Carbon 178 (2021) 753e766

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Activated carbon-based coloured titania nanoparticles with high

visible radiation absorption and excellent photoactivity in the
degradation of emerging drugs of wastewater
Safa Benjedim a, b, Jesica Castelo-Quibe
n a, Esther Bailo
n-García a, *, El Mostapha Lotfi b,

rez-Cadenas , Va
Agustín F. Pe a
clav Slova

k , Jirí Kalina c, Francisco Carrasco-Marín a
c

a
Grupo de Investigacio
n en Materiales de Carbo
nica/Universidad de Granada, Granada, Spain

n/Dpto. Química Inorga
b
Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, Environmental Materials Team, ENSET, Mohammed V
University of Rabat, Rabat, Morocco
c
University of Ostrava, Faculty of Science, Department of Chemistry, 30. Dubna 22, 702 00, Ostrava, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: Activated carbon/TixOy nanoparticles (CTi) were synthesized by a controlled hydrolysis method under
Received 9 February 2021 mild conditions of temperature (170e210
C) and pressure (8 bar). These new materials are presented as
Received in revised form visible-light driven photocatalysts with high performance in the degradation of emerging drugs in
14 March 2021
wastewater, like amoxicillin and paracetamol. The presence of Ti3þ self-structural modified TiO2 was
Accepted 19 March 2021
corroborated by XPS and Raman. The TiO2 reduction effectivity and consequently, the photocatalytic
Available online 29 March 2021
activity, is influenced by the treatment temperature and the presence of carbon matrix. The band-gap
decreases from 3.1 to 1.7 eV by the addition of carbon during the synthesis of coloured titania at
Keywords:
Black TiyOx
210
C and from 3.0 to 1.7 eV by increasing the solvothermal temperature from 170 to 210
C in the
Amoxicillin preparation of activated carbon-based coloured titania nanoparticles. The presence of carbon also im-
Paracetamol proves the electron transfer from titania nanoparticles to carbon (confirmed by XPS) minimizing
Activated carbon electron-hole recombination. All these factors improve the photocatalytic performance of the synthe-
Photocatalysis sized materials under visible irradiation providing a cost-effective method for the degradation of
persistent wastewater pollutants.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction byproducts and pesticides [5e7]. These emerging pollutants cannot

be effectively removed in the conventional wastewater treatment
Water will become a scarce and increasingly inaccessible plants, thus, most of them escape from wastewater treatment
resource due to the increasing population and living standard, the plants avoiding the reuse of treated effluents and reaching aquatic
growing water pollution, and the industrial growth. Thus, the ecosystems such as rivers and lakes [5]. Despite their low concen-
decontamination and reuse of water is one of the most serious tration, they can bioaccumulate due to their persistence with
global challenges [1e3]. hazardous consequences to the health of humans and flora and
Several technologies have been used in wastewater treatment fauna. Besides, the implementation of effective tertiary treatments
plants to decontaminate wastewater up to drinking water quality. is required in order to ensure the protection of the environment
However, new and more stable pollutants, called emerging pol- and a safe reuse of wastewater [8,9].
lutants (EPs), have been emerged in the wastewater in recent years Advanced methods to remove these emerging pollutants can be
[4]. These pollutants consist mainly in organic compounds biodegradation, chemical advanced oxidation or physical means
including steroids and hormones, perfluorinated compounds, such as adsorption by activated carbon or rejection by membranes
drugs, personal care products, endocrine disruptors, disinfection [10,11]. Advanced oxidation processes are considered the most
effective way to face the water pollution problems since contami-
nants are degraded by effective and highly reactive oxidizing radicals
generated “in situ” and thus, sub-product management problems
* Corresponding author.

n-García).
E-mail address: estherbg@ugr.es (E. Bailo such as regeneration of adsorbents and disposal of recovered

https://doi.org/10.1016/j.carbon.2021.03.044
0008-6223/© 2021 Elsevier Ltd. All rights reserved.
S. Benjedim, J. Castelo-Quib
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n-García et al. Carbon 178 (2021) 753e766

