Accepted Manuscript

Mechanism and Kinetics of Phenol Photocatalytic, Electrocatalytic and Photoelectrocatalytic Degradation in a TiO2-Nanotube Fixed-Bed Microreactor
Luka Suhadolnik, Andrej Pohar, Bla Likozar, Miran eh
PII:
DOI:
Reference:

S1385-8947(16)30834-8
http://dx.doi.org/10.1016/j.cej.2016.06.027
CEJ 15337

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Chemical Engineering Journal

Received Date:
Revised Date:
Accepted Date:

10 February 2016
22 April 2016
4 June 2016

Please cite this article as: L. Suhadolnik, A. Pohar, B. Likozar, M. eh, Mechanism and Kinetics of Phenol
Photocatalytic, Electrocatalytic and Photoelectrocatalytic Degradation in a TiO2-Nanotube Fixed-Bed Microreactor,
Chemical Engineering Journal (2016), doi: http://dx.doi.org/10.1016/j.cej.2016.06.027

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Mechanism and Kinetics of Phenol Photocatalytic, Electrocatalytic and

Photoelectrocatalytic Degradation in a TiO2-Nanotube Fixed-Bed Microreactor
Luka Suhadolnik,a,b Andrej Pohar,c,* Bla Likozar,c Miran eha

Department for Nanostructured Materials, Joef Stefan Institute, Jamova 39, SI-1000

Ljubljana, Slovenia
b

Joef Stefan International Postgraduate School, Jamova 39, SI-1000 Ljubljana, Slovenia

Laboratory of Catalysis and Chemical Reaction Engineering, National Institute of

Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia

* Corresponding author: tel.: +38614760283 email: andrej.pohar@ki.si

Abstract
Phenol photocatalysis, electrocatalysis and photoelectrocatalysis were performed under
different conditions (UV-light intensity, applied electrical potential, and flow rate) inside an
in-house-developed, coil-type, photoelectrocatalytic microreactor. The main part of the
microreactor is a photocatalytically active unit that was placed into a channel in a UVtransparent housing. The degradation reactions took place on the surface of a photoanode coil
that is made up of TiO2 nanotubes. The mechanisms of photocatalysis and
photoelectrocatalysis were proposed and validated with a mathematical model, which
described the governing processes occurring during the microreactors operation. In the case
of the photocatalysis there was not enough oxygen for complete phenol degradation, whereas
phenol was successfully mineralized with the help of an applied electrical potential. The
applied electrical potential successfully prevented electronhole recombination, which

allowed for unhindered hydroxyl radical formation and a high phenol degradation rate. The
highest initial phenol concentration used, approximately 45.7 mg L1, was completely
mineralized at an applied potential of 16 V, a UV-light intensity of approximately 2.8 mW
cm2, and a flow rate of 50 L min1. Finally, an energy-efficiency study was performed to
identify the optimal photoelectrocatalytic microreactors operating conditions for the phenol
degradation.

Keywords
Photoelectrocatalysis; Photocatalysis; Phenol mineralization; TiO2-nanotube catalyst;
Reaction mechanism

1 Introduction
The degradation of pollutants present in industrial wastewaters is of critical importance in
order to maintain a clean environment. Many processes used to degrade pollutants rely on the
use of different harmful chemicals or lead to the formation of potentially harmful by-products,
which to a certain extent negate the cleaning effect [1]. The degradation of organic
compounds by photocatalytic, electrocatalytic, or photoelectrocatalytic processes is a
promising alternative as it requires no addition of chemicals and can therefore be designated
as a green technology [2].
Heterogeneous photocatalysis induces the acceleration of a chemical reaction in the presence
of a catalyst and a light illumination source with sufficient energy to excite the electrons in a
chosen semiconductor [3], whereas electrocatalysis uses an external electric field to degrade
the organic molecules [4,5]. Photoelectrocatalysis is the combination of both catalytic
processes, and it significantly improves the efficiency of the mineralization reactions by

reducing the recombination rate of the photogenerated electrons and holes [6,7]. The electrons
are moved via an external circuit to the counter electrode, which enables more holes to react
with adsorbed H2O molecules or OH ions to produce OH radicals. These are the primary
oxidants in photocatalysis [8]. If the band gap of the semiconductor is wide enough, the
generated holes are also capable of directly oxidizing a wide range of compounds [9].
The most investigated photocatalyst is TiO2 [10], which has been used for photocatalytic
reactions for many different nanostructures, such as nanoparticles, nanotubes, nanowires, etc.
[11-14], which can be incorporated into the photocatalytic system in the form of a slurry or
can be immobilized inside the photocatalytic reactor [15, 16]. The latter option is preferable
for at least two important reasons. Firstly, an immobilized photocatalyst does not need to be
removed and recovered after the treatment, and, secondly, an electrical potential can be
applied directly to a conductive support, which leads to a synergistic effect between the
photocatalytic and electrocatalytic processes [17].
In recent years reactors with immobilized titanium dioxide have been of great interest for
many photocatalytic [19, 20] and photoelectrocatalytic processes [21, 22, 23]. Among these,
only a few are continuous-flow microreactors with an immobilized photocatalyst that can be
more easily optimized in a research laboratory and numbered-up or even scaled-up to meet
the required flow rates for the degradation of a particular waste water [24, 25]. The most
promising application would be the use of photoelectrocatalytic microreactors to degrade the
compounds that are the most difficult to degrade with a biological treatment.
However, photoelectrocatalytic reactors with an immobilized photocatalyst are still at the
exploratory stage and need to be further developed and tested for the degradation of different
groups of harmful compounds. Some papers reported the use of photoelectrocatalytic reactors
with immobilized TiO2 for the degradation of humic acid [26], dyes [27, 28, 29], diclofenac
[30], 2,4-diclorophene [31], phenol [32], and others.

