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Room-Temperature Synthesis of Carbon Dot/TiO2 Composites with

High Photocatalytic Activity
Hao Zhou,† Bin Zhang,† Zhan Jiang, Haiguang Zhao,* and Yuanming Zhang*
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ABSTRACT: Benefiting from the wide-range absorption and

adjustable energy gap, carbon dots (C-dots) have attracted a great
deal of attention and they have been used to sensitize
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semiconductor nanocomposites to boost the efficiency of energy

conversion devices, while there is still a lack of fundamental
understanding of the interaction between such materials and their
influence on the catalytic activity on the reaction process. In this
study, C-dots were used to modify TiO2 to form a direct Z-scheme
(DZS) junction for enhancement of the photocatalytic activity.
The C-dot/TiO2 composite was prepared by ultrasonication at
room temperature through coupling between the Ti−O−C bond
and electrostatic interaction. The C-dots can dramatically enhance
the absorption of the composite by forming the DZS, and the
composite is enabled to generate more free radicals, which facilitate ∼10 times higher photocatalytic activity compared to that of
TiO2. As a proof of concept, the as-prepared C-dot/TiO2 was used for textile wastewater dye degradation. This study provides an
efficient approach for room-temperature preparation of C-dot/TiO2 composites with high photocatalytic activity.

1. INTRODUCTION and they found that the incorporation of Ag effectively

Photocatalysis is a very promising approach for various types of
organic pollutant treatment, as this approach can use natural
sunlight as the energy resource and the generation of highly
reactive intermediates [e.g., hydroxyl radicals (•OH)] could
oxidize organic pollutants without additional treatment.1−4
Meanwhile, this approach might be cost-effective and environ-
mentally friendly, if the photocatalytic materials consist of
nontoxic materials and can be renewable during the water
treatment.
In recent years, many types of semiconductors have been
used as candidates for photocatalysts.5−8 Among these
materials, TiO2 is of great interest because of its high
photocatalytic activity, high chemical stability, low toxicity,
and low cost. However, because of its large band gap (∼3.2
eV), TiO2 only absorbs the sunlight in the UV region (<400
nm, 5% of the solar energy), which largely limits its potential
commercial use for waste dye degradation.2,9 To boost the
photocatalytic activity of the TiO2, researchers have modified
TiO2 with other types of semiconductors or use of other types
of semiconductors with narrow band gaps, which can either
improve the absorption of the composite or enhance the
charge separation.10−12 For example, Bayat et al. reported
graphene quantum dot-decorated rutile TiO2 nanoflowers for
water splitting with enhanced photocatalytic properties.13
Qutub et al. reported the use of CdS in improving the
photocatalytic efficiency of TiO2 in the visible region.14
Duduman et al. used Ag-doped TiO2 for dye degradation,
improved the photocatalytic activity of TiO2 by controlling the
carrier charge recombination.15 Pandiyan et al. reported the
synthesis of the Ag−Sn bimetallic nanocomposite for the dye
degradation in the visible region.16 Hossein et al. synthesized
the graphene dot-grafted TiO2 composite, which enhanced the
photocatalytic efficiency by 85% under UV light illumination,
because the graphene dot not only improved the charge
transfer but also enhanced the absorption of the composite.17
Qiao et al. synthesized two-dimensional heterojunctions of
Bi2MoO6 and Bi2S3, which exhibited good photocatalytic
activity for the reduction of Cr(VI) under visible light
irradiation.18 The currently obtained photocatalytic activity
of most of the photocatalysts is still low, which prohibits the
potential application of these materials for industrial
applications. Carbon dots (C-dots) are a new type of zero-
dimensional carbon nanomaterials. Due to their good
biocompatibility, low cytotoxicity, simple synthesis,19 and
abundant sources, C-dots have attracted a lot of attention as
a promising candidate for photocatalysis and energy con-
Received: March 10, 2023
Revised: April 27, 2023
Published: May 11, 2023

© 2023 American Chemical Society https://doi.org/10.1021/acs.langmuir.3c00652

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Figure 1. (a) Low-resolution and (d) high-resolution TEM image of the TiO2 nanoparticles, (b) TEM and (e) high-resolution TEM images of the
C-dots, and (c) TEM and (f) high-resolution TEM images of the 9 wt % C-dot/TiO2.
version.2 They have structure-dependent properties; thus, one
can easily control their optical and electrical properties by
controlling their sizes and surface functional groups, which can
have strong interactions with the -OH groups of the TiO2.20−22
Although the C-dots can efficiently boost the photocatalytic
activity of the TiO2, there are still several issues that remain:
(i) The use of high temperature to graft the C-dots on the
surface of TiO2 may affect the optoelectrical properties of the
C-dots during the reaction. (ii) The coupling mechanism
between the semiconductor and metal oxides is still unclear.
