International Journal of Environmental Science and Technology

https://doi.org/10.1007/s13762-018-1755-2

ORIGINAL PAPER

Photodegradation of humic acid in aqueous solution using

a ­TiO2‑carbonaceous hyper‑cross‑linked polystyrene polymer
nanocomposite
N. Chaukura1 · S. S. Mukonza1 · T. I. Nkambule1 · B. B. Mamba1

Received: 10 May 2017 / Revised: 23 January 2018 / Accepted: 11 May 2018

© Islamic Azad University (IAU) 2018

Abstract
The development of alternative methods to degrade natural organic matter or its components to harmless products is an area
that has been attracting significant research interest lately. This paper reports the photodegradation of humic acid using a
composite photocatalyst made up of ­TiO2 nanoparticles and a carbonaceous hyper-cross-linked polystyrene-type precursor
derived from post-consumer waste polystyrene. The physicochemical properties of the ­TiO2-carbonaceous hyper-cross-linked
polystyrene nanocomposites were determined using Fourier transform infrared spectroscopy, UV–visible spectroscopy, scan-
ning electron microscopy and X-ray diffraction spectroscopy. Batch experiments were used to evaluate the capacity of the
materials to photodegrade humic acid in synthetic wastewater samples using a solar simulator. Despite showing marginal
band-gap narrowing, the introduction of carbonaceous hyper-cross-linked polystyrene into ­TiO2 was accompanied by a 100%
increase in the degradation rate of humic acid at a contact time of 90 min. Overall, the photodegradation capacity of the
composites increased with an increase in the carbonaceous hyper-cross-linked polystyrene content. The use of post-consumer
waste polystyrene in preparing high-value materials is novel and a cost-effective way of water treatment that simultaneously
makes a contribution towards alleviating the environmental burden of waste polystyrene.

Keywords Photodegradation · Pollution · Polymers · Porosity · Waste polystyrene

Introduction organic matter (NOM), which is a bio-recalcitrant pollutant

Although water constitutes one of the most abundant natural
resources globally, a significant proportion of the world’s
population still lacks access to clean water (Adeleye et al.
2016; Gwenzi et al. 2017). Moreover, research has shown
that water scarcity is expected to increase in future even
in those regions that currently have enough water (Nkam-
bule et al. 2009; Neto et al. 2012). Additionally, sources of
water are increasingly contaminated with a range of emerg-
ing pollutants due to human activity and natural phenom-
ena (Gwenzi et al. 2017). One pollutant of concern that
has recently attracted the attention of researchers is natural
Editorial responsibility: Binbin Huang.
* N. Chaukura
nchaukura@gmail.com
1 bacterial re-growth; (4) it reacts with disinfectants to form
Nanotechnology and Water Sustainability Research Unit,
College of Science, Engineering and Technology, University
of South Africa, Johannesburg, South Africa
comprising of different organic compounds, from highly ali-
phatic to highly coloured aromatic compounds (Matilainen
et al. 2010; Oskoei et al. 2016; Gora and Andrews 2017; Li
et al. 2017). It originates from the microbiological degrada-
tion of plant and animal residues and has both hydrophilic
and hydrophobic components (Matilainen et al. 2010; Bho-
sale et al. 2016).
The hydrophobic component of NOM consists of ful-
vic and humic acids and is made up of phenolic structures,
aromatic carbon and conjugated double bonds (Matilainen
et al. 2010; Bhosale et al. 2016). Natural organic matter is
of concern for a variety of reasons, including: (1) it imparts
objectionable organoleptic properties to drinking water
(Pasandideh et al. 2016; Zulfikara et al. 2016; Chaukura
et al. 2017a; Shankar et al. 2017); (2) it binds toxic metals
and other organic pollutants, facilitating their transportation
in aquatic systems (Bhosale et al. 2016); (3) it promotes
disinfection by-products (DBPs), which are toxic and carci-
nogenic compounds (Chu et al. 2016; Li et al. 2016; Oskoei

