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Applied Surface Science 453 (2018) 394–404

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Applied Surface Science


journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Synergistic effect of adsorption and visible-light photocatalysis for organic T


pollutant removal over BiVO4/carbon sphere nanocomposites

Xiaotong Wang, Jianqing Zhou, Shuo Zhao, Xiao Chen, Ying Yu
Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China

A R T I C LE I N FO A B S T R A C T

Keywords: Photocatalysis and adsorption are considered as the effective methods to remove organic pollutants in waste-
BiVO4 waters. In this study, a novel composite, BiVO4 with reasonable bandgap (∼2.4 eV) and good photocatalytic
Carbon sphere performance combined with carbon sphere, is successfully prepared, which can be used to remove organic
Photocatalysis pollutants by the synergistic effect of adsorption and photocatalysis. In the composite, the carbon sphere has
Adsorption kinetics
good ability to adsorb the pollutants, which is beneficial for them to be further photodegraded. Besides, it has
good conductivity, which can facilitate the transfer of photogenerated electrons, thus reducing the re-
combination of photogenerated carriers for photocatalytic performance improvement. It is found that the
composite with optimized ratio shows good adsorption and photocatalytic performance. The photodegradation
rate for methylene blue over the best composite under visible-light irradiation is 11.56 times higher than that
over pure BiVO4 and that for rhodamine B is 4.42 times higher. The study provides a promising photocatalyst to
be used for organic pollutant removal in large scale.

1. Introduction applications due to its poor adsorption capacity and low separation
efficiency for its photo-generated electrons and holes [20,21]. To
Various kinds of effluent wastewaters from industries such as tex- overcome these problems, many bismuth-based photocatalysts have
tile, dyestuff, leather and paper production, contain coloring organic been improved by the modification with carbonaceous materials such
pollutants, which are toxic and need to be treated [1,2]. A wide range of as graphene [22], the decoration with noble metal nanoparticles, etc.
conventional treatment techniques (such as carbon adsorption, and As we all known, noble metal is very expensive while graphene is not
photocatalytic degradation, chemical coagulation, activated sludge and easy to prepare. As such, it is urgently necessary to find a way to im-
so on) for organic pollutant removal from aquatic bodies have been prove the adsorption and electroconductibility of this semiconductor
extensively investigated [3–5]. Among them, the photocatalytic de- simultaneously with a facile and cheap method.
gradation and carbon adsorption are considered as one of the most According to previous studies, carbon sphere prepared with glucose
effective methods. has large surface area and active groups on its surface, which is bene-
Photocatalysis is a kind of advanced oxidation technology for re- ficial to adsorb dye [23,24]. Besides, the carbon sphere is facile to
moving organic pollutants [6–8]. With the development of new semi- prepare, leading to its low cost. Thus, if BiVO4 and carbon sphere are
conductor photocatalysts, bismuth-based oxysalts have been explored combined together, the good adsorption ability and enhanced photo-
widely for their excellent visible-light photocatalytic activity, chemical catalytic performance can be achieved simultaneously for one photo-
and thermal stability and non-toxicity [9,10], in which bismuth vana- catalyst. It means that the organic pollutants are easily adsorbed onto
date (BiVO4) has attracted a great deal of scientific attention since it can the surface of the photocatalyst firstly and then quickly degraded with
be activated by visible light for organic pollutant degradation [11,12] strong possibility.
and oxygen production [13]. There are three main crystalline phases in In this study, a series of BiVO4 (BVO) with scheelite monoclinic
BiVO4, which are scheelite monoclinic (∼2.4 eV), scheelite tetragonal phase/carbon sphere (C) [25] (BVO-C) composites with different ratios
and zircon tetragonal structure (∼3.1 eV) [14–16]. Among them, the were synthesized via a hydrothermal process. The ratio of BVO and
scheelite monoclinic phase of BiVO4 has the best activity under visible carbon sphere was adjusted for the optimal proportion to possess good
light, far better than the other two types [17–19]. However, the limited photocatalysis and adsorption performance simultaneously. Ad-
photocatalytic activity of pure BiVO4 has restricted its further practical ditionally, scanning electron microscopy, X-ray powder diffraction, X-