Meanwhile, (iii) the photocatalytic activity of the composite is
still low and it is still difficult for industrialization.
In this work, we demonstrated a highly active photocatalyst
based on C-dot-grafted TiO2, which was prepared by a simple
sonication-assisted functional group coupling method at room
temperature. The C-dots can dramatically enhance the
absorption of the composite in the visible range and formed
DZS23 with TiO2, which achieved high photocatalytic activity,
showing dye degradation rate ∼10 times faster than that of
TiO2 under simulated sunlight. C-dot/TiO2 composites have
promising applications in solar-driven organic pollutant
treatment.
2. EXPERIMENTAL SECTION
2.1. Materials. TiO2 was purchased from Nano New Material
Technology Company. Citric acid monohydrate (CA), urea, form-
aldehyde, CaCl2, dichloromethane, methylene blue (MB), Rhodamine
B (Rh B), ethanol, and methanol were all purchased from Aladdin
Chemical Reagent Co., Ltd. Textile wastewater was received from
Jixing Knitting Factory company (Qingdao) and used as received.
2.2. Synthesis of the C-Dots and Purification. C-dots were
synthesized using CA and urea as precursors by using the vacuum
heating method.24 Briefly, CA was used as the carbon source with
urea as the nitrogen source, and the CA, urea, and CaCl2 powder were
dissolved in distilled water (4 mL) with a mass ratio of 1:2:1. The
mixture (4 g) was sonicated until the powder was completely
dissolved in water. The obtained clear solution was heated to 180 °C
for 20 min, and then, the temperature was increased to 250 °C and
kept at this temperature for 2 h under vacuum. The obtained powder
was dissolved in methanol. After centrifugation at 6000g for 10 min,
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the suspension was further purified by column chromatography. The
eluent contains methanol and dichloromethane with a volume ratio of
1:4. The obtained mixture was centrifuged at 6000g for 10 min and
freeze-dried. The obtained powder was used for further character-
izations and preparing the C-dot/TiO2 composite.
2.3. Preparation of the C-Dot/TiO 2 Composite. TiO 2
nanocrystals with different diameters (5, 10, 30, and 50 nm) were
dispersed in distilled water and further sonicated for 5 min. The
obtained clear mixture (5 g/L) was mixed with C-dot powder (with
the mass ratio ranging from 0 to 13%); subsequently, the mixture was
sonicated at 25 °C for different times (2−30 min) to obtain the C-
dot-grafted TiO2. The as-prepared mixture was directly used for
photocatalytic dye degradation. For the degradation of formaldehyde,
the mixture was sprayed on the paper with a concentration of 9% C-
dots and overall concentration of 2 g/L.
2.4. Photocatalytic Evaluation. The photocatalytic reaction
system mainly consists of a solar light source simulator (Newport
LCS100), a reactor, a cooling circulating water system, and a magnetic
stirrer, as shown in Scheme S1. To investigate the dye degradation
rate, typically, 50 mg of C-dot/TiO2 was dispersed in 100 mL of water
containing the dye (5 mg/mL). Different C-dot concentrations and
TiO2 sizes were also optimized for the dye degradation. The typical
weight concentration of the C-dots compared to that of TiO2 is 1, 5,
9, and 13%. The corresponding samples are defined as x wt % C-dot/
TiO2 (x is the mass concentration of the C-dots compared to TiO2).
The mixture was magnetically stirred in the dark for 30 min, and then,
the simulated sunlight was used for dye degradation (Scheme S1).
During the reaction, 3 mL of the mixture was extracted from the
reaction system every 5 min. Subsequently, the mixture was
centrifuged at 8000 r.p.m. to remove the C-dot/TiO2. Then, the
supernatant was filtered using a 200 nm membrane. The as-obtained
clear solution was measured using an absorption spectrophotometer.