13
Vol.:(0123456789)

et al. 2016; Zheng et al. 2016; Li et al. 2017; Marcoux et al.
2017; Wang et al. 2017); and (5) NOM interferes with water
treatment processes by increasing the quantities of coagu-
lant required, and by causing membrane fouling (Gora and
Andrews 2017; Shankar et al. 2017).
Methods commonly used for NOM removal from water
include coagulation, ozonation, activated carbon filtration
and adsorption, membrane filtration and photodegradation
(Pasandideh et al. 2016; Markad et al. 2017). Despite using
inexpensive feedstocks to produce activated carbons, the
energy required to produce high-quality activated carbon can
have a significant environmental impact especially if non-
renewable energy sources are used (Adeleye et al. 2016).
In addition, the regeneration capacity of biosorbents can
be limited, and the final disposal of pollutant-laden sludge
is problematic (Chaukura et al. 2016). While coagulation
mainly reduces colour, turbidity and eliminates pathogens
during water treatment (Matilainen et al. 2010), the con-
ditions for colour removal and turbidity are different from
those used for NOM removal. Increasing the coagulant dos-
age increases water treatment costs and sludge volumes,
whose disposal poses environmental and health risks (Adel-
eye et al. 2016). Recent work has shown that the hydrophilic
fraction of NOM is not effectively removed by coagulation
compared to the hydrophobic fraction (Matilainen et al.
2010). While NOM can be removed during filtration pro-
cesses, it decreases the efficiency of the removal of other
pollutants by competing for the adsorption active sites (Mat-
ilainen et al. 2010). Reverse osmosis, ultrafiltration, micro-
filtration and nanofiltration are pressure-driven membrane
methods with varying potential for NOM removal (Mati-
lainen et al. 2010). Some of the disadvantages of membranes
include high cost, fouling and decline in permeate flux due
to fouling, with NOM being reported as the major cause
(Matilainen et al. 2010). In order to overcome these adverse
effects, pre-treatment with coagulation is used, further
increasing the cost of water treatment and sludge burden.
Thus, commonly used removal technologies are either too
expensive or unable to efficiently remove NOM from water
treatment systems. These challenges necessitate research to
develop effective and robust methods for water treatment at
low cost, while keeping the use of chemicals with adverse
ecological impacts to a minimum to complement or replace
existing technologies.
A number of photocatalysts have been synthesised and
used to photodegrade and/or mineralise a variety of organic
pollutants. Examples include carbon nitride used to remove
sulphamethazine from aqueous solution (Zhou et al. 2018),
bismuth oxyhalides for the removal of azo dyes and other
organics (Jin et al. 2017), ­MgGa2O4 for photolysis of Rho-
damine B (Feng et al. 2017), ZnO/Ag hollow spheres for
dye degradation (Liu et al. 2018) and Ag-doped ­TiO2 for
the photodegradation of tetracycline (Xiong et al. 2017).
13
International Journal of Environmental Science and Technology
Extensive research has been done, and many reports are
available in the literature on photodegradation using ­TiO2
nanoparticles (e.g. Maletic et al. 2016; Oskoei et al. 2016;
Gora and Andrews 2017; Guo et al. 2017; Shi et al. 2017;
Xie et al. 2017; Zhang et al. 2017). This is mainly because
­TiO2 has chemical and biological stability, is non-toxic, is
insoluble in water, has photocatalytic activity and is avail-
able at low cost (Maletic et al. 2016; Guo et al. 2017). In
addition, ­TiO2 can effectively photodegrade large organic
molecules to smaller and less harmful compounds (Mal-
etic et al. 2016; Gora and Andrews 2017; Shi et al. 2017).
However, ­TiO2 has a wide band gap of 3.2 eV, which cor-
responds to the UV region, and thus, only 4–5% of the solar
spectrum can be used in photoexciting ­TiO2 (Maletic et al.
2016; Guo et al. 2017). This limits its photocatalytic effi-
ciency under solar light, which in turn restricts its suitability
in environmental remediation (Guo et al. 2017). Like other
semiconductors, ­TiO2 undergoes electron–hole recombina-
tion which reduces the quantum yield and the photocatalytic
efficiency (Markad et al. 2017; Zhang et al. 2017). Use has
been made of metal-doped T ­ iO2 to facilitate charge carrier
separation and reduce electron–hole recombination; how-
ever, this approach is limited by poor economic viability
(Markad et al. 2017). Consequently, instead of the expensive
metal or non-metal dopants, research has lately focused on
using carbon-based materials for ­TiO2 modification (e.g.
Markad et al. 2017; Xie et al. 2017; Zhang et al. 2017).
For example, bisphenol-A was successfully removed from
synthetic wastewater using a molecular imprinted ­TiO2/gra-
phene photocatalyst (Lai et al. 2016). In this regard, carbo-
naceous hyper-cross-linked polystyrene (CHCPS) derived
from post-consumer waste polystyrene (WPS) has to date
not been exploited for this application.
Pollution due to WPS is well documented (Hussain et al.
2012; Meng et al. 2013; Bartoli et al. 2015; Ruziwa et al.
2015; Vinodh et al. 2015; Gu et al. 2016; Ling et al. 2016).
The disposal of WPS is problematic because burning can
cause formation of polyaromatic hydrocarbons (PAHs), and
land-filling is limited by space and can result in leaching
of toxins into the soil and potentially contaminating sur-
face water and groundwater (Chaukura et al. 2016). Among
other properties, conjugated microporous polymers have
been reported to be photoactive owing to the presence of
the π-electron system within their structure (Xu et al. 2013;