contaminants are avoided [12e14]. Among them, TiO2-based solar Alternatively, another interesting solar-driven material is the
photocatalysis is presented as an attractive solution to remove Ti3þ self-structural modified TiO2 or the also known as black or
emerging pollutants because TiO2 present non-toxicity, high stability coloured titania. Coloured titania can absorb the entire or a high
and low cost and the ease of the process; the only required reagents part of the solar spectral range showing a high photoactivity under
of the process are a source of light and oxygen and the process is visible light. This coloured titania is commonly obtained from white
performed under ambient temperature and pressure conditions. titania by hydrogenation, but high temperatures and pressures are
Moreover, the use of renewable solar energy makes the process cost- required [27e29]. Other methods have been studied in order to
effective and environmentally friendly [15]. All these reasons makes reduce the production costs of coloured titania, either reductive or
the solar photocatalysis a feasible route for its implementation in oxidative methods [30], however they still are high energy
conventional wastewater treatment plants and for its use for water demanding alternative which limits the mass-production capacity.
decontamination in developing countries [5]. In a previous work, we have designed a new strategy to obtain TixOy
Nevertheless, UV radiation is required to activate TiO2 due to its nanocrystals in mild synthesis conditions of temperature (180
C)
band-gap is 3.0e3.2 eV which means that only the 5% of the solar and pressure (8 bar) by a controlled hydrolysis method [31]. This
spectrum is able to be used for the photocatalytic process [16]. method allows the stabilization of small titania crystallites, the
Therefore, solar-driven TiO2-based materials must be synthesized narrowing of the band-gap and thus, strong visible light absorption,
to allow the use of solar radiation in the photocatalytic process. the creation of Ti3þ defects/oxygen vacancies and the improvement
Several approaches have been performed in order to extend the of surface area and pollutant-surface interactions which strongly
TiO2 response to the visible range of the solar spectrum, such as improves the photocatalytic activity in the degradation of organic
metal or non-metal doping, dye sensitization, noble metals depo- pollutants under visible light.
sition, or heterojunctions building [16e19]. Nevertheless, each of Taking in mind the benefits of coloured titania and considering
these approaches still suffer from some technical deficiencies pre- that the addition of carbon matrix can also improve the Ti3þ sta-
venting their real application and therefore, further research and bilization, TixOy dispersion, electron-hole recombination reduction
development are required to obtain materials which offer optimal and pollutant adsorption, in this work, the synthesis of activated
performance for its industrial implementation and commerciali- carbon-based coloured titania nanoparticles (AC/TixOy composites)
zation [20]. are presented for the first time as an improved method to obtain
Carbon-sensitization seems to be an excellent alternative to TiO2 highly visible light responsive, narrow band gap TiO2-based pho-
doping with metal and non-metal elements. Carbon matrix im- tocatalysts with high performance in the degradation of emerging
proves the TiO2 photocatalytic performance through three funda- drugs in wastewater, such as amoxicillin and paracetamol. These
mental approaches: promotion of pollutants adsorption, band-gap new AC/TixOy composites were synthesized following a stirred
tuning and enhancement of visible light absorption and improve- solvothermal method in presence of activated carbon and under
ment of charge-separation and transportation [22,23]. Carbon hydrogen atmosphere. The effect of the solvothermal temperature
matrix (i) favors the stabilization of Ti3þ states which reduces the on the properties of the synthesized materials was also explored.
band-gap and thus, improves the photoactivity under visible light,
(ii) improves the TiO2 dispersion and thus, minimizes the electron- 2. Experimental section
hole recombination and (iii) provides active sites for the pollutants
adsorption and surface photocatalytic reactions [21]. Moreover, in 2.1. Catalyst preparation
industrial applications, the separation and recovering of the cata-
lyst after the water treatment must be also considered. The easy The raw materials and reagent used in this paper were P25
recuperation of the catalysts favors the catalyst reuse and reduces (Degussa), KOH (>85%, Sigma-Aldrich), methanol (99.9%,
the separation costs [21]. In that sense, the dispersion of TiO2 on a Applichem-Panreac), acetonitrile (99.9%, Panreac), titanium (IV)
carbon matrix helps the photocatalyst recovery and reutilization isopropoxide (TTIP, >97%, Aldrich) and hexadecyl-
reducing the separation costs. trimethylammonium bromide (CTAB, >99%, Sigma).
Considering these advantages, many efforts have been made to The activated carbon (AC) was synthesized using argan seed
obtain highly active C/TiO2 photocatalysts under solar or even shells from Morocco. The activated carbon was synthesized by
visible light radiation. R. Wang [24] prepared graphdiyne-modified chemical activation with KOH as described elsewhere [32]. For that,
TiO2 nanofibers and demonstrated that the reactive oxygen species grounded and washed argan shells were impregnated with KOH
($OH, $O2, 1O2, and $OOH) generation ability of TiO2 nanofibers (activating agent) using a KOH/argan shell weight ratio of 2. The
was significantly enhanced after graphdiyne assemblage. J. Zhang argan shell/KOH mixture was dried and subjected to a two-step
et al. [25] observed that N-Doped TiO2-carbon composite fibers carbonization/activation thermal program under 300 cm3 min1
enhances the photocatalytic oxidation of phenol due to the Ti3þ and of N2 flow consisting in 1 h at 300
C and 2 h at 800
C (heating rate
oxygen vacancies formation during the carbonization process of 10
C min1). Finally, KOH-activated sample was treated with HCl
induced by the N-doping of the TiO2 crystal lattice and the pro- (0.1 N) and then, washed with distilled water until no chloride ions
motion of charge transfer and inhibition of the electronhole were detected in the washing water.
recombination resulting from the interfaces formed between TiO2 AC/TixOy composites were prepared following a similar meth-
and the carbon. M. Shaban et al. [26] observed an enhancement in odology as described in a previous work [31] to synthesize black
the photocatalytic degradation of methylene blue dye under sun- titania but adding activated carbon during the synthesis. Briefly,
light using Nanoribbons/Carbon Nanotubes Composite (TiO2 NRs/ 0.546 g CTAB (structure-directing agent) was dissolved in 150 mL of
CNTs) which was explained based on the interaction effect of CNTs. methanol/acetonitrile solution and stirred for 10 min. Then, 5 mL of
The presence of CNTs facilitates the adsorption capacity of the dye TTIP and 1 g of AC were added. This mixture was quickly transferred
in the surface of the catalyst, decreases the band gap to 3.09 eV and into a sealed stirred reactor (Parr reactor model 5500) to avoid the
increases the lifetime of the generated electron/hole pairs. How- hydrolysis under atmospheric conditions, purged with hydrogen
ever, to the best of our knowledge, the band-gap of the most of the flow and heated at 60
C under stirring (2000 rpm). At this point,
carbon/TiO2 composites is still very high and new synthesis method 10 mL of deionized water was added into the stirred reactor using a
must be explored to obtain highly visible light responsive pump to produce the hydrolysis and condensation reactions. After
photocatalysts. that, the tank was pressurized at 8 bar and heated at 170, 190 or
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n-García et al. Carbon 178 (2021) 753e766