To date, there are not many published papers that describe a three-dimensional mathematical
model of the processes taking place inside the photoelectrocatalytic reactors, although it is an
important accompanying method that provides an insight into the mechanism of the
photoelectrocatalytic oxidation and can lead to efficient new designs for future reactors.
In the present work, phenol was chosen as a model degradation molecule as it is one of the
important organic pollutants that can accumulate in the environment and which poses health
problems to living organisms [33, 34]. The aim of our study was to describe the
photocatalytic, electrocatalytic, and photoelectrocatalytic degradation in a highly efficient,
continuous-flow, coil-type microreactor with a three-dimensional mathematical model and to
determine the effect of the individual processes. For this purpose, a systematic study of the
effect of the influential parameters on the performance of the microreactor was conducted.
Phenol degradation was determined using high-performance liquid chromatography. As the
energy consumption is as important as the complete mineralization of the compound being
degraded, the energy efficiencies of the photocatalytic, electrocatalytic, and
photoelectrocatalytic processes were also determined.

2 Material and methods

2.1 Photoelectrocatalytic microreactor fabrication and assembly
A coil-type photoelectrocatalytic microreactor was made from a UV-transparent Plexiglas
(Acrytech d.o.o.) housing with a mechanically engraved cylindrical channel, in which a
photocatalytically active unit was placed. The active unit of the photoelectrocatalytic
microreactor was made of an anodized titanium-anode coil with a length of approximately 64
mm and two titanium-cathode coils with lengths of approximately 12 mm. All the coils were
made of 250-m titanium wire (99.8%, Advent Research Materials Ltd), which was wound
into tightly packed coils. The photoanode coil was anodized under constant-voltage

conditions at 60 V in an electrolyte consisting of 0.3 wt. % NH4F (99.99%, Sigma-Aldrich)

and 2 vol. % deionized water in ethylene glycol (99.5%, Carlo Erba Reagents) to obtain
highly ordered, vertically oriented, titania nanotubes (Figure 1). After 3 hours of anodization
the coil was washed with deionized water and ethanol, and then annealed at 450 C for 3
hours to transform the amorphous TiO2 nanotubes into the photocatalytically active anatase.

Figure 1. SEM micrograph of the anodized titanium coil. The average nanotube outer
diameter is approximately 120 nm, while the inner diameter is approximately 80 nm. The
length of the nanotubes was estimated from the SEM images to be approximately 15 m.

The anode coil was placed in the middle of a 3-mm-diameter silica glass rod, whereas the
cathode coils were placed on each side of the anode coil, separated by 2-mm plastic spacers to
prevent a short-circuit. The length of the entire active unit of the photoelectrocatalytic
microreactor was approximately 92 mm. Figure 2 shows the longitudinal section and the
cross-section of the reactor; it displays how the silica rod was mounted within the channel of
the Plexiglas housing. Figure 2b shows the cross-section of the reactor along the line AA of
Figure 2a. It can be seen that the chamber provides retaining sections which are adapted to
hold the ends of the silica rod. This assures a strong mounting of the silica rod, which, as

shown in Figure 2a, has some extension beyond the area, occupied by the cathode and anode
coils.

Figure 2. The longitudinal section (a) of the reactor and the cross-section (b) along the line A
A of (a), where the silica rod is mounted to the Plexiglas housing.

The calculated surface of the anodized titanium coil that could be reached by the UV light
was 9.50.4 cm2. The distance between the outer diameter of the anodized titanium coil and
the inner diameter of the channel was approximately 200 m. The volume of the reactor in the
part of the photoactive TiO2 was determined to be 1708 L, which gives a surface-tovolume ratio of approximately 5550 m2 m3, if the specific surface area of the TiO2-nanotube
film is not taken into account.