Ma et al. 2015). The development of photocatalysts from
WPS is particularly attractive owing to the cost-effective-
ness of the resulting material, and the concurrent benefit of
mitigating the ecological burden of solid waste. This work
investigated the photodegradation of humic acid (HA) using
nanocomposites derived from CHCPS to ­TiO2. To the best
of our knowledge, the use of T ­ iO2–CHCPS (TCHCPS) for
the photodegradation of HA is a novel approach that has
not been reported elsewhere. The aims were to: (1) prepare
International Journal of Environmental Science and Technology
a carbonaceous hyper-cross-linked polystyrene and use it as
a precursor for a ­TiO2 nanocomposite (TCHCPS); and (2)
evaluate the photodegradation of HA using the said materi-
als. The study was carried out in the period March–April,
2017 at the University of South Africa, Florida Science cam-
pus, South Africa.
Materials and methods
Preparation of ­TiO2‑carbonaceous
hyper‑cross‑linked polystyrene nanocomposites
The chemicals used in this work were exclusively of analyti-
cal grade and purchased from Sigma-Aldrich (Germany).
The water used in the preparation of all solutions was
obtained from a Milli-Q Micropore water purification sys-
tem. WPS was used as the main raw material in the prepara-
tion of CHCPS. The synthesis of CHCPS was via an inter-
mediated reported by the authors elsewhere (Chaukura et al.
2017b). Briefly, dry WPS (10 g) was dissolved in 100 mL
dichloromethane in a 500-mL two-neck round-bottom flask.
To this was added dimethoxymethane (5 mL) and catalytic
amounts of ­FeCl3 and refluxed for 8 h at 80 °C with stirring.
The cross-linked polymer was precipitated out of solution
by slowly adding methanol (100 mL) and washed with an
acidified 1:1 acetone/water mixture. This material was then
oven-dried at 70 °C for 10 h and crushed to pass through
a 800-micron sieve before being sulphonated to produce
sulphonated hyper-cross-linked polystyrene (SHCPS).
The sulphonation process entailed slowly adding 100 mL
of concentrated ­H2SO4 to 5 g of CMP in a 250-mL round-
bottomed flask. This was followed by refluxing the mixture
for 1 h at 70 °C; then, the synthesised polymer was washed
with deionised water and dried at 70 °C for 10 h. Prepa-
ration of the carbonaceous hyper-cross-linked polystyrene
(CHCPS) was performed by pyrolysis of SHCPS in a tube
furnace under a continuous ­N2 gas flow at 800 °C for 2 h,
followed by cooling to room temperature before further use.
The ­TiO2–CHCPS (TCHCPS) composite was synthesised
by coating CCMP with ­TiO2 using a one pot acid-catalysed
sol–gel method (Li et al. 2007; Guo et al. 2017). In brief,
CHCPS was added to 2-propanol (50 mL), followed by
30 min of high frequency sonication at 40 °C. Titanium iso-
propoxide (10 mL) was added to the mixture to give 2.5, 5,
7.5 and 10% CHCPS (w/w) followed by further sonication
for 30 min. To this was added formic acid (10 mL) drop-
wise under continuously stirring for at most 1 h until a white
sol–gel was observed. This was subsequently aged for 24 h
in air at room temperature and then oven-dried at 80 °C for
10 h. Thereafter, the sample was pulverised and calcined at
450 °C for 4 h in a muffle furnace.
Characterisation
Specific surface area and porosity were measured using
a porosimeter (TriStar II 3020, Germany). Infrared spec-
tra were recorded by collecting 4 scans in the range
4000–400 cm−1 using an FTIR spectrometer (Thermo Sci-
entific, Nicolet iS5, USA) on samples prepared by the KBr
method. The surface morphology of ­TiO2, CHCPS and
TCHCPS was determined using scanning electron micros-
copy (SEM) (QuantaTM 250 FEG, Questar, USA) at 40 µm
magnification after coating the sample surfaces with a 15 µm
carbon film. The UV–Vis data were collected on powder
samples using a Lambda 650S, Perkin Elmer spectropho-
tometer. Using UV–Vis data, the Kubelka–Munk function
was used to determine the absorption coefficient for pre-
dicting reflectance based on radiation transfer (Eq. 1) (Shen
et al. 2016):
(1 − R)2
F(R) = (1)
2R
where F(R) is the Kubelka–Munk function, and R is the per-
centage reflectance.
From the Kubelka–Munk coefficient, Tauc plots [Eq. 2]
were computed in order to estimate the band gap (Eg) of the
materials (Dolgonos et al. 2016):
1
[h𝜈 × F(R)] n = A(h𝜈 − Eg )n (2)
where h is Planck’s constant, v, c and λ are the frequency,
speed and wavelength of the radiation, respectively.
The type of transition, n can take values of 1/2, 2, 3/2 or 3
corresponding to allowed direct, allowed indirect, forbidden
direct or forbidden indirect transition. For ­TiO2, n =2 is used
to estimate the indirect band gap.
Photodegradation experiments
Humic acid working solutions were prepared in deionised
water. The photocatalytic degradation experiments were per-
formed in triplicate on an admixture of 40 mL of prepared
HA samples at pH 6.8 with 0.1 g of TCHCPS in a 100-
mL beaker following a variation of the method reported by
Zhang et al. (2017). All samples were stirred in darkness
for 1 h to attain absorption equilibrium prior to solar light
irradiation. The admixture was loaded into a 100 mW/cm2
solar simulator (HAL-320, Asahi Spectra, Japan) equipped
with a 300 W compact Xenon lamp at 60% intensity at an
illumination distance of 3.70 cm and stirred at room temper-
ature. Fluorescence excitation–emission matrices (FEEM)
were collected for neat HA and after photolysis using a Per-
kin Elmer LS 45 fluorescence spectrometer. Samples were
withdrawn at 30 min intervals so that the total volume of
the withdrawn sample was less than 2% (v/v) of the solution
13
 International Journal of Environmental Science and Technology

