7 Framework Programme of the European Council
“Photocatalytic materials for treatment of persistent organic industrial waste”, it showed that the
wastewater of some seafood processing plants in Ho Chi Minh City contained persistent organic
compounds in which n–lauryl diethanolamine (C16H35NO2) had the highest concentration from
50 to 100 μg/L. n–Lauryl diethanolamine (n–LDA) is a surfactant discharged from the cleaning
stage of processing tools as well as floor after every workday. By conventional biological
treatment used in all plants, it is impossible to decompose this surfactant. Up to now, no study
about treating of this substance has been announced.
Therefore, the scope of this work is to apply TiO2–P25 catalyst in the photodegradation of
n–lauryl diethanolamine and cinnamic acid under UV light (λ = 365 nm) using oxygen as
oxidizing agents and propose the optimum reaction conditions.

2. MATERIALS AND METHODS

Before reaction, catalyst TiO2–P25 (Degussa, Merck) was activated at 450 °C for 2 hours in
the air flow of 3 L/h. Photoactivity of catalyst in the decomposition of n–LDA or CA
(concentration ~ 50 mg/L) was surveyed under the light of 365 nm in wavelength. n–LDA and
CA were purchased from Sigma–Aldrich. All chemicals were used without further purification.
The reaction was conducted in batch, reaction volume of 250 mL and stirrer speed of 250 rpm.
To determine optimum conditions, the influence of initial pH, solution temperature,
concentration of oxygen and catalyst was studied.
n–LDA concentration in solution was determined by high–performance liquid
chromatography HPLC (Scharlau – Spain) in Faculty of Chemistry, University of Science –
VNUHCM. Stationary phase: ACE3–C1 column (diameter of 4.6 mm, length of 150 mm, the
particle size of 3.5 µm) was stabilized at 40 °C. The mobile phase has ratio phase A: phase B of
20:80 (v/v) with the flow speed of 0.5 mL/min. In which, phase A is deionized aqueous solution
containing 0.1% formic acid and phase B is a MeOH solution containing 0.1 % formic acid. CA
concentration was analyzed by a spectrum analyzer UV–1800 (Shimadzu, Japan) in Institute of
Chemical Technology – VAST at a wavelength of 272 nm [26].

3. RESULTS AND DISCUSSION

TiO2–P25 catalyst used in this study has anatase/rutile ratio of 80/20, crystal size of 23 nm,
pore diameter of 3.3 nm, pore volume of 0.037 cm3/g, specific surface area of 43.6 m2/g,
absorbable light wavelength λ = 390 nm, band gap energy Eg = 3.17 eV, and point of zero
charge PZC of 6.3.

250
 Loc L. C., Anh H. C.,
C Anh N. P. , Tot N. T. N.,
N Quy N. N.,, Tri N., Cuonng H. T., Van
n N. T. T.

3.11. Adsorptioon and photo

olysis

Survey reesults of adssorption (wiith catalyst, no lights) and

a photolyssis (no catallyst, with
t CA was adsorbed veery little on TiO
ligghts) (Figure 1) showed that T 2–P25 whhile n–LDA adsorbed
noo more than 20 mg/g an nd adsorptionn reached saaturation afteer 40 minutees. Thereforre, before
connducting phootocatalytic reaction, thee adsorption should be implementedd for 40 minu utes. The
ammount of n––LDA and CA C metaboliized in pho otolysis is very low. Thhis proved bothb two
subbstances are difficult to decompose
d uunder UV rad diation.

(a)) (b)
(

Fiigure 1. Concentration variation of n–LD

DA (a) and CA A (b) in adsorrption (Ccat = 00.5 g/L) and photolysis
p
(UV–LED, λ = 365 nm) at T = 25 °C; pHinitial = 7,0;; Vstirrer = 250 v/ph;
C n–LDA or CA ~ 50
5 mg/L.