Formaldehyde was monitored by coupling the reaction flask with gas
chromatography. The area of the sample is 1 m2, and the initial
concentration of the formaldehyde is 1 mg/m3.
2.5. Characterizations. Transmission electron microscopy
(TEM) characterization of the TiO2, C-dots, and C-dot/TiO2 was
carried out using a JEOL 2100F TEM assisted with selected area
electron diffraction (SAED). X-ray photoelectron spectroscopy (XPS)
was carried out for the TiO2, C-dots, and C-dot/TiO2 using an AXIS
Supra photoelectron spectrometer. A solution-phase NMR (Agilent
600 MHz DD2) was used to characterize the structure of the MB
before and after photodegradation. Absorption spectra were acquired
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Figure 2. (a) C 1s and (b) Ti 2p XPS spectra of pristine TiO2 and 9 wt % C-dot/TiO2 nanocomposites.
Figure 3. (a) ζ-potential plot obtained in water suspension of the TiO2, C-dots, and C-dot/TiO2. (b) Schematic diagram of the interaction
between C-dot and TiO2 nanocomposites by chemical bonds or electrostatic interactions.
with a Lambda 750 UV/visible spectrometer (PerkinElmer). The
surface charge of the C-dots, TiO2, and C-dot/TiO2 was measured by
using a ZetaSizer Nano-ZS. The electron paramagnetic resonance
(EPR) technique was used to measure the free radials •OH and •O2−
in the dark and upon illumination (light source: xenon lamp; capture
agent: DMPO). Steady-state and time-resolved photoluminescence
(PL) characterizations of the C-dots and C-dot/TiO2 dispersed in
water were performed on an Edinburgh FLS1000 instrument. The
quantum yields (QYs) of the C-dots were measured using an
integration sphere.
3. RESULTS AND DISCUSSION
3.1. Preparation and Structure of the Nanocompo-
sites. The C-dots were synthesized using a vacuum heating
approach, and the details are included in the Experimental
Section. The composite was obtained by mixing the C-dots
with the TiO2 mixture, following sonication. For a fair
comparison, we keep the same weight concentration of TiO2
in water but with varying the amount of C-dots. The structures
of TiO2, C-dots, and 9 wt % C-dot/TiO2 composites were
measured using TEM. As shown in Figure 1a, most of the TiO2
has an average particle size of 4.7 ± 1 nm with a lattice spacing
of 0.34 nm (Figures 1d and S1a), which is indexed to the
(101) plane of the anatase structure of the TiO2. As shown in
Figure 1b, the C-dots exhibited a quasispherical shape with a
size of ∼4.1 ± 1 nm (Figure S1b). The measured d spacing is
around 0.24 nm, corresponding to the (100) plane of the
hexagonal graphene structure (Figure 1e.). For the composite,
we clearly found that the C-dots were dispersed on the surface
of the TiO2 (Figure 1c). The lattice spacing of C-dots (0.24
nm) and TiO2 (0.34 nm) can be observed in the same region
(Figure 1f), confirming the existence of a tight interfacial
contact between C-dots and TiO2 nanoparticles, which is
favorable for the efficient change transfer between the two
semiconductors.
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XPS was used to verify the chemical composition of the
TiO2 before and after coupling with C-dots. Both the samples
consist of Ti/O elements (Figure S2). The Ti 2p peaks of
pristine TiO2 demonstrated two peaks located at 464.60 and
458.84 eV (Figure 2a), which are attributed to the Ti 2p1/2
bond and Ti 2p3/2 bond, respectively.20 The Ti 2p1/2 and Ti
2p3/2 peaks shifted to lower binding energy with a value of 0.26
eV after the C-dots were grafted on the TiO2. This energy
shifting is due to the formation of the C−O−Ti bond.20
Consistently, the XPS C 1s peaks were located at 288.8, 285.2,
and 284.1 eV, which are corresponding to the C�O, C−O
and Ti−O−C, respectively (Figure 2b), consistent with the
FTIR results (Figure S3b). These results indicate that the C-
dots can strongly attach on the surface of the TiO2 by chemical
bonds (Figure 3b).