using a 10-mL syringe and filtered through the GH Polypro p/p0= 0.955 of 0.4425, 0.2511, 0.1933 cm3/g, respectively.
(GHP) membrane disc filter. The absorbance of the filtrate The surface area of synthesised T ­ iO2 is an order of magni-
was determined using a UV–Visible spectrophotometer tude greater than that reported for the commercial anatase
(Lambda 650S, Perkin Elmer) at λmax = 254 nm. The frac- Degussa P-25 ­TiO2 by Sutisna et al. (2017). In addition,
tional degradation η was calculated from [Eq. (3)] (Shi et al. when ­TiO2 is combined with CHCPS there is a loss of sur-
2017): face area and porosity, probably due to pore blocking by
agglomeration of T ­ iO2 particles (Gora and Andrews 2017;
Co − Ct
𝜂= (3) Reza et al. 2017). Among other properties, the BET surface
Co
area and porosity influence the degradation rate of organic
where Co and Ct are the respective UV absorbances of HA compounds by photocatalysts. Pyrolysis was performed to
at 254 nm at initial time and after contact time t under solar give the polymer mechanical and chemical integrity and
irradiation. improve the porosity of the material. Overall, carbonis-
To investigate the photocatalytic mechanism, the photo- ing organic materials produces materials with controllable
degradation data were fitted to the Langmuir–Hinshelwood morphology and other intrinsic properties (Matsushita et al.
model [Eq. (4)] (Chiche and Schweitzer 2017): 2016).
( )
Co
Ln = kt (4) FTIR
Ct