2.2 Photocatalytic, electrocatalytic, and photoelectrocatalytic measurements

The inlet of the microreactor was connected to a syringe pump (Aladdin, World Precision
Instruments, Sarasota, USA) with fluorinated ethylene propylene tubing (internal diameter:
0.5 mm, Vici AG International). The initial phenol (99.9%, Sigma-Aldrich) concentrations of
approximately 10.8 ppm, 23.5 ppm or 46.5 ppm were continuously pumped through the
reactor at a volumetric flow rate in the range 7 to 600 L min1. Deionized water was used to
dissolve the phenol prior to all the measurements. For the electrocatalytic and
photoelectrocatalytic experiments, the electrolyte conductivity was varied with sodium
chloride (99.99%, Acros Organics) in pure water. The calibration curve (Figure 1S) and
conductivity measurements (Table 3S) are provided in the Supplementary material. The
conductivity was measured with a ProLine Plus M330 conductivity meter. The applied
potential was in the range 4 to 30 V. For the photocatalytic and photoelectrocatalytic
experiments, the anode coil was illuminated from the top and the bottom using two UV-light
sources (Shenzhen Justar Electronic Technology CO., LTD, Guangdong, China), as can be
seen in Figure 3. The emission maximum of the UV lights was 365 nm and the light intensity
was set from 0.1 to 2.8 mW cm2 by changing the operating potential of the lights. Before
collecting the samples for the individual experimental conditions, 1 mL of the phenol solution
was pumped through the microreactor to clean the products of the previous experiment. The
experiments were performed at room temperature (25 C). For each experiment, three samples
were collected at the outlet of the microreactor and analyzed with a high-performance, liquidchromatography apparatus (HPLC, Agilent 1100 Series, Agilent, Santa Clara, CA). The
degradation of the phenol and the amounts of the intermediates produced were determined
from the calibration curves, which were made for the model degradation compound and all
the intermediates that were detected by the HPLC. The method was the same as in a previous
study [35]. The HPLC was equipped with a UVVis detector (G1315A) and a solventdelivery pump (G1312A) with a Phenomenex (Torrance, CA) SynergiTM 4- Hydro-RP 80

analytical column (250 4.6 mm2, 4-m packing), with a 70:30 (vol:vol) Milli-Q water and
acetonitrile mixture as the solvent. The species in question were analyzed at 254 nm. The
retention times for the phenol, hydroquinone and benzoquinone were 8.8, 7.4 and 5.3 min.

Figure 3. The experimental set-up for measuring the photoelectrocatalytic activity of the coiltype microreactor (1) with an anodized titanium coil as the photocatalytically active unit.
Other components of the system are: (2) UV LED lights, (3) DC power supplies, (4) glass
syringe, (5) syringe pump, (6) high-performance liquid chromatography (HPLC) system, (7)
vials for sample collection, and (8) computer.

3 Modelling
3.1 The mechanism of photocatalysis
Upon UV-light illumination with sufficient energy, the photons excite the electrons in the
TiO2 semiconductor, moving them from the valence to the conduction band, which generates
electronhole pairs. These electronhole pairs are prone to recombination, which reduces the
catalytic capability of the catalyst and limits its applications to a great extent [36, 37]. The
holes (positive charges) react with the water, forming hydroxyl radicals (OH), while the

electrons react with the dissolved O2, forming the superoxide radical (O2). The O2 prevents
the recombination of e and h+ by reacting with the electrons on the surface of the
photocatalyst. One dissolved O2 molecule reacts with one e, which allows for the existence
of one h+. In this way, one or two OH can be produced (Figure 4) [38]. Our photocatalytic
results showed that the amounts of decomposed phenol and produced benzoquinone
correspond to one OH being produced from one O2.
TiO2 + h e + h +

(1)

Figure 4. The relevant reaction mechanism for OH radical generation taking place at the
electronhole pairs on the TiO2 catalyst.

3.2 The mechanism of photoelectrocatalysis

UV light excites electrons, moving them into the conductive band. The externally applied
anodic bias can forward the excited electrons to a counter electrode, which results in a
decrease in the recombination rate of the photogenerated electrons and holes [39]. The applied
potential greatly improves the efficiency of the charge separation, driving the photogenerated
electrons via the external circuit to the counter electrode [40]. Electron holes are therefore

available for the production of the hydroxyl radical OH. The number of available holes
depends on the strength of the current and the intensity of the light.
With the application of an electrical current, there are other considerations, which need to be
taken into account. When NaCl is used for increasing the solutions conductivity, phenol is
also oxidized by the chlorine radicals. Chloride ions are electrochemically oxidized at the
anode surface, forming chlorine radicals, which have a high oxidizing power. Another
phenomenon taking place is water splitting in which case water is split at the anode, forming
O2 and H2. A more detailed discussion can be read in section 4.4 in the discussion regarding
the obtained results.

4 Results and discussion

4.1 Phenol decomposition
Phenol (Ph) adsorbs onto the TiO2 catalyst, where it reacts with the hydroxyl radicals and
decomposes to benzoquinone (Bq) and simultaneously to acids, CO2 and H2O. The
benzoquinone also decomposes to acids, CO2 and H2O. Hydroquinone was only detected in
two experiments, both at the highest voltage of 30 V, the highest UV-light intensity of
approximately 2.8 mW cm2 and for very short residence times (at flow rates of 200 and 600
L min1). Since it is a rapidly decomposed intermediate, it was not specifically treated in the
model.

Figure 5. The mechanism of phenol degradation that applies to the current investigation.