210
C under stirring for 6 h to hydrogenate the titania nano- obtained from the pollutant (AMX or PAR) adsorption isotherms on
particles obtained by the TIPP hydrolysis. After this time, the ob- materials. These isotherms were obtained in dark at 25
C using a
tained suspension was centrifuged at 4000 rpm for 20 min and the thermostatic bath (results not shown). Flasks with different
recovered solid washed with methanol several times up to a clean pollutant concentrations were placed inside the thermostatic bath
solution was obtained. A reference TixOy sample was prepared under shaking for 6 h to ensure the equilibrium is achieved and,
following the same procedure but without adding AC. The obtained after adsorption, the concentration was measured. Each sample
composites were labeled as CTi170, CTi190, CTi210 and Ti210, ac- prior to analysis was filtered through a 0.22 mm PTFE filters, 13 mm
cording to their temperature of preparation and the presence or not (CHS Filterpure Syringe Filers, supplier Chromservis s.r.o., Czech
of carbon material. P25 from Sigma-Aldrich was also used as Republic).
reference material. The concentration of pollutant and the possible intermediate
obtained during the photocatalytic reaction was analyzed by a
2.2. Catalyst characterization high-performance liquid chromatography (UHPLC system Ultimate
3000, supplier Bruker s.r.o., Brno, Czech Republic) equipped with
The textural properties of AC/TixOy composites and reference column Kinetex 5m C18 100A (Phenomenex, Torrance, USA) coupled
samples were analyzed by N2 and CO2 adsorption at 196 and 0
C, to mass spectrometry. The mobile phase was a mixture of 10% HPLC
respectively using a Quadrosorb equipment from Quantachrome. grade methanol (LC-MS purity, Biosolve chimie SARL, France) and
The surface area (SBET) was calculated by applying the Bru- 90% ultrapure water (HPLC purity, Chem-Lab NV, Belgium) with
nauereEmmetteTeller (BET) method to the N2 isotherm. The 0.1% formic acid (purity 98e100%, Merck KGaA, Germany) in iso-
DubininRadushkevich (DR) equation was applied to the N2 and cratic mode with an elution flow rate of 250 mL min1. The detector
CO2 adsorption data to determine the micropore volume, W0 (N2) wavelength was 229 nm for AMX and 244 nm for PAR. The injection
and W0 (CO2), and the average pore diameter, L0(N2) and L0(CO2). volume was 30 mL for all samples.
The Quenched Solid Density Functional Theory (QSDFT) was used The mineralization degree was followed by the evolution of total
to determine the pore size distribution. The total volume of pore organic carbon (TOC) present in the solution during the photo-
(V0.95) was calculated as the N2 volume adsorbed at a relative degradation experience using an analyzer Shimadzu V-CSH analy-
pressure of 0.95. The volume of mesopores, Vmeso, was determined ser with ASI-V autosample.
as V0.95-W0(N2).
Crystallinity of samples was studied by powder X-ray diffraction 3. Results and discussion
(XRD) in a Bruker D8 Advance X-ray diffractometer (CuKa radiation
at a wavelength (l) of 1.541 Å). The 2q angles were scanned from 10 3.1. Textural and chemical characterization of photocatalysts
to 80
. The average crystallite sizes (D) were estimated by the
Debye-Scherer equation. The incorporation of TiO2 into the activated carbon depends on
Morphology of samples was studied by Scanning Electron Mi- its surface area and surface chemistry. The reductive conditions of
croscopy (SEM) using a LEO (Carl Zeiss) GEMINI-1530 microscope the modified solvothermal treatment used in the synthesis of ma-
coupled EDX microanalysis system (Super X). HRTEM images were terials can affect the surface chemistry of activated carbon and
recorded using a FEI TITAN G2 80e300 microscope equipped with a therefore, such TiO2 incorporation. The amount of TiO2 anchored on
scanning transmission electron microscopy (STEM) detector-type the activated carbon surface was analyzed by thermogravimetric
HAADF (high-angle annular dark-field detector). analysis, and results are collected in Fig. 1 and Table 1. The pristine
Thermogravimetric (TG) analysis of the samples was performed activated carbon (AC) starts to burn at 400
C and finishes at 570
C.
in a flow of air with a Mettler TA 4000 system from 25 to 900
C at a The ash content determined was 8.5 wt %. A weight loss of 4.1 wt %
heating rate of 10
C/min. occurs between 150 and 310
C for pure Ti210 reference which can
The surface chemistry was analyzed by X-ray photoelectron be ascribed to the removal of OH surface groups and/or carbonates
spectroscopy (XPS) using a Kratos Axis Ultra-DLD X-ray photo- anchored on the titania surface [33]. A slight weight loss occurs
electron spectrometer equipped with MgKa X-ray source from 150 to 400
C for the CTiX composites, similar to those
(hy ¼ 1253.6 eV) and a hemispherical electron analyzer. C1s, O1s and
Ti2p spectral regions were recorded. The binding energy scale was
fitted using the C1s peak position at 284.6 eV as reference.
Raman spectra were recorded using a Micro-Raman JASCO NRS-
5100 dispersive spectrophotometer with a 532 nm laser line.
Optical absorption spectra were obtained on a double-beam
UVevis spectrophotometer (CARY 5E from VARIAN) equipped
with a Praying Mantis diffuse reflectance accessory (DRS). The
band-gap (Eg) of samples was calculated from the reflectance
spectra according to the KulbelkaeMunk (KM) method.

2.3. Photocatalytic tests

The photoactivity of the prepared materials was examined in

the photodegradation of two emerging drugs: amoxicillin (AMX)
and paracetamol (PAR) under visible light (see Emission spectrum
of LED lamp, Figure S1) using a 100 W/m2 LED lamp (ShenZhen
GeTian Technology Co., Ltd, GT-P03W54103260). Prior to illumi-
nation, the catalysts (1 mg per mL) were saturated in dark under
stirring with a pollutant solution with the proper concentration to
obtain a final concentration of 10 mg L1 after reach the Fig. 1. TGA profiles of samples. AC (fx1), TiC170 (fx2), TiC190 (fx3), TiC210 (fx4) and
adsorptionedesorption equilibrium. This proper concentration was Ti210 (fx5). (A colour version of this figure can be viewed online.)

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n-García et al. Carbon 178 (2021) 753e766

Table 1
XPS results of samples: the surface content (wt. %), binding energy and percentage of the components used to fit the Ti2p, O1s and C1s spectral regions of CTiX composites and Ti
wt. % determined by TGA (TiTGA).

Sample C1s Ti2p O1s CXPS (%) OXPS (%) TiXPS (%) TiTGA (%)

BE (eV) % peak BE (eV) % peak BE (eV) % peak

P25 284.7 88 459.5 100 530.4 80 6.0 30.8 63.6 n.d.

286.0 12 532.5 17
534.3 3
Ti210 284.6 38 458.2 78 529.3 65 18.2 40.1 37.7 57.5
286.0 39 459.1 22 530.8 32
287.9 13 531.8 3
289.4 10
CTi170 284.6 40 459.5 68 530.8 58 38.5 30.5 31.0 26.4
285.8 33 460.9 32 531.4 21
286.8 13 532.7 13
287.9 6 533.7 8
289.7 8
CTi190 284.6 53 459.7 91 530.8 52 41.5 29.3 29.2 22.5
285.8 24 460.3 9 531.4 27
286.8 11 532.7 14
287.9 5 533.6 7
289.7 7
CTi210 284.7 62 459.7 96 530.8 36 73.9 15.0 11.0 6.8
285.8 18 460.3 4 531.7 19
286.8 10 532.6 27
288.0 6 533.8 18
289.6 4