3.22. Photodegrradation of n–lauryl

n dieethanolamin
ne

Influence of reaction conditions on photodeg

gradation off n–LDA oveer catalyst TiO
T 2–P25
waas presented in Figure 2.
Figure 2aa showed th hat with low w concentratiions of TiO2–P25 (0.0255 and 0.05 g/L), the
n––LDA converrsion reached d stable valuue after 60 miinutes. If catalyst concenntration was increased
i
to 0.1 g/L, the t time off reaching sstabilization reduced to o 30 minutees. When TiO T 2–P25
conncentration was
w increaseed from 0.0255 to 0.05 g/L L, treatment efficiency
e off n–LDA sign nificantly
inccreased, and the stable co onversion wwas increased d from 74 to ~ 100%. Hoowever, when n catalyst
conncentration was
w increaseed to 0.1 g/L L, the n–LDDA degradatiion was reduuced to 71% %. This is
because when the concentrration of TiO O2 was too high,
h reactionn solution haad high turb
bidity and
ligght adsorptioon coefficiennt would bee decreased. Besides thaat, residual TiO2 particlles could
gennerate light shielding
s efffect that reduuced the surfa
face area of thhe TiO2 expoosed to lightt [27, 28].
Soo the optimum m concentrattion of 0.05 gg/L was chossen.
Figure 2bb showed thaat n–LDA coonversion waas increased whenw airflow
w supplied to o reaction
sollution was inncreased from
m 0.5 to 0.7 LL/min. This was becausee oxygen suppported the generation
of OH* and HOO*
H a importantt role in the capture of electrons,
radicaals, oxygen aalso played an e
lim
miting electrrons–holes recombinatioon. Howeveer, when aiirflow was increased too t high
(1..0 L/min) n––LDA degraadation was decreased due d to foam m appearancee, this preveented UV
t solution. On the otheer hand, with
absorption of the h strong distu
urbance, cataalyst particlees moved
to the surface of liquid and d air bubbless, reducing the
t catalyst amount
a direcctly involvedd reaction
and leading to decrease in the
t treatmentt efficiency.

251
Ap
pplication of TiO
T 2–P25 in the photode
egradation off n–lauryl diethanolaminee and cinnam
mic acid…

Figure 2cc showed thaat when initiaal pH solutioon was increaased from 5 to 7 and 9, the
t initial
speeed of reactiion was increeased, the tim
me of reachin
ng stabilizatiion was reduuced from 90 0 down to
600 and 20 minnutes, respecctively. How wever, the coonversion in three cases was the sam me about
999−100 %. Acccording to th he authors [229], solution
n pH had an impact on thhe electrical property
of catalyst surfface. When solution
s pH wwas greater than
t PZC off catalyst, cattalyst surfacee became
negatively chaarged, adsorb bed cationic ccompounds and conversely, when soolution pH was w lower
thaan PZC of caatalyst, cataly
yst adsorbedd anionic commpounds acco ording to thee reactions:
pH < PZ H2+
ZC: TiOH + H+  TiOH (1)
H⁻  TiO⁻ + H2O
pH > PZC:: TiOH + OH (2)
Accordingg to analysiis, PZC of T
TiO2–P25 was
w 6.3 and n–LDA hadd pKa = 8.7
7 [30] so
phhotodecompoosition of n–L
LDA occurreed favorably at pH = 9 was suitable.

a) Effect of catalyst concentrationn b) Effect of aairflow

(Qair = 0..7 L/min; pH = 7; T = 25 °C
C) (Ccat = 0.05
0 g/L; pH = 7; T = 25 °C
C)

c) Efffect of initial pH solution d) Effeect of reactionn temperature

(Ccat = 0.05 g/L;
g Qair = 0,7 7 L/min; T = 225 °C) (Ccat = 0.05
5 g/L; Qair = 0..7 L/min; pH = 9)

Figure 2. Inffluence of variious factor onn n–LDA conv

version (X) ovver photodecom
mposition tim
me with
oxyggen on TiO2–P
P25 catalyst.

Figure 2dd showed when

w reactioon temperatture increaseed from 200 to 30 °C, n–LDA
connversion inccreased not much and after 60 minutes,
m thee degradatioons of n–LD DA were
appproximately the same and
a reached ~ 99.8 %. Therefore, reaction
r tem
mperature waas chosen
about 25 °C − common tem mperature of water samplle at weather condition inn Vietnam.