4.2 The proposed model

The reactions inside the reactor take place at the TiO2 surface, where the electronhole pairs
induce the oxidation reactions. Phenol decomposes to benzoquinone with the aid of four
hydroxyl radicals, while total mineralization is achieved with 28 hydroxyl radicals.
Benzoquinone requires 24 hydroxyl radicals for complete mineralization. Water and CO2 are
formed in the process.
C 6 H 6 O + 4 OH C 6 H 4 O2 + 3 H 2 O

(2)

C 6 H 6 O + 28 OH 6CO 2 + 17 H 2 O

(3)

C 6 H 6 O + 24 OH 6CO 2 + 14 H 2 O

(4)

The partial differential mass-balance equations (with the transient, convection and diffusion
terms in cylindrical coordinates) are:

2 c Ph 2 c Ph 1 c Ph
c Ph
c
= v(r ) Ph + DPh
+
+
2
t
x
r r
r 2
x

(5)

 2 c Bq 2 c Bq 1 c Bq
+ DBq
+
+
2
x 2
x
r r

(6)

2 cO2 2 cO2 1 cO2

= v(r )
+ DO2
+
+
x 2
t
x
r r
r 2

(7)

c Bq
t

cO2

= v(r )

c Bq

cO2

where ci are the species concentrations, t represents the time, v is the linear velocity, x is the
axial dimension, r is the radial dimension, and Di are the diffusion coefficients. v is dependent
on the radial position, due to the formation of a parabolic laminar-velocity profile. The
domain in the radial direction extends from R1, which is 1.625 mm, to R2, which is 1.95 mm.
The reaction takes place on the TiO2 catalyst, which is positioned on the inner channel wall at
R1 .

Since the catalyst consists of TiO2 nanotubes and the phenol concentrations are small, the
saturation of the catalyst surface was not considered to be a restrictive factor governing the
overall kinetics. The boundary conditions and the reaction-rate expressions on the catalyst
surface are therefore dependent on the adsorption coefficients of each individual species (Ki),
and on the kinetic constants (kii):
rPh Bq = k Ph Bq K Ph c Ph c OH

(8)

rPh min = k Ph min K Ph c Ph c OH

(9)

rBq min = k Bq min K Bq c Bq c OH

(10)

During photocatalysis, the reduction of oxygen on the catalyst surface removes the e and
allows for OH generation on the holes. The rate expression is:
nl 1
rO2 = IUV
kred KO2 cO2

(11)

The boundary conditions and the mass balance for the hydroxyl radicals involved in
photocatalysis at the catalytic wall are:

DO2

DPh

DBq

dc OH

dt

dcO2

dr

= rO2

dcPh
= rPh Bq rPh min
dr
dcBq

dr

= + rPh Bq rBq min

= rO2 4rPh Bq 28rPh min 24rBq min

(12)

(13)

(14)

(15)

During photoelectrocatalysis the UV light excites the electrons and the electrical current
moves them to the cathode. The OH radicals are produced from water on the available holes.
Dissolved oxygen does not play a part in the degradation of the phenol, since the applied
electrical current suppresses the recombination and enables the holes on the photocatalyst
surface to produce the OH. The rate expression can be written as:
nl 2
nc
relect . = ( IUV
kelect .
+ I 0 ) I current

(16)

The boundary conditions and the mass balance for the hydroxyl radicals at the catalytic wall
for the photoelectrocatalysis are:

DPh

D Bq

dc OH

dt

dc Ph
= rPh Bq rPh min
dr
dc Bq

dr

= + rPh Bq rBq min

= relect 4rPh Bq 28rPh min 24rBq min

(17)

(18)

(19)

A zero concentration-gradient boundary condition was imposed on the R2 boundary (noncatalytic outer wall) for all the species. The diffusion coefficients were determined using the
correlation provided by Siddiqi and Lucas [41] from the molar volumes of the liquid solutes at
their normal boiling points. The diffusion coefficient of the oxygen was calculated using the
WilkeChang correlation [42]. The modeling was performed with Matlab using the finitedifference method. The finite difference scheme of the partial differential mass balance
equation (eq. 57) can be seen in the Supplementary material. Grid independence was
achieved at a 4140105 discretization of the computational domain
(radiallongitudinaltime dimensions). At higher phenol conversions, a finer discretization of
the time dimension was required. The solution was obtained when the calculations converged
to the steady state. For the parameter estimation, a regression analysis was performed using
the trust-region-reflective algorithm.
The kinetic parameters were obtained by a simultaneous regression analysis of all the
experimental data and are presented in Table 1. The reaction and adsorption constants are
coupled in the reactionadsorption constant.

Table 1. The kinetic parameters for photocatalysis and photoelectrocatalysis obtained using
the regression analysis of the experimental data.
parameters

value

kPhBq KPh (L s1 mol1)

9.51 10 2

kPhmin KPh (L s1 mol1)

1.48 10 3

kBqmin KBq (L s1 mol1)

1.36 10 4

nl1

0.91

kred KO2 (mW cm2)nl1 s1)

1.18 10 5

I0 (mW cm2)nl2

0.25

nl2

0.94

Ne

0.96

kelect ((mW cm2)nl2mAnemol L1 s1)

1.18 10 8

All the experiments were performed under laminar flow conditions. The highest Reynolds
number at the highest flow rate of 600 L min1 was less than 1. The electrical current (Icurrent
in mA) measured was 0.153 mA V1 electrical potential (U in V). A detailed discussion
follows in the subsequent sections.