observed for AC and Ti210 reference samples which is attributed to peaks at higher binding energies assigned to the presence of
the removal of labile surface groups of carbon and titania. Never- oxygen-containing surface groups. The pristine activated carbon
theless, in this case, the carbon phase combustion starts at around was obtained by KOH activation of argan shell, hence, a high con-
500
C and it is not completed until 640
C. This carbon burn delay tent of oxygen was obtained; elemental analysis (Table S1) indi-
(about 80e100
C) compared to pristine AC can be ascribed to the cated an oxygen content of 15.3 wt %. This oxygen content can be
blockage of the activated carbon microporosity by the titania reduced after the reductive solvothermal treatment and be affected
nanoparticles deposition on its surface and consequently, diffu- by the treatment temperature. In that sense, note that the contri-
sional restrictions to oxygen and combustion gases to/from the bution of these smaller peaks (oxygen-containing surface groups)
interior of carbon porosity. decreases by increasing of the solvothermal temperature being this
The amount of titania incorporated in the composites at each oxygen-containing groups reduction more significant at 210
C.
solvothermal temperature was obtained from the residual content This is due to the more efficient reduction of the carbon surface
after burning, considering the ash content of the activated carbon under H2 atmosphere at higher temperatures. The increased
(Table 1). Taking into account the amount of titania precursor and reduction of carbon surface can affect the TiO2 anchoring. M.J.
activated carbon used during the synthesis, a TiO2 weight percent Sampaio et al. [34] show that the introduction of oxygen surface
of 58 was expected. However, the amount of titania incorporated groups in CNT is crucial to prepare TiO2/CNT composites. Oxygen
on AC was 44.0, 37.6 and 11.3 wt % for carbon solvothermally groups on the carbon surface act as anchoring points for the TiO2
treated at 170, 190 and 210
C, respectively. Therefore, this fact particle [34e36]. Therefore, the increased reduction of the carbon
indicates that not all the titania is incorporated to the activated surface by increasing the solvothermal temperature from 170 to
carbon and moreover, the solvothermal temperature clearly in- 210
C avoid the TiO2 anchoring, decreasing the amount of TiO2
fluences such titania incorporation on the carbon surface. incorporated on the activated carbon from 44.0 to 11.3 wt %
As commented above, the surface chemistry of the activated (Table 1).
carbon can explain the different titania content anchored on its The solvothermal temperature also affects the reduction of the
surface. Note that, despite the same amount of TiO2 precursor, TiO2 nanoparticles. During the solvothermal treatment under H2
water and activated carbon were used during the synthesis and atmosphere occurs the effective reduction of Ti4þ ions into Ti3þ by
therefore, similar titania contents would be expected indepen- introducing oxygen vacancies [31]. This effective reduction and the
dently of the solvothermal temperature; the carbonaceous product influence of the temperature and carbon matrix in such reduction
was washed with methanol until a clean washing solution was was corroborated by XPS (Fig. 2b and Table 1). Only Ti4þ species
obtained in order to remove the unincorporated titania from the (peak at 459.5 eV) is obtained for P25 while Ti3þ is the main
activated carbon, thus avoiding the presence of isolated phases. In component (78%) in Ti210 reference material (peak at 458.2 eV)
this way, depending on its chemical surface, only the titania corroborating the effective reduction of titania nanoparticles by the
anchored on the activated carbon remains after the cleaning pro- solvothermal treatment under H2 atmosphere. Nonetheless, the
cess, as it was observed by TGA (Fig. 1). presence of carbon as well as the treatment temperature affect this
To explain the different titania contents anchored on the acti- TiO2 reduction. Two peaks were also detected for TiCX composites
vated carbon surface, the surface chemistry of composites was at BE of 459.6 and 460.5 eV assigned to Ti3þ and Ti4þ, respectively. It
analyzed by XPS. C1s spectral region of CTiX (X ¼ 170, 190 or 210
C) is important to highlight that Ti and O peaks in TiCX composites
composites was depicted in Fig. 2a and data obtained from its (Table 1 and Fig. 2 and S2) are shifted to higher BE (~1.2 eV)
deconvolution included in Table 1. Five peaks were required to compared to Ti210 and P25 references. The upshift in the binding
deconvolve the C1s spectral region of TiCX composites, showing a energy suggested the change of chemical state and/or coordination
main peak at 284.6 eV attributed to CeC bonds joined to other environment of Ti due to the formation of strong electronic

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n-García et al. Carbon 178 (2021) 753e766

Fig. 2. a) C1s and b) Ti2p XPS regions for CTiX composites and reference samples (X ¼ temperature of the solvothermal treatment, X ¼ 170, 190 or 210
C). (A colour version of this
figure can be viewed online.)

interactions, such as a charge transfer from TiO2 to carbon [37,38]. (Fig. 3), respectively. Clearly-resolved and well-ordered crystal
This poorest electronic environment can be explained based on the domains of around 25 nm with well-defined lattice fringes were
carbon phase ability to accommodate electrons from the inorganic observed for P25 by HRTEM. In contrast, nanoparticles of around
phase which indicates a carbon-TiO2 intimate contact in the com- 6e7 nm with highly-disorder nanosized crystal domains with a
posite materials. Moreover, the presence of carbon phase enhances relatively unclear fringe pattern owing to the introduction of
the titania reducibility; 78% of Ti3þ was obtained for Ti210 sample amorphous regions between crystal domains were observed in
whereas the content of Ti3þ increases to 96% in presence of carbon Ti210 sample. SEM images (Fig. 3) showed that titania spherical
(CTi210). This TiO2 reduction also increases by increasing the sol- nanoparticles are localized mainly on the external surface of the
vothermal temperature; the Ti3þ content increases from 68% to 96% activated carbon. The amount and agglomeration of these titania
by increasing the temperature from 170 to 210
C indicating, as nanoparticles on the AC surface decreases by increasing the sol-
expected, a more effective reduction of titania at higher vothermal temperature corroborating the less TiO2 anchoring at
temperatures. higher temperatures observed by TGA.
Analyzing the C and Ti surface contents (CXPS and TiXPS, Table 1), This different TiO2 content and agglomeration affects the
note that carbon is obtained for both reference samples which is textural properties of samples (Fig. 4). AC is mainly a microporous
attributed to the adventitious carbon contamination after being material with a low volume of narrow mesopores (2.4 nm, Fig. 4b)
exposed to the atmosphere. However, the detectable quantity of whereas Ti210 is exclusively mesoporous (Table 2) with a mesopore
adventitious carbon contamination is higher for Ti210 compared to width of 10.5 nm (Fig. 4b) which are created due to the agglom-
P25. The nature of this adventitious carbon is also quite different: eration of titania nanoparticles (Fig. 3b). In turn, CTiX composites
note that a main peak around 284.69 eV is observed in the C1s re- are micro-mesoporous materials where the microporosity is pro-
gion of P25 (Fig. 2) attributed to the delocalized alternant hydro- vided by the carbon matrix, whereas the mesoporosity
carbon [39]. However, C1s region of Ti210 reveals the presence of (5.3e7.5 nm) is provided by the titania phase. Since the micropo-
other peaks, characteristic of oxygen surface groups assigned to the rosity of AC is very narrow (L0(N2) ¼ 1 nm, Table 2) and the average
presence of carbonates in the sample [39] corroborating the weight titania particles size is larger than 3 nm (see XRD results, Table 2),
loss observed in TGA at temperatures of 150e300
C attributed to the titania particles are mainly localized at the activated carbon
carbonated species. This higher amount of carbon on Ti210 external surface blocking in part the micropores entrance, as it is
compared to P25 indicates the more reactive surface of Ti210 denoted by the high decrease of the volume of N2 adsorbed at low
sample. The higher population of oxygen vacancies could enhance relative pressures. As it was explained above, the titania anchoring
the chemisorption of CO2 and thus, the carbonation of Ti3þ-rich on the carbon surface and, therefore, its dispersion depends on the
titania surface [40,41]. Regarding CTiX composites, the carbon carbon surface chemistry (oxygen-containing surface groups). The
content increases by increasing the solvothermal temperature due oxygen-containing surface groups, which act as titania anchoring
to the decrease of TiO2 anchored as it was detected by TGA. In fact, points, decrease by increasing the solvothermal temperature,
the TiXPS contents of CTiX composites are slightly higher than the Ti inducing a less agglomeration of titania nanoparticles and
contents obtained by TGA (TiTGA) manifesting a distribution of TiO2 improving the nanoparticles dispersion on the carbon surface (see
nanoparticles mainly on the external surface of the activated SEM images). This less titania agglomeration and better dispersion
carbon. of titania favors the carbon porosity blockage of carbon surface and
The morphology of TiO2 nanoparticles and its distribution on decreases the micropores (W0) and mesopores (Vmeso) volume
the activated carbon surface was analyzed by HRTEM and SEM provided by carbon and titania phase, respectively, and as a result