where k is the apparent reaction rate constant.
In order to determine the amount of organic carbon in
a sample to evaluate the degree of mineralisation of HA, a
fusion total organic carbon (TOC) analyser (Teledyne Tek-
mar Company, Inc., USA) was used.
Results and discussion
Characterisation
Textural properties
The BET surface areas of ­TiO2, CHCPS and TCHCPS were
109, 214 and 123 m2/g, respectively, with pore volumes at
The presence of certain functional groups in the stud-
ied samples was inferred on the basis of the FTIR spectra
(Fig. 1). All FTIR spectra showed major OH peaks (broad
O–H stretch peak) in the range 3200–3600 cm−1, which was
attributed to OH bending, probably due to adsorbed mois-
ture (Maletic et al. 2016). The OH functional groups can be
trapped by the holes generated under UV radiation to form
hydroxyl radicals which enhance photocatalytic efficiency
by suppressing electron–hole recombination. The C=C–C
bond appearing around 1 650 cm−1 suggests the existence of
appreciable conjugation (Chaukura et al. 2017b). The inten-
sity of the CS bending at 1 160 cm−1 increased with CHCPS
loading, indicating an increase in surface sulphonic groups
derived from the CHCPS. This showed that the incorpora-
tion of CHCPS into ­TiO2 increased the amount of oxygen-
carrying groups on the ­TiO2 surface, which are important in

Fig. 1  FTIR spectra for ­TiO2

Ti-O-Ti
Ti-O-C
(bold black), T
­ iO2 with 2.5%
C=C
O-H

O-H

C-S
OH

CHCPS (red), ­TiO2 with 5%

CHCPS (blue), ­TiO2 with 10%
CHCPS loading (orange), and
CHCPS (black dashed)
% Transmittance (a.u.)

3900 3400 2900 2400 1900 1400 900 400

Wavenumber (cm-1)

13
International Journal of Environmental Science and Technology

improving the photocatalytic activity. High-intensity sym-
metrical peaks around 500–750 cm−1 and the peak around
1 100 cm−1 in the spectra are ascribed to the Ti–O–Ti and
Ti–O–C bonds, respectively (Xie et al. 2017). The pres-
ence of Ti–O–C bonds shows chemical bonding interaction
between the ­TiO2 nanoparticles and CHCPS (Zhang et al.
2017).
UV–visible spectra
Based on UV–Visible reflectance spectra, a progressive
red-shift with increasing CHCPS loading was observed
(Fig. 2a). The increased absorption intensity in the
UV–visible region of the CHCPS loaded ­TiO2 is due to
the electronic transitions to the CHCPS π-electron system,
where the CHCPS structure is acting as an electron sink
(Markad et al. 2017). Carbonaceous hyper-cross-linked
polystyrene molecules and similar graphenic molecules
have been reported to abstract electrons from the con-
duction band of T ­ iO 2-based materials (Lai et al. 2016;
Markad et al. 2017). The diffuse reflectance data were
converted to the Kubelka–Munk function F(R), which is
a coefficient that indicates the magnitude of absorption
for a sample (Fig. 2b) (Shen et al. 2016), and confirms the
UV–Vis spectral data (reflectance). Estimated band-gap
energy values from Tauc plots for T ­ iO 2, 2.5% CHCPS,
5% CHCPS and 10% CHCPS were 3.26, 3.24, 3.23 and
3.21 eV, respectively (Fig. 2c). The estimated band gap
for ­TiO2 was comparable to the value reported in litera-
ture that ranges from 3.0 to 3.2 eV (Samsudin and Hamid
2017), and increasing CHCPS loading showed shifts of
the band gap towards the UV and near-infrared regions.
Overall, introducing CHCPS into T ­ iO2 showed marginal
band-gap narrowing, and consequently, the wavelength
absorption edge of the TCHCPS exhibited a red-shift.
This is due to the fact that the CHCPS introduces impuri-
ties which cause intra-band-gap energy states between the
­TiO2 valence band and conduction band. This result sug-
gests that the interaction between T­ iO2 and CHCPS in the
TCHCPS became progressively stronger with increasing
CHCPS loading. This may be due to the formation of a
Ti–O–C chemical bond between the T ­ iO2 and the specific