4.3 Photocatalysis

The photocatalysis was performed at different flow rates, initial phenol concentrations and
light intensities. Figure 6 shows the results for the UV-light intensity of 2.8 mW cm2. The
experimental symbols are the microreactor exit concentrations for the different residence
times, which correspond to the appropriate flow rates. During the photocatalysis the phenol
was not decomposed to any great extent, i.e., only to 83.7% and 83.3% (experiment and
model) at an approximately 10.8 ppm initial phenol concentration, to 90.7% and 91.7% of its
initial value (experiment and model) at approximately 23.5 ppm, and to 92.8% and 95.5%
(experiment and model) at approximately 46.5 ppm. This was found to be due to the depletion
of oxygen inside the microchannel. Oxygen has a determining role in the photodegradation,
since it consumes the photogenerated electrons and prevents their direct recombination with
the holes. In the case of O2 depletion, extensive recombination stops the photocatalytic
activity of the TiO2 catalyst. From the model it was determined that one reacted O2 results in
one OH being produced from H2O at the positive hole, in which case the final experimental
conversions matched the final model conversions.

Figure 6. Phenol concentrations at different microreactor residence times for different initial
phenol concentrations and at approx. 2.8 mW cm2 UV-light intensity. The symbols represent
the experimental results, whereas the lines are the results from the model.

The detailed concentration profiles of phenol, benzoquinone and oxygen are presented in
Figure 7 (a, b and c) for the 2.1 mW cm2 UV-light intensity and a flow rate of 50 L min1.
The concentration profiles are presented in ppm along the axial (x) and radial (r) dimensions.
The reaction takes place at the boundary for r = 1.625 mm. At the beginning of the
microchannel at the cathode coil there is no hydroxyl radical generation and decomposition
does not occur. Further along the microchannel at the anode, hydroxyl radicals decompose the
phenol into benzoquinone and induce mineralization; oxygen is depleted in the process
(Figure 7c). After this oxygen depletion, the reactions taking place come to a halt. The initial
oxygen concentration corresponds to the saturated oxygen concentration at 25 C, which is
4.59 mol L1. The concentration profiles in the radial (r) direction are dependent on the rate of
diffusion for each species. Figure 7d presents the average concentration at the exit of the
microreactor for different residence times (for flow rates of 7, 10, 20, 50, 200 and 600 L

min1). The flow rates 7 to 50 L min1 yield the same result, since the oxygen was depleted
in all cases prior to reaching the exit of the microreactor.
The majority of the phenol was converted to benzoquinone, which is also expressed in the
reactionadsorption constant k PhBqKPh of 9.51 10 2 L s1 mol1, which is the highest of the
constants for the competing reaction pathways. Second is the reactionadsorption constant for
phenol mineralization, which is almost two orders of magnitude lower (1.48 103 L s1
mol1). Benzoquinone, once formed, does not decompose readily; the reactionadsorption
constant for benzoquinone mineralization is one order of magnitude lower than the constant
for direct phenol mineralization.

Figure 7. The concentration profiles of (a) phenol, (b) benzoquinone and (c) oxygen along the
length and radius of the reactor in ppm for a flow rate of 50 L min1. (d) The average outlet

concentrations for various residence times (different flow rates). The light intensity was 2.1
mW cm2.

The effect of light intensity is presented in Figure 8. Its effect on the kinetic constant, in the
studied range from 0 to approximately 2.8 mW cm2, follows an almost linear dependency,
with a power-law coefficient of 0.91. Nevertheless, higher phenol conversions were not
achieved at higher light intensities due to an oxygen deficiency. The model predictions were
in good agreement with the experimental results.

Figure 8. The effect of light intensity on the phenol (red) and benzoquinone (green)
concentrations. The symbols represent the experimental, while the lines represent the
modeling results for a flow rate of 200 L min1.
The complete experimental list with the operational conditions, the degradation extent and the
rate of degradation can be seen in the Supplementary material. A maximum 0.25 degradation
extent was achieved at 2.1 mW cm2, 7 L min1, whereas the maximum degradation rate of
3.3 ppm min1 was achieved at 2.8 mW cm2 and 600 L min1.

4.4 Photoelectrocatalysis and electrocatalysis

Photoelectrocatalysis was performed at different flow rates, light intensities, and under an
applied electrical potential (U) of 4, 8, and 16 V. The oxygen did not play a decisive role in
the phenol degradation; the existence of the positive holes was stabilized by the electrical
current. At higher currents, more hydroxyl radicals were generated, which increased the rate
of the reaction. Photoelectrocatalysis allowed for a complete mineralization of the phenol.
The reactionadsorption constants were the same as with the photocatalysis (Table 1). Phenol
degradation also took place in the dark (0 mW cm2); without UV illumination, the reactions
were undergoing electrocatalysis only. It is presumed that the hydroxyl radicals were
electrochemically produced at the anode surface, with chlorine radicals also being generated,
because of the presence of chloride ions, which were electrochemically oxidized at the anode
surface. Figure 9 shows the effect of the applied electrical potential on phenol degradation for
various light intensities. The concentrations depict the average outlet phenol concentration.
The expected trend is evident, except in the case of electrocatalysis, at zero illumination and
16 V, when a very high phenol concentration drop can be observed, as compared to the
experiments performed at 8 V and 4 V. At approximately 1.4, 2.1, and 2.8 mW cm2 and 16
V, the model results are similar, since at a high reaction rate, the diffusion transport to the
catalytic wall becomes the limiting factor. This was not observed for the photocatalytic
experiments, since the reaction rate was slower. The calculated diffusion coefficients were
7.96 10 10 m2 s1 for the phenol and 7.68 1010 m2 s1 for the benzoquinone.