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n-García et al. Carbon 178 (2021) 753e766

Fig. 3. (aec) HRTEM images of P25 and Ti210 and (def) SEM Images of CTiX samples. (A colour version of this figure can be viewed online.)

Fig. 4. a) N2 adsorption-desorption isotherms and b) pore size distribution of samples: AC (fx1), TiC170 (fx2), TiC190 (fx3), TiC210 (fx4) and Ti210 (fx5). (A colour version of this
figure can be viewed online.)

758
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n-García et al. Carbon 178 (2021) 753e766

Table 2
Textural characteristics, TiO2 content (wt. %) determined by TGA and crystal size (dXRD) of the CTiX composites and reference materials. Total adsorption capacities of
amoxicillin and paracetamol (qm).

Sample SBET W0(N2) W0(CO2) L0(N2) L0(CO2) V0.95 Vmeso TiO2 dXRD qm (mg g1)

m2/g cm3/g cm3/g nm nm cm3/g cm3/g % nm AMX PAR

Ti210 116 0.030 0.022 1.74 1.16 0.506 0.475 95.9 6.6 30.17 15.20
CTi170 381 0.114 0.127 1.15 0.87 0.263 0.149 44.0 7.8 107.65 51.22
CTi190 225 0.067 0.166 1.30 0.89 0.234 0.167 37.6 7.0 63.39 33.43
CTi210 54 0.018 0.098 1.64 0.86 0.057 0.039 11.3 4.0 10.97 8.54
AC 1635 0.612 0.440 1.00 0.78 0.707 0.095 e e 453.39 228.39

the surface area. In the case of CTi210, the distribution of TiO2 is based on a different surface reduction of TiO2 nanoparticles. Several
high enough to block the porosity entrance avoiding the N2-diffu- authors have pointed out the presence of a disordered shell in the
sion into the carbon porosity despite the less amount of titania and surface of coloured titania caused by the creation of oxygen va-
consequently, higher content of carbon phase which provides the cancy/Ti3þ, surface hydroxyl groups or TieH bonds. Due to the
microporosity. amorphous character of this shell, the crystallite sizes and diffrac-
The crystallinity of the samples was analyzed by XRD and results tion intensity decrease after the reduction treatment [31,42,43]. A
are collected in Fig. 5 and Table 2. XRD patterns of samples reveal good correlation between the amount of Ti3þ detected by XPS and
the stabilization of anatase TiO2 (JCPDS 21e1272) in all samples. the crystal size is obtained for the synthesized CTiX composites and
Ti2O3 was not detected in any case. This indicates that TiO2 reference sample (TiC210). The higher is the Ti3þ content, the
reduction takes place mainly at the surface since Ti3þ is the ma- smaller is the crystal size denoting a more effective TiO2 reduction
jority specie detected by XPS whereas only TiO2 phase is observed at higher temperature and in presence of carbon.
by XRD because this Ti2O3 shell is amorphous and therefore, no The structural changes of the TiO2 nanoparticles were further
diffraction is detected. Note that the graphite-TiO2 relative intensity studied by Raman spectroscopy and results are depicted in Fig. 6a.
increases at a treatment temperature of 210
C compared to 170 Raman spectroscopy is very sensitive to short-range distortions and
and 190
C because the amount of TiO2 anchored on the carbon therefore, structural defects such as oxygen vacancies can be
surface at 210
C is four times less decreasing the diffraction in- pointed out by this technique [44]. Five characteristic Raman peaks
tensity since graphitization of carbon matrix is not affected by the are described for anatase TiO2 phase at 143.6, 199.8, 397.2, 516.3
solvothermal treatments as denoted by the Raman spectra (See and 639.6 cm1 which are ascribed to the Eg (1), Eg (2), B1g,
Fig. 6b). A1g þ B1g and Eg (3) vibrational modes, respectively [45]. The Eg
The crystallite size was obtained by using the Scherrer equation modes are attributed to planar OeO interactions whereas A1g and
and data are included in Table 2. The TiO2 crystal size decreases by B1g modes come from TieO stretching modes, therefore Eg mode is
increasing the solvothermal temperature and, consequently, the more sensitive to oxygen defects [46e48]. Note that these five
titania reduction (see XPS results). Since hydrolysis always occurs peaks are also observed for both Ti210 reference material and CTiX
at 60
C under stirring, similar crystal size would be expected for all composites, however, the frequency of the strongest Eg mode
samples, even in presence of the carbon matrix. If this was not the shows a pronounced blue shift around 179 cm1 together with a
case, even bigger crystal size could be expected for TiCX composites peak broadening which depend on the treatment temperature and
by increasing the solvothermal temperature owing to the removal presence of carbon matrix. This blue shift and band broadening
of oxygen surface groups which acts as anchoring centers favoring could be attributed, according to the bibliography, to a lattice
the TiO2 dispersion [34] and the sintering of titania particles by the contraction because of the presence of oxygen vacancies [45,46].
temperature effect. However, the crystal size decreases by The Eg (1) band position and full width at half maximum (FWHM)
increasing the treatment temperature. Thus, the different crystal of composites and TiC210 reference are included in Table 3. The
size cannot be explained based on different particle dispersion but blue shift and the FWHM in CTiX composites increase by increasing
the treatment temperature denoting a more oxygen defective
titania at higher temperatures in agreement with XPS results. Note
also that the Eg (1) band is shifted from 178.9 cm1 to 181.4 cm1
and the FWHM increases from 29.5 to 31.7 cm1 by the addition of
carbon to the material (see Ti210 and CTi210 samples) manifesting
that carbon favours the titania reduction.
It is also important to highlight that this shift is very high
compared to other black titania-based materials described in
bibliography [45,49e51] denoting a highly defective oxygen sub-
lattice of the prepared materials. Note also that a new peak appears
at around 211 cm1 (Fig. 6a). G. Liu et al. [52,53] have observed a
remarkable surface reconstruction in oxygen-deficient TiO2 sheets,
which is demonstrated by two new Raman modes at 155 and
171 cm1. These new modes are the synergistic effects of the oxy-
gen vacancy and surface fluorine probably by changing both atomic
coordination numbers and bonding length of the TieOeTi network
in oxygen-deficient anatase TiO2 sheets. Similar surface recon-
struction was observed in iodine doped anatase TiO2 photocatalyst
by, again, the appearance of two new Raman-active modes at 182
Fig. 5. XRD profiles of samples: TiC170 (fx2), TiC190 (fx3), TiC210 (fx4) and Ti210 (fx5).
and 192 cm1 [54]. Peak broadening and extra peaks were also
(A colour version of this figure can be viewed online.) detected for black titania due to the disordered nature of the