(a) 2.5 (b)

100

2
80
% Reflectance

1.5
F(R)

60

40 1

20 0.5

0 0
340 350 360 370 380 390 400 350 360 370 380 390 400
Wavelength (nm) Wavelength (nm)

(c)
[F(R)x hv]1/2

0
3 3.1 3.2 3.3 3.4 3.5
hv(eV)

Fig. 2  a Diffuse reflectance UV–Vis spectra; b Kubelka–Munk function plots; and c Tauc plots for T
­ iO2 (black), ­TiO2 with 2.5% CHCPS load-
ing (orange), T­ iO2 with 5% CHCPS loading (blue), and ­TiO2 with 10% CHCPS loading (red)

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 International Journal of Environmental Science and Technology

carbon sites of CHCPS. Zhang et al. (2017) reported a Xrd

similar result for ­TiO2-graphene oxide composites.
The XRD peaks of the T ­ iO2 and TCHCPS photocatalysts
Sem showed almost identical peaks (Fig. 4). For these two pho-
tocatalysts, the anatase phase is predominant, with peaks at
Whereas SEM micrographs show a dispersion of aggre- 2θ positions of 25.4°, 38.2°, 48.1°, 54.3°, 55.2°, 62.8° and
gated spherical T ­ iO2 nanoparticles (Fig. 3a), the CHCPS 75.4°, corresponding to the crystal planes of (101), (004),
is characterised by irregular porous particles (Fig. 3b). A (200), (105), (211), (204) and (215), respectively (Guo et al.
composite of ­TiO2 and 10% CHCPS to produce TCHCPS
showed a micrograph that closely resembles that for T ­ iO2,
with a slightly lower aggregation (Fig. 3c). Although it is
difficult to observe CHCPS particles due to the low amount

Intensity (a.u)
of CHCPS added, the presence of CHCPS seems to result
in increased aggregation of ­TiO2 particles. A similar obser-
vation was reported for ­TiO2 nanoparticles immobilised on
cellulose fibres (Zhang et al. 2017). The complete wrapping
of CHCPS by T ­ iO2 particles is required in order to improve
the photoactivity of the TCHCPS photocatalyst. 20 30 40 50 60 70 80
2θ

Fig. 4  XRD spectra for T

­ iO2 (black), CHCPS (dashed), and TCHCPS
with 10% CHCPS loading (red)