The as-prepared C-dot/TiO2 using 5 and 10 nm TiO2 shows
a very good stability in water. We did not observe the
aggregation of the composite, while for the composite prepared
using 30 and 50 nm TiO2, the composite started to precipitate
after 1 h. In order to understand the colloidal stability of the
as-prepared materials, the surface charge of the C-dots, TiO2,
and C-dots/TiO2 dispersed in water before and after
sonication was measured using a ZetaSizer Nano-ZS. The ζ-
potential of the C-dots is between −30 and 0 mV with a peak
around −9.2 mV (Figure 3a), confirming that the C-dots have
a negative charge on the surface, which is contributed by the
hydroxyl and carboxyl groups, consistent with the FTIR results
(Figure S3).25 In big contrast, the TiO2 nanoparticles
dispersed in water show the ζ-potential peak of ∼38.2 mV,
which endows the TiO2 with very good dispersion in water.
The positive charge of the TiO2 is explained by the formation
of an electric double layer in the polar solvent.26 Upon mixing
the C-dots with TiO2 in water, after 30 min, the average ζ-
potential of the mixture is 33.9 mV (Figure 3), indicating the
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Figure 4. (a) UV−vis absorption spectra, (b) PL spectra, and (c) time-resolved fluorescence spectra of the as-prepared various types of samples.
The excitation wavelength is 405 nm.

Figure 5. PL spectra of the samples during sonication: (a) without sonication and (b) with sonication. The integrated PL area as a function of
sonication time. (c) PL intensity of the composite with or without sonication as a function of time. The excitation wavelength is 405 nm.

Figure 6. EPR spectra of (a) •OH and (b) •O2− of the 9 wt % C-dot/TiO2 and TiO2 in the dark and upon illumination. (c) Photocatalytic
mechanism of photocatalytic C-dot/TiO2 with a DZS-type junction upon sunlight illumination.

electrostatic interaction between the negatively charged C-dots
and positive charged TiO2. Due to the high charge density of
the TiO2, the mixture still has a positive charge, which
facilitates the very good stability of the mixture. After
sonication for 30 min, the composite still has a positive charge
(30.1 mV) with a narrower distribution compared to the
composite without sonication (Figure 3), which indicates that
sonication can improve the interaction between the C-dots and
TiO2 , thus modifying the surface charge and charge
distribution.
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TEM, XPS, and ζ-potential results confirmed the strong
interaction between the C-dots and TiO2 through both the
chemical bond and electrostatic interaction. Thus, we conclude
that sonication can assist in the interaction between the Ti-O
and C�O bonds, while without sonication, the electrostatic
interaction contributed to the interaction between C-dots and
TiO2 nanoparticles as shown in Figure 3b.
3.2. Optical Property of the Composite. The as-
prepared C-dots have a high quantum yield of 70%, which is
useful for the efficient charge transfer, other than the surface
trap/defect-induced PL quenching. The composite has
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Figure 7. (a) Comparison of MB degradation by using the photocatalyst with different C-dot concentrations under simulated sunlight irradiation;
(b) reaction kinetic study; (c) degradation rates of MB using different photocatalysts; and (d) degradation rate constants of MB by using different
photocatalysts. Photoreduction reaction conditions: MB concentration of 5 mg/L, photocatalyst dosage of 0.5 g/L, and simulated sunlight intensity
of 70 mW/cm2.