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n-García et al. Carbon 178 (2021) 753e766

Fig. 6. Raman spectra of samples. a) TiO2 and b) carbon vibrational modes. (A colour version of this figure can be viewed online.)

Table 3 treatment temperature of 170, 190 and 210
C, respectively (Fig. 7a).
Band position and Full width at half maximum (FWHM) of the Eg (1) Raman mode. This improved adsorption of visible light is ascribed to the
Sample Band position (cm1) FWHM (cm1) efficient reduction of titania Ti4þ ions into Ti3þ by introducing ox-
ygen vacancies during the controlled hydrogenation treatment. As
Ti210 178.9 29.5
CTi170 175.0 28.7
it was pointed out by XPS and Raman, the higher is the sol-
CTi190 180.6 29.6 vothermal temperature, the higher is the amount of oxygen va-
CTi210 181.4 31.7 cancies/Ti3þ and therefore, the lower is the band gap (Fig. 7b). The
presence of carbon favors the titania reducibility increasing the
amount of Ti3þ and thus, TiC210 composite shows a lower band gap
surface layer [55]. Consequently, the new peak at around 211 cm1 than its corresponding Ti210 reference.
observed for CTiX and Ti210 samples can be an indicative that The conclusions obtained from the characterization of materials
structural changes occur after hydrogenation [56]. Note that the are summarized in Fig. 8. Overall, the hydrolysis of the titania
intensity of this peak increases by increasing the solvothermal precursor occurs when water is injected at 60
C under H2 flow
treatment and therefore, the Ti3þ/oxygen vacancies on the samples obtaining TiO2 nanoparticles which, in presence of the microporous
(see XPS results); the higher is the Ti3þ content detected by XPS, the activated carbon, are in part anchored on the external carbon sur-
higher is the intensity of this new peak. face favoured by the presence of oxygen surface groups on the
The effect of the solvothermal treatment and temperature on activated carbon. Then, the temperature and H2 pressure is
the graphitization degree of carbon matrix was analyzed also by increased, which favours the carbon and titania surface reduction.
Raman spectroscopy (Fig. 6b). The ratio between the intensity of This carbon and titania surface reduction increases by increasing
the defect band (ID) and the graphitization band (IG) and the G the solvothermal temperature as corroborated by XPS. The removal
bandwidth (WG) are indicative of the graphitization degree of of oxygen groups of the carbon surface by increasing the treatment
carbon architectures. WG reveals the graphitization degree, and ID/ temperature affects the amount of titania anchored on the carbon
IG ratio is affected by both the graphitization degree and the crys- composites. Therefore, after the washing and carbon recovery, only
tallite size [57]. Note that the ID/IG relative ratio and WG do not the titania anchored on the activated carbon surface remains and
change after the solvothermal treatment compared to pristine AC, thus, the titania content decreases by increasing the solvothermal
indicating that the solvothermal treatments does not affect the temperature as it was pointed out by TGA. After this mild condition
graphitization degree of the carbon matrix. solvothermal hydrogenation of titania, Ti3þ self-structural modified
The presence of this Ti3þ shell affects the optical properties of TiO2 was obtained as corroborated by XPS and Raman. Nonetheless,
TiO2 nanoparticles since creates new hybrid states localized be- the amount of Ti3þ and thus, the effectivity of the TiO2 reduction
tween the TiO2 conduction and valence bands narrowing the band increases by increasing the treatment temperature. XRD manifests
gap and enhancing a significant visible light adsorption. Diffuse that this amorphous Ti3þ shell increases with the increase of the
reflectance spectroscopy was performed to calculate the band gap solvothermal temperature being this titania reduction much more
(Eg) of samples (Figure S3). The band gap obtained for P25, used as severe at 210
C at which a TiO2 core particle size of 4.0 nm is ob-
reference material, was 3.5 eV which is in agreement with litera- tained vs 7.8 or 7.0 nm obtained at 170 or 190
C, respectively. The
ture values. This band gap decreases for samples prepared by the presence of carbon matrix also affects the effectivity of such
solvothermal treatment; however, this decrease depends on the reduction, so that higher amount of Ti3þ was detected on CTiX
presence of carbon matrix as well as the treatment temperature. composites compared to Ti210 reference material. Moreover, the
Regarding Ti210 and CTi210 samples, note that the presence of presence of carbon also improves the electron transfer from titania
carbon decreases the band gap from 3.1 to 1.7 eV (Fig. 7a). The nanoparticles to carbon, as it was confirmed by XPS, favoured by
temperature of the solvothermal treatment also affects this band the intimate carbon-titania contact obtained, which ruled out the
gap decrease; the obtained band gaps were 3.0, 2.5 and 1.7 for a presence of isolated phases after the washing process. This

760
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n-García et al. Carbon 178 (2021) 753e766

Fig. 7. Band gap (Eg) obtained from DRS data by using KubelkaeMunk theory as a function of the solvothermal temperature (a) and the Ti3þ content determined by XPS (b). (fx6)
CTiX composites (X ¼ 170, 190 or 210) and (fx7) Ti210 reference sample. (A colour version of this figure can be viewed online.)