Fig. 3  SEM micrographs for a ­TiO2; b CHCPS; and c ­TiO2 with 10% CHCPS

13
International Journal of Environmental Science and Technology

2017; Xie et al. 2017; Zhang et al. 2017). The CHCPS par- observed in the degradation of HA; and (2) an increase in
ticles seem to inhibit the phase transformation of ­TiO2 from the contact time increased the hydroxyl radicals produced
the anatase to the rutile structure, leaving the anatase as the by UV radiation, which in turn increased the photodegrada-
dominant phase. Materials such as activated carbon have tion rate (Oskoei et al. 2016). After irradiation for 90 min,
been reported to have a similar effect on T ­ iO2 phases (Li the degradation efficiency of HA decreased in the order:
et al. 2007). The spectra for CHCPS showed that the mate- 10% CHCPS (60%) > 5% CHCPS (50%) > 2.5% CHCPS
rial was amorphous, and the peaks were dwarfed because it (40%) > TiO2 (30%) > CHCPS (Fig. 5a). However, these
is present in low concentrations. removal efficiencies were found to be lower than the 73.43
and 81.4% reported for the removal of HA using ZnO pho-
Photodegradation of HA tocatalysts (Oskoei et al. 2016). Overall, TCHCPS materials
showed superior performance compared to ­TiO2, indicat-
Adsorption and photodegradation occur simultaneously ing that CHCPS played a vital role in improving the pho-
on the surface of the photocatalyst (Maletic et al. 2016). tocatalytic activity of ­TiO2. The CHCPS shows very low
A FEEM illustration of the degradation shows a dramatic (< 5%) and constant removal efficiency, which could be due
decrease in HA concentration from the initial to the final HA to adsorption. Due to fact that CHCPS is capable of adsorb-
concentration (Fig. 5a Insert). The HA removal efficiency ing organics, the introduction of CHCPS into ­TiO2 to form
was initially rapid for two reasons: (1) at the outset there the TCHCPS composite increases the contact between HA
was a large population of photoactive sites on the photo- and ­TiO2 particles where the ­h+ and •OH photoreactive spe-
catalysts surface, but then these sites gradually diminished cies are located, improving the removal of HA. Khraisheh
with the degradation of HA, and consequently, a decline was et al. (2014) reported a similar finding for the photodegra-
dation of carbamazepine using ­TiO2–coconut shell powder
composites. Owing to the large number of ­TiO2 particles
(a) photolysis
on the CHCPS, the rapid adsorption of HA by TCHCPS
0.8 significantly increases the contact between HA and T ­ iO2
surfaces. Moreover, the introduction of CHCPS into T ­ iO2
0.6 progressively reduced the band gap, pushing the absorption
range of solar radiation towards the UV and near-infrared
η 0.4 regions. Additionally, CHCPS particles facilitate the trans-
portation of photo-induced electrons from the T ­ iO2 parti-
0.2
cles to the CHCPS support, thus expediting electron–hole
0
separation. The enhanced electron–hole separation ensures
0 50 100 150 200 a higher population of electrons, and a higher population
Irradiation time (min) of holes reacting with H ­ 2O to produce a greater amount of
•OH, which are responsible for mineralising HA to ­CO2 and
(b) 1.5 ­H2O (Markad et al. 2017; Xie et al. 2017). Besides improv-
ing the quantum efficiency of T ­ iO2, CHCPS effectively acts
as an electron sink for photo-induced electrons reducing the
electron–hole recombination rate and thus improving the
1
photocatalytic activity (Markad et al. 2017).
Ln(C o/C t)

The degradation kinetics of HA over an irradiation

time of 180 min was used to approximate the reaction
0.5
rate constants, k (Fig. 5b). Linear correlations with r2 val-
ues ranging from 0.86 to 0.98 were observed, indicating
that all the photodegradation reactions followed pseudo-
first-order kinetics. The HA degradation reaction veloc-
0 ity by the photocatalysts increased in the order CHCPS
0 50 100 150 200 (k = 0.0 min−1) < TiO2 (k = 2 × 10−3 ­min−1) < 2.5% CHCPS
irradiation time (min) (k = 3 × 10−3 ­min−1) < 5% CHCPS (k = 4 × 10−3 ­min−1) < 10%
CHCPS (k = 5 × 10−3 ­min−1). The fact that the rate constant
Fig. 5  a Photodegradation of HA using T ­ iO2 (black diamonds), T
­ iO2 for CHCPS is very small suggests that the material on its
with 2.5% CHCPS (orange crosses), T ­ iO2 with 5% CHCPS (blue tri-
own is not significantly photoactive. Generally, the k values
angles), ­TiO2 with 10% CHCPS (red squares), CHCPS (green circles)
with FEEM matrices for the photodegradation of HA (insert), and b obtained in this work were comparable to those reported
pseudo-first-order kinetics for degradation of HA for ­TiO2 supported on slag-made calcium silicate for the