Figure 9. The effect of an applied electrical potential on phenol degradation for various light
intensities and an initial phenol concentration of approx. 45.7 ppm at a 200-L min1 flow
rate. The 0 mW cm2 demonstrates the results of the electrocatalysis only.

Detailed concentration profiles for the phenol and benzoquinone are presented in Figure 9 for
the case of an initial phenol concentration of approximately 45.7 ppm, a flow rate of 600 L
min1, a light intensity of approximately 2.8 mW cm2, and an electrical potential of 8 V. In
Figure 10a the phenol decomposes to 0 ppm at the inner catalytic wall, while the average
outlet concentration is 78.2% of the initial concentration. The diffusion of phenol from the
outer to the inner wall is slow, which produces a high concentration gradient in the radial
direction. Benzoquinone (Figure 10b) is formed and decomposed at the catalytic wall. These
results show that the process would be intensified in a narrower (radial-wise) channel, where
the rate of the diffusional transport to and from the catalytic wall would be improved. The
velocity profile, presented in Figure 10c, formed between the two walls is parabolic and the
flow was laminar in all the experiments and simulations. The exit phenol and benzoquinone
concentrations at 600 L min1 for different electrical potentials are shown in Figure 10d.

Figure 10. The concentration profiles of (a) phenol, (b) benzoquinone and (c) the velocity
profile along the length and radius of the reactor in ppm at a flow rate of 600 L min1, light
intensity of 2.8 mW cm2, and an electrical potential of 8 V. (d) The average outlet
concentrations at different electrical currents (0 to 16 V).

At 16 V there was a large discrepancy between all of the modeling results and the
experimental values (Figure 11). Much higher conversions were achieved for low UV
irradiation than could be predicted using the model. This is most pronounced at 0 mW cm2
and a 16 V electrical potential, in which case the phenol concentration dropped to 45.1% of
the initial concentration.

Figure 11. The effect of light intensity on phenol degradation at 200 L min1.

At 16 V it is clear that the light intensity did not have a substantial effect on the phenol
degradation. The reason for this was the different reaction mechanism governing the process.
The phenol was not only oxidized by the OH, but also by the chlorine radicals. In order to
verify this assumption, NaNO3 was added to the phenol solution instead of NaCl. As shown in
Figure 12 the change in the inorganic salt plays a significant role in the phenol degradation,
which was especially visible at higher applied potentials and higher phenol-solution
conductivities. With a high enough Cl ion concentration in the solution and a zero applied
potential, chloride ions inhibit the phenol degradation (Figure 12b). By increasing the applied
electrical potential, more and more chlorine radicals are generated, which contribute to the
overall degradation. Water is also split into hydrogen and oxygen at 16 V, but the amount of
released gases during mineralization is extremely low.
The limiting current density for chlorine evolution is already achieved at the applied potential
of 4 V. From this applied potential the NaCl exceeds the performance of the phenol

degradation in comparison to NaNO3. This can be seen regardless of the NaCl concentration
in the phenol solution.
The difference in the degradation rate between both cases, the addition of NaCl or NaNO3, is
increasing with an increasing applied potential due to the presence of Cl ions, which
generates additional radicals that further enhance the phenol degradation rate. The main role
of the NaNO3 addition is therefore only to increase the conductivity of the solution and enable
the suppression of electronhole pair recombination with the application of the external
electrical potential. Up to a certain applied potential value, the phenol degradation rate is
increasing due to the better separation of electron-hole pairs and, consequently, a greater OH
generation. The use of NaNO3 to adjust the solutions conductivity shows that the applied
potential of 8 V is enough to suppress the recombination of the electrons and holes generated
at a light intensity of approximately 2.8 mW cm2 (Figure 12b). All the additional degradation
is attributed to the high oxidizing power of the chlorine radicals.

Figure 12. Photoelectrocatalytic degradation of phenol with an initial concentration of

approximately 46 mg L1 at different applied electrical potentials, a light intensity of approx.
2.8 mW cm2 and at a phenol solution conductivity of (a) approx. 230 S cm1 and (b)

approx. 10.5 mS cm1. The phenol solutions conductivity was adjusted with NaCl or NaNO3
and the flow rate was set to 200 L min1 for both sets of experiments.

Figure 13 shows the concentration profiles of phenol and benzoquinone in Cartesian

coordinates for the case of 0.85 mW cm2 UV-light intensity, at 16 V and at a flow rate of 200
L min1. The animation showing the concentration change over time until the steady state is

reached can be seen in the supplementary data. The microchannel is divided into 10 planes
along the axial direction. The reactions take place at the inner wall, and a nonhomogeneous
concentration distribution can be observed at the planes due to the slow molecular diffusion,
as opposed to the rate of the chemical reactions.

Figure 13. The concentration profiles of phenol and benzoquinone in Cartesian coordinates at
0.85 mW cm2, 16 V and 200 L min1. An animation, representing the change in
concentration with time, is available on-line in the supplementary data.

The complete experimental list with the operational conditions, the degradation extent and the
rate of degradation is also available in the Supplementary material. With
photoelectrocatalysis, 100% degradation was readily achieved. The highest degradation rate
of 26.76 ppm min1 was achieved at 16 V, 2.8 mW cm2, and 600 L min1.
The stability of the catalyst was monitored throughout the experimentation process. After 200
h of operation, there was no measurable lowering of the catalytic activity of the TiO2nanotube catalyst.