Fig. 8. Schematic representation of the synthesis process and the changes that occurred during the same. (A colour version of this figure can be viewed online.)

improved surface reduction of titania nanoparticles enhances the increasing the treatment temperature from 170 to 210
C because of
visible light absorption of the synthesized coloured titania-based the more effective reduction process. This band gap also decreases
materials. The band-gap decreases from 3.0 to 1.7 eV by by the addition of carbon; 1.7 vs 3.1 eV for samples treated at 210
C

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n-García et al. Carbon 178 (2021) 753e766

in presence and absence of activated carbon, respectively. There- reduction as a result of the creation of oxygen vacancies/Ti3þ spe-
fore, the presence of carbon matrix enhances the titania reduction cies (3.1 eV vs 3.5 eV of P25), ii) the stabilization of low titania
decreasing the band-gap and favours the electron transfers from crystal size (6.6 nm vs 25 nm of P25) which improves the accessible
titania to carbon minimizing electron-hole recombination. Thus, surface for the adsorption of contaminants and minimizes the
activated carbon-based coloured titania nanoparticles are pre- probability of electron-hole recombination and iii) the surface
sented as promising solar-driven photocatalysts. localization of defects arising from a synergistic effect of the oxygen
vacancies on core and surface disorder which is demonstrated to
significantly improve the efficiency of the electron-hole separation,
3.2. Photocatalytic tests
enhancing the activity [58,59].
This removal activity is highly improved using activated carbon-
The photocatalytic activity of activated carbon-based coloured
based coloured titania (CTiX composites) photocatalysts despite
TiO2 nanoparticles was analyzed in the degradation of two com-
less amount of the photocatalytic TiO2 active phase is presented per
mon wastewater drugs, paracetamol (PAR) and amoxicillin (AMX),
gram of photocatalyst used in the degradation tests (less than 45%
under visible light irradiation. It is important to remember that
of TiO2 active phase). This enhancement of the activity despite the
prior to the photocatalytic tests, catalysts were saturated with the
less amount of TiO2 manifests the real degradation power of TixOy
drug in the dark (adsorption capacities for each sample are
active phase in these composites. This exceptional catalytic per-
included in Table 2). and the initial concentration was set at
formance of CTiX composites can be explained to synergetic ben-
10 mg L1 in all cases to avoid adsorption interferences. Fig. 9a and
efits provided by the combination of coloured titania and the
b shows the removal of AMX and PAR, respectively, as a function of
carbon matrix: i) the carbon matrix favours the TiO2 reducibility
the irradiation time for CTiX composites compared to Ti210 and P25
and thus, the creation of a higher population of oxygen vacancies/
reference materials. Note that the photoactivity of P25 is, as ex-
Ti3þ species at the surface which, in turn, decreases the band-gap
pected, very low for both AMX and PAR drugs due to its large band
enhancing the visible light absorption and minimizes the
gap. This activity is highly enhanced by using coloured titania
electron-hole recombination by decreasing the relative bulk de-
(Ti210) as photocatalyst in the degradation of both drugs due to the
fects/surface defects concentration ratio in TiO2 nanocrystals
optimization of several factors which favours the photodegradation
[58,59]; and ii) the intimate contact between coloured TiO2 and
activity: i) the enhanced visible light absorption and band-gap

Fig. 9. Photocatalytic degradation of AMX and PAR using CTiX composites and Ti210 and P25 reference materials. a and b) drug removal (%) and c and d) drug removed (mg)
normalized per volume of treated solution (L) and weight (g) of TiO2 active phase present in the photocatalyst as a function of time. TiC170 (fx8), TiC190 (fx9), TiC210 (fx10), Ti210
(fx11) and P25 (C). (A colour version of this figure can be viewed online.)

762
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n-García et al. Carbon 178 (2021) 753e766

carbon phases improves the electron transfer from TiO2 to carbon

matrix (see XPS) increasing the electron-hole separation efficiency
an thus, improving the photoactivity.
In order to analyse the effect of the solvothermal temperature
on the photocatalytic performance, the photocatalytic activity was
normalized by the amount of TiO2 active phase in the composite
since, as TGA results pointed out, a different amount of TiO2 was
anchored on the activated carbon surface depending on the treat-
ment temperature. Therefore, the amount of drug removed (mg)
normalized per volume of treated solution (L) and weight (g) of
TiO2 active phase present in the photocatalyst as a function of time
was plotted in Fig. 9c and d. At 120 min of treatment, the amount of
AMX removed using coloured titania (Ti210) was twice as high as
that of obtained using P25. This removed amount increases from
3 mg L1 g1 for coloured titania (Ti210) to 57.7 mg L1 g1 for
activated carbon-based coloured titania synthesized in the same
Fig. 10. % AMX removed and % TOC at 120 min of irradiation using activated carbon-
based coloured titania nanoparticles. (A colour version of this figure can be viewed
experimental conditions (CTi210), manifesting the synergistic role
online.) of the activated carbon on the photoactivity enhancement. The
synthesis temperature also affects the drug degradation. The

Table 4
Photocatalytic performance of carbon-TiO2 composites from the literature.

Sample TiO2 content Drug Mcata C0 Light/power Eg RTOCa D30a Ref.

(wt. %) (g/L) (ppm) (W) (eV) (%) (%)