13

photolysis of methylene blue dye (Shi et al. 2017). Overall,
all the TCHCPS composite materials performed better than
pristine ­TiO2, indicating that CHCPS improved the photo-
catalytic activity of T
­ iO2. Other organic materials have been
reported to possess similar properties (Markad et al. 2017).
Photodegradation mechanism
In the mechanism for electron transfer and photodegrada-
tion of HA by TCHCPS catalyst under visible light illumi-
nation, CHCPS acts as visible light sensitiser and electron
shuttle, which can transfer electrons to ­TiO2 (Fig. 6). The
CHCPS has the ability to transfer energy to ­TiO2 which
helps generate electron–hole pairs in ­TiO2. These excited
electrons from ­TiO 2 can be transferred to the CHCPS
π-electron system where CHCPS acts as an electron sink
(Markad et al. 2017). Subsequently, the electrons from the
CHCPS surface reduce oxygen to reactive oxygen species
which react with water, eventually producing hydroxyl rad-
icals for mineralisation of HA. At the same time, the oxi-
dation of water on the ­TiO2 surface through valence band
holes leads to the formation of hydroxyl radicals (•OH),
which take part in the degradation of HA. Alternatively,
Fig. 6  Possible mechanism for electron transfer and photocatalytic decolouration of HA on TCHCPS catalyst under visible light illumination
13
International Journal of Environmental Science and Technology
valence band holes can directly react and mineralise HA
molecules (Khraisheh et al. 2014). Generally, the electron
accepting ability of the CHCPS surface helps to reduce
electron–hole pair recombination in T­ iO2, thus enhancing
the quantum efficiency through synergistic effects (Gora
and Andrews 2017; Markad et al. 2017).
Thus, it is presumed that upon applying simulated solar
irradiation (photon energy (hv) in eV), the TCHCPS parti-
cles would be excited so that they produced different pho-
toreactive species to react with HA (Xie et al. 2017), as
described by the following sequence of reactions:
TiO2 + hv → TiO2 e− + h+ (photo - excitation)
( )
TCHCPS + hv → h+ + e− (photo - sensitiser)
H2 O + e− → ∙OH + H+
HA + ∙OH → CO2 + H2 O
HA + h+ → CO2 + H2 O
while ­TiO2 achieved a 38% decrease in TOC, TCHCPS at
10% CHCPS loading achieved about 60%. This is consist-
ent with HA degradation efficiencies measured by UV–Vis.
International Journal of Environmental Science and Technology
Although the above mechanism assumes complete minerali-
sation of HA, it is important to monitor the degradation in
order to determine the degree of mineralisation and to iden-
tify the products of photodegradation using techniques such
as LC–MS, due to the fact that some intermediate products
like nitrated polyaromatic compounds which are toxic, can
potentially form and further pollute the water.
Conclusion
A range of photocatalytically active T
­ iO2-CHCPS nanocom-
posites were prepared by the acid-catalysed sol–gel method.
Both ­TiO2 and TCHCPS photocatalysts showed crystalline
particles of predominantly anatase phase. The incorpora-
tion of CHCPS significantly reduced the ­TiO2 band gap and
improved the quantum efficiency of the photocatalyst, result-
ing in an enhanced photocatalytic efficiency of TCHCPS
relative to that of T
­ iO2 by a factor of 2. The photodegra-
dation reactions followed pseudo-first-order kinetics, and
optimum degradation of HA was observed after 90 min of
solar irradiation. The photoactivity of TCHCPS composites
is higher than that of T­ iO2, possibly due to the following
reasons: (1) the presence of CHCPS increases the concentra-
tion of organic pollutants on the surface of ­TiO2 facilitating
the contact of the reactive species with the organic mol-
ecules for photocatalytic degradation to take place and thus
increasing the photocatalytic activity of T
­ iO2 particles; near
micron-sized ­TiO2 particles were found to be well-dispersed
on the surface of CHCPS, (2) CHCPS reduces the band gap
of ­TiO2, increasing the range of absorption of photo-radi-
ation; and (3) CHCPS acts as an electron sink, thus reduc-
ing electron–hole recombination and increasing quantum
efficiency. Further research is required on: (1) the potential
of the photocatalysts to be reused multiple times. This will
provide information on the robustness of the photocatalyst
and on the cost-effectiveness and hence potential for scal-
ability of the technology; and (2) identifying the products of
photodegradation. Use of TCHCPS for the degradation of
HA in aqueous solution is thus an innovative post-treatment
method that valorises post-consumer waste into a novel and
potentially cost-effective water treatment material.
Acknowledgements Support from the Nanotechnology and Water Sus-
tainability (NanoWS) Research Unit at the University of South Africa
(Research Fund: 139000) is acknowledged.
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