252
 Loc L. C., Anh H. C.,
C Anh N. P. , Tot N. T. N.,
N Quy N. N.,, Tri N., Cuonng H. T., Van
n N. T. T.

3.33. Photodegrradation of cinnamic accid

Influence of reaction conditions on photooxiidation of CA

A with oxyggen as an ox
xidant on
cattalyst TiO2–P
P25 was pressented in Figgure 3.
Similarly to n–LDA photodegraddation, in CA A photooxiddation the coonversion off CA was
inccreased overr time (Figurre 3a) but itt was slowerr than the n––LDA case, after 90 minutes the
connversion couuld not reach a stable vvalue. In the other words, the metabbolic rate off CA was
lowwer than thaat of n–LDA despite usinng higher cattalyst amoun nt. This can bbe explained
d that CA
conntaining arommatic ring th
hat was moree persistent th
han acyclic n–LDA.
n Wheen increasingg catalyst
conncentration from 0.125 to 0.5 g/L L, efficiency y of CA degradation affter 90 minutes was
inccreased from
m 68 to 86 %. % If contennt of catalystt was continnuously increeased to 0.5 g/L, the
connversion waas not increassed substantiially, followed by a decrrease (down to 78 %) at 0.75 g/L
of catalyst.

a) Effect of catalyst concentrationn b) Effect of aairflow

(Qair = 0.3
0 L/min; pH = 7; T = 25 °C C) (Ccat = 0.25
0 g/L; pH = 7; T = 25 °C
C)

c) Efffect of initial pH
p solution d) Efffect of reactionn temperature
(Ccat = 0.25 g/L; Qair = 0.3 3 L/ph; T = 255 °C) (Ccat = 0.255 g/L; Qair = 0..3 L/ph; pH = 3.8)

Figure 3. Influeence of reactio

F on factors on pphotodecomp
position of CA
A with oxygenn on TiO2–P25
5 catalyst.

CA degraadation increeased when increasing airflow

a suppplied to the solution fro
om 0.1 to
0.33 L/min (Figgure 3b). After 90–minutte reaction, th
he conversio
on of CA inccreased from
m 72 up to
822 %. Howevver, if airflow w was increeased to 0.5 5 L/min, treatment efficciency was increased
i

253
Application of TiO2–P25 in the photodegradation of n–lauryl diethanolamine and cinnamic acid…

slowly, and CA conversion was slowly increased from 82 to 85% after 90–minute reaction. So
the efficiency is highest with airflow of 0.3 L/min. Compared to n–LDA photooxidation, in CA
photoreaction the airflow supplied to the reactor was low (0.3 compared to 0.7 L/min) as the
complete oxidation of a n–LDA molecule (C16H35NO2) needed 25 O2 molecules, while a CA
molecule (C9H8O2) was fully oxidized with 10 O2 molecules.
When increasing initial pH solution from 3.8 to 5 and 7, the initial rate of reaction
decreased. At pH = 3.8 and pH = 5 the conversion was reached stable value (X ~ 100%)
respectively after 40 and 80 minutes, while at pH = 7 the conversion could not reach stable even
after 90 minutes (X ~ 80 %). This was explained that pKa of CA was 4.4, so low pH was
appropriate for reaction.
When temperature was increased from 25 to 35 °C, CA conversion was increased not much
and after 90–minute reaction, the conversion of CA reached approximately the same about 96 %
(Figure 3d). Thence, reaction temperature was chosen to be the natural temperature of water
environment 25 °C.
The optimum conditions to degrade n–LDA and CA is summarized in the following Table 1.

Table 1. The optimal conditions for photocatalytic degradation of n–LDA and CA on TiO2– P25 catalyst.

Reactant Oxidizing Temperature Catalyst Oxidizing Initial Stable Conversion after

agent (°C) concentration flow pH time 90 minutes (%)
(g/L) (min)
n–LDA O2 25 0.25 0.7 L/min 9 20 100
CA O2 25 0.25 0.3 L/min 3.8 40 96

4. CONCLUSIONS

The adsorption and photolysis of n–LDA and CA with TiO2–P25 catalyst were not
substantial. The nature of reactant played a decisive role in determining the optimal reaction
condition. Photodecomposition of CA occurred more hardly than n–LDA and higher catalyst
concentration was needed. n–LDA with pKa = 8.7 should be photodecomposed favorably at
pH = 9, when CA with pKa = 4.4 so it’s photodegradation occurred favorably at pH = 3.8. TiO2–
P25 catalyst performed high activity in photooxidation of persistent organic compounds such as
n–LDA and CA and it enables to decompose completely these compounds after 20−40 minutes
at a temperature of 25 °C. The results were contributed to the affirmation that TiO2–P25 catalyst
had high activity in the treatment of cyclic organic compounds and persistent surfactants.

Acknowledgements. This work was supported by the HCMC University of Technology (VNU–
HCM) under the grant “Investigation of photo–degradation of phenolic compounds in water using TiO2
catalyst” and grand PCATDES 309846 of Seventh Framework Programme – European Commission.

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