CTi170 44.0 AMX 1 10 Visible/100 3.0 92 at 2 h 82 Our work

PAR e 88
CTi190 37.6 AMX 1 10 Visible/100 2.5 97 at 2 h 92
PAR e 100
CTi210 11.3 AMX 1 10 Visible/100 1.7 95 at 2 h 88
PAR e 96
2
TiO2 100 AMX 1.2 50 UV/20 W/m e n.d. 50 [60]
PAR 22
2
TiO2/AC 67 AMX 1.2 50 UV/20 W/m e n.d. 50
PAR 26
Graphene (GN)/titania nanotubes (TNT) 97 AMX 0.1e0.4 5 UV/19 n.d. n.d. 8 (23) [61]
95 12 (32)
90 37 (60)
85 27 (92)
TNT 100 AMX 0.1e0.4 5 UV/19 3.2 n.d. 4 (7)
TiO2/AC (Solvothermal) 76 PAR 0.25 5 Solar/600 W/m2 3.38 43 at 6 h 9 (80) [62]
TiO2/AC (Microwave) 79 PAR 0.25 5 Solar/600 W/m2 3.35 47 at 6 h 9 (80)
TiO2/AC (Sol-gel) 77 PAR 0.25 5 Solar/600 W/m2 3.28 15 at 6 h 3 (29)
TiO2/AC (FeeC) 75.9 PAR 0.25 5 Solar/600 W/m2 3.28 43 at 6 h 20 (82) [63]
TiO2/AC (ZneC) 68.5 PAR 0.25 5 Solar/600 W/m2 3.42 24 at 6 h 8 (47)
TiO2/AC (PeC) 81.3 PAR 0.25 5 Solar/600 W/m2 3.50 36 at 6 h 11 (57)
TiO2/AC (KeC) 83.9 PAR 0.25 5 Solar/600 W/m2 3.45 30. at 6 h 11 (63)
TiO2 100 PAR 0.25 5 Solar/600 W/m2 3.33 59 at 6 h 44 (100)
TiO2 100 AMX 1 37 near-UV/Vis 3.16 n.d. 53 [64]
TiO2/NDD (pristine nanodiamons: NDs) 85 AMX 1 37 near-UV/Vis 3.19 18 at 1 h 91
TiO2/NDH (hydrogen monofunctionalized NDs) 85 AMX 1 37 near-UV/Vis 3.24 11 at 1 h 79
TiO2/NDO (carboxylic monofunctionalized NDs) 85 AMX 1 37 near-UV/Vis 3.22 11 at 1 h 75
TiO2/NDA (amine monofunctionalized NDs) 85 AMX 1 37 near-UV/Vis 3.22 15 at 1 h 87
Ti n.d. PAR 0.25 5 Solar/600 W/m2 3.25 n.d. 4 [65]
Ti-500air n.d. PAR 0.25 5 Solar/600 W/m2 3.12 n.d. 60
CeTi n.d. PAR 0.25 5 Solar/600 W/m2 2.95 n.d. 17
CeTi-300air n.d. PAR 0.25 5 Solar/600 W/m2 3.28 n.d. 20
CeTi-400air n.d. PAR 0.25 5 Solar/600 W/m2 2.25 n.d. 83
CeTi-500-air n.d. PAR 0.25 5 Solar/600 W/m2 3.18 n.d. 88
CeTi-500 N2 n.d. PAR 0.25 5 Solar/600 W/m2 n.d. n.d. 9
CeTi-750 N2 n.d. PAR 0.25 5 Solar/600 W/m2 n.d. n.d. 14
TiO2 100 PAR 3 25 UV/16 3.24 3.5 15 [66]
TiO2-graphite >98 PAR 3 25 UV/16 3.24 30 65
1MWCNT-TiO2-SiO2 n.d. PAR n.d. 10 Visible 3.22 50 at 1 h 71 at 1 h [67]
5MWCNT-TiO2-SiO2 n.d. PAR n.d. 10 Visible 3.07 44 at 1 h 78 at 1 h
10MWCNT-TiO2-SiO2 n.d. PAR n.d. 10 Visible 2.94 61 at 1 h 82 at 1 h
20MWCNT-TiO2-SiO2 n.d. PAR n.d. 10 Visible 2.82 34 at 1 h 63 at 1 h
40MWCNT-TiO2-SiO2 n.d. PAR n.d. 10 Visible 2.93 32 at 1 h 62 at 1 h
1%GR-TNT 99 PAR 0.1 5 UV/14 3.03 n.d. 15 (80) [68]
5%GR-TNT 95 PAR 0.1 5 UV/14 2.98 n.d. 27 (86)
10%GR-TNT 90 PAR 0.1 5 UV/14 2.86 n.d. 21 (89)
20%GR-TNT 80 PAR 0.1 5 UV/14 2.34 n.d. 2 (41)

() ¼ degradation at 180 min.

a
Photocatalyst dosage (Mcat) and TOC Removal (RTOC) and % of degradation at 30 min (D30).

763
S. Benjedim, J. Castelo-Quib
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n-García et al. Carbon 178 (2021) 753e766

removed AMX increased from 13.8, to 18.1 mg L1 g1 by increasing CRediT authorship contribution statement
the synthesis temperature from 170 to 190
C. However, this
removed amount is multiplied by 3, increasing the temperature Safa Benjedim: Investigation, Formal analysis. Jesica Castelo-
from 190
C (18.1 mg L1 g1) to 210
C (57.7 mg L1 g1). As it was Quibe
n: Investigation, Formal analysis. Esther Bailo
n-García:
commented in the characterization section, the increase of tem- Conceptualization, Methodology, Formal analysis, Writing e orig-
perature favours the Ti3þ and oxygen vacancies generation, being inal draft. El Mostapha Lotfi: Supervision, Validation. Agustín F.
this titania reduction much more severe at 210
C as it was pointed Pe
rez-Cadenas: Conceptualization, Methodology, Supervision,
out by XRD, RAMAN and DRS. Moreover, titania nanoparticles are Funding acquisition. Va
clav Slova

k: Supervision, Conceptualiza-
less agglomerated on the activated carbon for CTi210 samples due tion, Validation. Jirí Kalina: Investigation, Formal analysis. Fran-
to the less amount of titania, thus the accessibility of drugs to TiO2 cisco Carrasco-Marín: Conceptualization, Methodology,
active sites is improved. This greater population of Ti3þ/oxygen Validation, Project administration, Funding acquisition.
vacancies, the ultra-low band gap (1.7 eV) and the less agglomer-
ated of titania particles observed for CTi210 explain the deep Declaration of competing interest
improvement of the degradation activity. Same conclusions are
obtained analysing the PAR degradation (Fig. 9b). However, as ex- The authors declare that they have no known competing
pected, it is observed that the activity toward the PAR degradation financial interests or personal relationships that could have
is higher than towards AMX. appeared to influence the work reported in this paper.
It is important also to highlight that the presence of in-
termediates was studied by high-performance liquid chromatog- Acknowledgements
raphy coupled to mass spectrometry (HPLC-MS). Intermediates
were not detected by HPLC-MS measurement (Figure S4) denoting This work was financially supported by the Spanish projects ref.
a complete mineralization of the drug. This complete mineraliza- RTI2018-099224-B-I00 from ERDF/Ministry of Science, Innovation
tion was confirmed by TOC analysis (Fig. 10). and UniversitiesdState Research Agency and ref. P12-RNM-2892
A comparison of the AMX and PAR degradation efficiency among
n-García is grateful
and, RNM172 from (Junta de Andalucía). E. Bailo
different catalysts and reaction conditions from literature is shown to Junta de Andalucía for her postdoctoral fellowship (P18-RTJ-
in Table 4. The degradation efficiency of using other Carbon/TiO2 2974).
composites as photocatalysts, even using UV radiation, was not as
high as the results obtained in this study. Irradiation times longer
Appendix A. Supplementary data
than 180 min are required to obtain a degradation efficiency similar
or even lower than that obtained using the activated carbon-based
Supplementary data to this article can be found online at
coloured titania nanoparticles described in the present manuscript
https://doi.org/10.1016/j.carbon.2021.03.044.
(<30 min) and total mineralization is not obtained in any case at
this time for other C/TiO2 composites.
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