absorption ranging from 300 to 500 nm as the C-dots can
efficiently absorb UV and visible light (Figure 4a); in a huge
contrast, TiO2 can only absorb light at wavelengths below 380
nm because of its large band gap (∼3.2 eV). The enhanced
absorption may significantly improve the photocatalytic
performance of the TiO2.27 With the increase of the C-dot
concentration, the absorption of the composite increases
significantly. We also observe scattering in the range of 500−
600 nm, especially for the composite with a higher
concentration of C-dots (Figures 4a and 5). It is worth
mentioning that we did not observe the absorption peak at 405
nm of the C-dots in the composite samples, which might be
due to the scattering of the system. To understand the
coupling effect on the optoelectrical properties of the
composite, we measured the static and transient fluorescence
spectra of the sample. In the emission range (450−700 nm),
we did not observe the PL from the TiO2, while the composite
exhibited a clear PL with an emission peak centered at 520 nm
(Figure 4b). For all the samples, we diluted the original
solution to obtain an identical concentration of the C-dots for
the PL measurements for a fair comparison. The composite
with 1% C-dots exhibited the lowest PL compared to other
samples. PL intensity deceases gradually with increasing ratio
of C-dots/TiO2 (Figure 4b), indicating that the interaction
between the C-dots and TiO2 becomes weak with the increase
of the weight ratio of the C-dot/TiO2. This might be explained
by the presence of the free C-dots or weakly bonded C-dots in
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the sample with high C-dot concentration. Furthermore, time-
resolved fluorescence spectroscopy was used to measure the
PL decays of the pristine C-dots, 1 wt % C-dot/TiO2, and 9 wt
% C-dot/TiO2. The average lifetimes of the composite are 6.4
± 0.1 and 5.9 ± 0.1 ns for 1 wt % C-dot/TiO2, and 9 wt % C-
dot/TiO2, respectively, which are significantly longer than that
of the C-dots (4.1 ± 0.1 ns) (Figure 4c). This result indicates
the formation of a DZS between the TiO2 and C-dots as
shown in Figure 6c. Upon illumination, the e−h pairs of the
TiO2 and C-dots were generated separately. Subsequently, part
of the photoexcited electrons in the conduction band (CB) of
TiO2 could be recombined with the photogenerated holes in
the valence band (VB) of the C-dots as shown in Figure 6c, as
this kind of recombination may have a low-resistance
interface.28 This effect leads to the decrease of Coulomb
attraction, giving a longer lifetime of the exciton in the C-dot/
TiO2 compared to the C-dots. As a result, electrons in the CB
of the C-dots react with oxygen molecules (O2) and convert
them into superoxide radicals (•O2−) and holes in the VB of
TiO2 react with water and release hydroxyl radicals (•OH).29
Both •O2− and •OH are able to oxidize wastewater dyes to
CO2 and H2O without secondary pollutions.11
To figure out the effect of the coupling between the C-dots
and TiO2 on the charge dynamics in the composite, we in situ
measure the PL spectra of the composite as a function of time
during the sonication. To investigate whether ultrasound has
an impact on the PL of C-dots, we conducted experiments to
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Table 1. Comparison of Photocatalytic Performance of MB by Various Types of Photocatalystsb
catalyst concentration
catalysts (g/L) MB (c, mg/L)
C-dots/BiVO4 0.5 10
carbon aerogel/Na2Ti3O7 1 20
Ag−AgCl/TiO2 1 50
Al-Fe/ZnO 1 10
Si-C-dots 0.5 10
carbon/C3N4 0.4 10 (RhB)
C-dots/Cu2Oa 0.25 20
Zr−N−S-doped C-dots 0.5 1 (malachite green)
C-dot/TiO2 0.5 5 30
a
H2O2 (30%, w/w) was added into the suspension during the photocatalytic experiment. b----The authors did not give the light intensity.
compare the PL of C-dots under different ultrasound times.
Our experimental findings revealed that ultrasound has little
impact on the PL of C-dots during the sonication process
(Figure S5). As a comparison, we also characterize the PL
spectra of the composite without sonication. As shown in
Figure 5, the PL intensity of the composite decreases as a
function of time with or without sonication, while there is no
PL peak variation. The decrease of the PL is due to the
formation of the DZS. As shown in Figure 5c, after 15 min, the
composite maintains 80% of its initial PL, which is higher than
that of the sample under sonication, keeping only 45% of its
original value. After 20 min of sonication, the PL maintains
only 30% of its initial value (Figure 5c). This result indicates
that the chemical bond induces tight coupling between the C-
dots and TiO2, which boosts the e−h recombination efficiency
through the DZS-type junction compared to the C-dot/TiO2
coupling with electrostatic interactions.