4.5 Energy efficiency

During the reactors operation, the energy consumption of the UV lights and the electrical
power needed to apply the external electrical potential were monitored. Our results show that
the electrical power consumed by the potentiostat to apply the electrical potential during the
photoelectrocatalytic and electrocatalytic measurements is negligible compared to the power
consumption for the UV lights. Namely, the power consumption for photocatalytic
degradation at a light intensity of 1.4 mW cm2 is 10.7 W, whereas for photoelectrocatalytic
degradation at the same light intensity and an applied potential of 16 V it is 10.74 W.
However, in the case of photocatalytic degradation some other purification treatment has to be
applied afterwards in order to fully degrade the pollutant, or oxygen has to be continuously
introduced into the microreactor. In the case of using electrocatalytic water purification alone,
the electrical current densities used here are much lower than those normally used in such
treatments [34]. When the potential of 16 V was applied, the current density was only 0.26
mA cm2. Such a current density was high enough to mineralize all the 45.7 mg L1 initial
phenol concentration when photoelectrocatalytic degradation was used at a flow rate of 50 L
min1 and a light intensity of approximately 2.8 mW cm2. Usually, a much lower bias is
applied for photoelectrocatalysis [43], and some authors state that it is counterproductive to

apply electrical potentials larger than 1.229 V because of the water electrolysis reaction [43,
45]. However, our results showed that the application of the relatively low electrical potentials
used for photoelectrocatalytic degradation is not only decisive for mineralization completion
but is also negligible compared to the energy consumption needed to power the light-emittingdiode UV lights.

5 Conclusions

A TiO2-nanotubes-based, coil-type, photoelectrocatalytic microreactor was used to study the

photocatalytic, electrocatalytic, and photoelectrocatalytic degradation of phenol. The results
were used to describe the reaction mechanisms and governing phenomena occurring inside
the microreactor with the help of a mathematical model. It was determined that the
photocatalytic reaction stops due to the increased electronhole recombination resulting from
an oxygen deficiency. The role of the dissolved oxygen is to react with the photogenerated
electrons and therefore enable the holes to react with the water molecules and generate OH.
Our model shows that one reacted O2 results in one OH being produced from H2O at the
positive hole. In the case of electrocatalytic degradation there is a huge jump in the
degradation rate for external applied potentials higher than 8 V. The reason for such behavior
is the high oxidative power of the chlorine radicals that were present because NaCl was used
to increase the phenol solution conductivity. Finally, the results of the photoelectrocatalytic
degradation show a strong synergistic effect between the photocatalytic and electrocatalytic
processes. The oxygen-depletion issue was remedied as the electronhole recombination was
suppressed by the externally applied potential. Only the photoelectrocatalytic degradation
completely mineralized the phenol. The limiting factor influencing the conversion rate of the
photoelectrocatalytic process was the slow diffusion transport of the species to the catalytic
wall. Therefore, the most important augmentation of the studied microreactor would be the

utilization of a narrower microchannel, which would accelerate the overall phenolmineralization process.

Acknowledgments

The provision of financial support for the research and the preparation of the manuscript by
the Slovenian Research Agency (ARRS) within the research program P20084 and the
research program P20152 is gratefully acknowledged.

References

[1] P. C. Singer, Water Sci. Technol. 40 (1999) 2530.

[2] C. C. Kaan, A. A. Aziz, S. Ibrahim, M. Matheswaran, P. Saravanan, Studies on Water
Management Issues, InTech, 2012.
[3] J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo, D. W.
Bahnemann, Chem. Rev. 114 (2014) 99199986.
[4] E. Brillas, I. Sirs, M. A. Oturan, Chem. Rev. 109 (2009) 65706631.
[5] B. P. Chaplin, Environ. Sci.: Processes Impacts 16 (2014) 11821203.
[6] V. Augugliaro, G. Camera-Roda, V. Loddo, G. Palmisano, L. Palmisano, J. Soria, S.
Yurdakal, J. Phys. Chem. Lett. 6 (2015) 19681981.
[7] K. Rajeshwar, M. E. Osugi, W. Chanmanee, C. R. Chenthamarakshan, M. V. B. Zanoni,
P. Kajitvichyanukul, R. Krishnan-Ayer, J. Photoch. Photobio. C 9 (2008) 171192.
[8] R. Andreozzi, V. Caprio, A. Insola, R. Marotta, Catal. Today 53 (1999) 5159.

[9] R. Nakamura, T. Tanaka, Y. Nakato, J. Phys. Chem. B 108 (2004) 1061710620.