To verify the radicals produced upon simulated sunlight
illumination, the EPR technique was used to detect the free
radicals •OH and O2−, and the results are shown in Figure
6a,b. Under dark conditions, neither TiO2 nor C-dot/TiO2
composites showed the characteristic signal peaks of •OH and
• calculated to be 56.5 × 10−3 min−1, which is approximately 10
O2−, indicating that the photocatalysts could not generate free
radicals in the absence of light excitation. After 5 min of
simulated light exposure, the characteristic signal peaks of •OH
and •O2− appeared for both TiO2 and the C-dot/TiO2
composite, indicating that both TiO2 and the C-dot/TiO2
composite could produce •OH and •O2− upon illumination
(Figure 6a,b). The TiO2 generated more •OH compared to the
C-dot/TiO2 composite. This may be attributed to the presence
of the free C-dots in the solution, which serves as •OH
scavengers, leading to a decrease in •OH concentration, while
the C-dot/TiO2 composite produced more •O2− compared to
TiO2 under identical measurement conditions. This phenom-
enon can be well explained with the DZS-type junction of the
C-dot/TiO2 composite (Figure 6c). After internal recombina-
tion between the photogenerated electrons in TiO2 and holes
in the C-dots, the number of photogenerated electrons of the
C-dots is higher than that of the TiO2; meanwhile, the
photogenerated holes of the C-dots is lower than that of the
TiO2, which explained the more •O2− and less •OH in the
composite than those of the TiO2. The EPR result is consistent
with that of the lifetime, confirming that the presence of C-
dots can dramatically enhance the concentration of free
radicals in the composite system.
3.3. Photocatalytic Activity of the C-Dot/TiO 2
Composite. The photocatalytic properties of TiO2 with
different loading amounts of C-dots were investigated by using
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time degradation efficiency light intensity
(min) (%) (mW/cm2) refs
200 90 ---- (Xe lamp) 30
90 98.3 ---- (sunlight) 31
120 90 95 mW/cm2 (sunlight) 32
75 90 ---- (Xe lamp) 33
75 98.8 ---- (halogen lamp) 34
20 90.4 ---- (Xe lamp) 35
8 100 ---- (Xe lamp) 36
37
90 99 50−58 (sunlight)
90 70 (sunlight) this work
MB, and the setup is shown in Scheme S1. For all the
measurements, without specification, simulated sunlight (70
mW/cm2) was used and the concentration of TiO2 was kept
constant (5 g/L). The absorption of MB was monitored by the
absorption spectra, and the ratio of At/A0 was used to estimate
the value of Ct/C0, where At and A0 are the absorbance of MB
at certain time (t) and the initial stage (t0) and Ct and C0 are
the concentration of MB at certain time (t) and the initial stage
(t0), respectively. The degradation rate was calculated as (C0 −
Ct)/C0. In the dark, there is no dye degradation with the
presence of the C-dots, TiO2, or composite; in light, there is no
degradation of MB with or without the presence of C-dots.
Upon sunlight illumination, the blue color of the MB gradually
fades (inset of Figure 7d), indicating the degradation of MB.
As shown in Figure 7a, the remaining MB concentration with
respect to its initial concentration (denoted as Ct/C0)
decreased the fastest in the presence of 9 wt % C-dot/TiO2
among all samples. In detail, after 30 min of illumination, about
90% of the MB was degraded using 9 wt % C-dot/TiO2, which
was eightfold higher than that of TiO2 (Figure 7c). Specifically,
the first-order rate constant (k) of 9 wt % C-dot/TiO2 was
times higher than that of pure TiO2 (5.9 × 10−3 min−1)
(Figure 7b−d). Our results are comparable with the best of
photocatalytic systems reported in the literature for dye
degradation (Table 1). These results confirmed that the C-dots
can significantly enhance the catalytic properties of the TiO2
due to the following reasons: (i) the wide-range absorption of
the C-dots enhances the absorption of TiO2 and (ii) benefiting
from the enhanced absorption and the formation of the Z-
scheme, the number of free radicals increases significantly.
We performed the recycling experiment by using rhodamine
B (Rh B) as the RhB has broad absorption with the first
excitonic absorption peak of 552 nm, which well separates the
absorption of the C-dots, guaranteeing the accurate measure-
ment of the dye concentration. After four cycles of degradation
experiments, the degradation rate of the Rh B does not have a
significant variation, indicating the very good photocatalytic
stability of the composite (Figure S6a). It is worth mentioning
that even under room light (40 μW/cm2), the catalysts can
efficiently degrade the Rh B (Figure S6b). After 12 h of
illumination, the pink color fades and the dye was completely
degraded (inset of Figure S6b). The NMR experiments further
confirmed that the dyes were degraded other than discolor-
ation (Figure S7). These results indicate that the as-prepared
composite can be used as an efficient photocatalyst for dye
degradation, even at low sunlight intensity.