[10] M. D. Hernandez-Alonso, F. Fresno, S. Suarez, J. M. Coronado, Energ. Environ. Sci. 2
(2009) 12311257.
[11] S. Y. Chae, M. K. Park, S. K. Lee, T. Y. Kim, S. K. Kim, W. I. Lee, Chem. Mater. 15
(2003) 33263331.
[12] J. B. Joo, M. Dahl, N. Li, F. Zaera, Y. Yin, Energ. Environ. Sci. 6 (2013) 20822092.
[13] J. Lin, X. Liu, S. Zhu, Y. Liu, X. Chen, Nanoscale Res. Lett. 10 (2015) 16.
[14] Y. Yu, D. Xu, Appl. Catal. BEnviron. 73 (2007) 166171.
[15] T. Sauer, G. Cesconeto Neto, H. J. Jos, R. F. P. M. Moreira, J. Photochem. Photobiol.,
A 149 (2002) 147154.
[16] K. Hofstadler, R. Bauer, S. Novalic, G. Heisler, Environ. Sci. Technol. 28 (1994) 670
674.
[17] X. Quan, S. Yang, X. Ruan, H. Zhao, Environ. Sci. Technol. 39 (2005) 37703775.
[19] S. Mozia, P. Brozek, J. Przepiorski, B. Tryba, A. W. Morawski, J. Nanomater. 2012
(2012) 10.
[20] C. M. Ling, A. R. Mohamed, S. Bhatia, Chemosphere 57 (2004) 547554.
[21] M. Zhou, X. Ma, Electrochem. Commun. 11 (2009) 921924.
[22] M. Neumann-Spallart, S. S. Shinde, M. Mahadik, C. H. Bhosale, Electrochim. Acta 111
(2013) 830836.
[23] I. Tantis, E. Stathatos, D. Mantzavinos, P. Lianos, J. Chem. Technol. Biotechnol. 90
(2015) 13381344.

[24] M. Krivec, K. agar, L. Suhadolnik, M. eh, G. Drai, ACS Appl. Mater. Interfaces 5
(2013) 90889094.
[25] N. Wang, X. Zhang, B. Chen, W. Song, N. Y. Chan, H. L. Chan, Lab Chip, 12 (2012)
39833990.
[26] G. Wang, S. Chen, H. Yu, X. Quan, J. Hazard. Mater. 299 (2015) 2734.
[27] G. G. Bessegato, J. C. Cardoso, B. F. da Silva, M. V. B. Zanoni, Appl. Catal., BEviron.
180 (2016) 161168.
[28] E. R. A. Ferraz, G. A. R. Oliveira, M. D. Grando, T. M. Lizier, M. V. B. Zanoni, D. P.
Oliveira, J. Environ. Manage. 124 (2013) 108114.
[29] I. Tantis, M. Antonopoulou, I. Konstantinou, P. Lianos, J. Photochem. Photobiol., A 317
(2016) 100107.
[30] X. Cheng, Q. Cheng, X. Deng, P. Wang, H. Liu, Chemosphere 144 (2016) 888894.
[31] X. Cheng, G. Pan, X. Yu, Chem. Eng. J. 279 (2015) 264272.
[32] Z. Liu, X. Zhang, S. Nishimoto, M. Jin, D. A. Tryk, T. Murakami, A. Fujishima, J. Phys.
Chem. C 112 (2008) 253259.
[33] J. Michaowicz, W. Duda, Pol. J. Environ. Stud. 16 (2007) 347.
[34] M. Zhou, Z. Wu, D. Wang, J. Environ. Sci. Health, Part A: Environ. Sci. Eng. 37 (2002)
12631275.
[35] M. Krivec, A. Pohar, B. Likozar, G. Drai, AIChE J. 61 (2015) 572581.
[36] Q. Chen, H. Liu, Y. Xin, X. Cheng. Chem. Eng. J. 241 (2014) 145154.
[37] D. Wang, X. Li, J. Chen, X. Tao. Chem. Eng. J. 1 (2012) 547554.

[38] M. A. Lazar, S. Varghese, S. S. Nair, Catalysts 2 (2012) 572601.

[39] Y. Xiaoli, S. Huixiang, W. Dahui, Korean J. Chem. Eng. 20 (2003) 679684.
[40] K. Vinodgopal, U. Stafford, K. A. Gray, P. V. Kamat, J. Phys. Chem. 98 (1994) 6797
6803.
[41] M. A. Siddiqi, K. Lucas, Can. J. Chem. Eng. 64 (1986) 839843.
[42] C. R. Wilke, P. Chang, AIChE J. 1 (1955) 264270.
[43] G. Li, L. Wu, F. Li, P. Xu, D. Zhang, H. Li, Nanoscale 5 (2013) 22182125.
[44] T. A. Egerton, J. Chem. Technol. Biotechnol. 86 (2011) 10241031.
[45] F. E. Osterloh, B. A. Parkinson, MRS Bull. 36 (2011) 1722.

Table 1. The kinetic parameters for photocatalysis and photoelectrocatalysis obtained using
the regression analysis of the experimental data.
parameters

value

kPhBq KPh (L s1 mol1)

9.51 102

kPhmin KPh (L s1 mol1)

1.48 103

kBqmin KBq (L s1 mol1)

1.36 104

nl1

0.91

kred KO2 (mW cm2)nl1 s1)

1.18 105

I0 (mW cm2)nl2

0.25

nl2

0.94

Ne

0.96

kelect ((mW cm2)nl2mAnemol L1 s1)

1.18 108

A novel coil-type TiO2-nanotube photoelectrocatalytic microreactor was designed.

The mechanisms and kinetics of phenol photoelectrocatalysis were described.
There was a strong synergistic effect between photo- and electro- catalysis.
The applied electric current prevented electron-hole recombination.
The energy for the electrical current is insignificant compared to the UV lamps.