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Figure 8. (a) Degradation of textile effluent by using C-dot/TiO2. (b) Degradation of turmeric by using C-dot/TiO2. Turmeric concentration of
100 mg/L and photocatalyst dosage of 0.5 g/L. (c, d) Photographs of the dyes (c, textile effluent; d, turmeric) upon illumination (100 mW/cm2) at
different times.
As a proof of concept, we also used 9 wt % C-dot/TiO2
composite as photocatalysts for the textile wastewater dye and
formaldehyde degradation. Two types of textile wastewater
dyes were used for the experiments, including chemical dyes
and natural dyes, which were obtained from the textile
company as a gift. Upon simulated sunlight illumination (100
mW/cm2), the color of the dyes gradually fades off (Figure
8c,d), which indicates the degradation of the dyes. As shown in
Figure 8a, 90% of the textile chemical effluent was degraded
within 100 min. In a huge contrast, 97% of the textile natural
effluent (turmeric) was degraded within 8 min. As shown in
Figure 8d, after 8 min of illumination, there is almost no color
for the turmeric. Obviously, the natural dye (turmeric) is easier
oxidized compared to chemical dyes, which might be due to
the stable structure of the synthesized dyes. Our result suggests
that the use of natural dyes for printing and dyeing could cause
less water pollution compared to that of the synthesized dyes.
For the formaldehyde degradation, we used a heater to
evaporate the formaldehyde solution; after 24 h of illumination
(xenon lamp, 400−900 nm, 10 mW/cm2), the concentration
of the formaldehyde decreases to 30 ± 2% of its initial value,
indicating that the as-prepared composite can also oxide the
formaldehyde.
4. CONCLUSIONS
In summary, the high-quality C-dots were used to graft the
TiO2 nanoparticles with sizes ranging from 5 to 10 nm to form
a DZS-type junction for efficient photocatalytic degradation of
textile wastewater dyes and formaldehyde. As the as-prepared
C-dots have a broad absorption and functionalized surface, a
simple ultrasonic approach can assist in the coupling between
the C-dots and TiO2. The C-dot/TiO2 composite dramatically
enhances the number of free radicals, which leads to ∼10 times
higher photocatalytic dye degradation rate compared to that of
TiO2. As a proof of concept, the C-dot/TiO2 with optimized
C-dot concentration can efficiently photodegrade textile
wastewater dyes and formaldehyde. This study provides an
efficient photocatalytic system, which might be used for textile
wastewater dye and formaldehyde degradation, water splitting,
and organic pollution removal.
■ ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.3c00652.
7190
Article
Photographs of the experimental setup; size distribution;
XPS spectra; 1H NMR spectra; and PL of C-dots during
sonication (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Haiguang Zhao − College of Textiles and Clothes, State Key
Laboratory of Bio-Fibers and Eco-Textiles, Qingdao
University, Qingdao 266071, P. R. China; orcid.org/
0000-0003-1057-9522; Email: hgzhao@qdu.edu.cn
Yuanming Zhang − College of Textiles and Clothes, State Key
Laboratory of Bio-Fibers and Eco-Textiles, Qingdao
University, Qingdao 266071, P. R. China;
Email: Zhangyuanming001@163.com
Authors
Hao Zhou − College of Textiles and Clothes, State Key
Laboratory of Bio-Fibers and Eco-Textiles, Qingdao
University, Qingdao 266071, P. R. China
Bin Zhang − College of Textiles and Clothes, State Key
Laboratory of Bio-Fibers and Eco-Textiles, Qingdao
University, Qingdao 266071, P. R. China
Zhan Jiang − College of Textiles and Clothes, State Key
Laboratory of Bio-Fibers and Eco-Textiles, Qingdao
University, Qingdao 266071, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.3c00652
Author Contributions
†
H.Z. and B.Z. contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
H.Z. acknowledges the funding support from the Key Research
and Development Program of Shandong Province (Grant No.
2021CXGC011003). H.Z. acknowledges the funding support
from the Youth Innovation Team Project of Shandong
Provincial Education Department.
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