Corresponding author.
E-mail address: yuying01@mail.ccnu.edu.cn (Y. Yu).

https://doi.org/10.1016/j.apsusc.2018.05.073
Received 11 February 2018; Received in revised form 28 April 2018; Accepted 11 May 2018
Available online 17 May 2018
0169-4332/ © 2018 Elsevier B.V. All rights reserved.
X. Wang et al. Applied Surface Science 453 (2018) 394–404

ray photoelectron spectroscopy, Brunauer-Emmett-Teller, UV–vis-dif- as the reference. Additionally, a 0.02 M Na2SO4 aqueous solution was
fuse reflectance spectra, electrochemical impedance spectroscopy, used as the electrolyte. The photocurrent of the samples was measured
transient photocurrent, Raman spectra, FT-IR spectra and so on were under a chopped irradiation from a 350 W xenon lamp (Lap Pu, XQ)
used to characterize the samples. Methyl blue (MB) and rhodamine-B with 420 nm cutoff filter right above the reactor (light on/off cycle:
(RhB) were used as the target pollutants to test the photocatalytic 20 s). The output current for the lamp was controlled to be 15 A with an
performance under visible-light irradiation and adsorption property. average intensity of irradiation 97.3 mW/cm2 determined by a light
Besides, the adsorption kinetic models of pseudo-first-order and meter (LICOR Biosciences, LI-250A). The photoluminescence (PL)
pseudo-second-order models were employed to investigate the adsorp- spectra of photocatalysts were recorded using a fluorescence spectro-
tion mechanism of MB and RhB onto the surface of BVO-C, which was photometer (F-7000, Hitachi) with the excitation wavelength of
based on the difference in equilibrium adsorption capacity and ad- 420 nm.
sorbed amount, and the assumption that the rate-limiting step involves
chemisorption, respectively [26,27]. 2.3. Photocatalytic activity measurement

2. Experimental section The experimental apparatus for the photocatalytic reactions was
consisted of a 350 W xenon lamp (Lap Pu, XQ) as light source. Besides,
2.1. Sample synthesis 420 nm cutoff filter (Shanghai Seagull Colored Optical Glass Co. Ltd.,
China) was employed to allow desired irradiation wavelengths to pe-
All the chemicals used in this study were purchased from Shanghai netrate. The distance between the lamp and the top of reaction vessel
Guoyao Chemicals Ltd. The chemicals were analytical reagents and was approximately 20 cm. Based on the distance, the average intensity
used without further purification. Deionized water was used for the of irradiation was approximately 97.3 mW/cm2 (LICOR Biosciences, LI-
preparation of all aqueous solutions. 250 A). The mixture of dye solution and the photocatalysts was con-
In this study, carbon sphere was synthesized by a facile solvent tained in a thermostatted bath with circulating cooling water at
method [25]. 1 M glucose solution had been kept magnetically stirring 20 ± 3 °C.
at 160 °C for 6 h. After that, black precipitate was collected by cen- The photocatalytic activity of the BVO-C was evaluated by the de-
trifugation and washed for three times with deionized water and colorization of MB and RhB. In this operation, 0.1 g the prepared
ethanol. After being dried off at 70 °C for 10 h, carbon sphere was ob- samples were added into 100 mL 1 × 10−4 mol/L MB solution or
tained. 5 × 10−5 mol/L RhB solution, followed by ultraphonic dispersion for
The preparation of BVO-C was carried out with a solvent hydro- 20 min and magnetic stirring for 40 min to ensure the adsorption-des-
thermal method [28]. 2 mmol Bi(NO3)3 was dissolved into 20 mL glycol orption equilibrium between the dye and the samples. All the processes
with stirring for 20 min to form a transparent solution. And 2 mmol of adsorption-desorption equilibrium were undertaken in dark. Then,
NH4VO3 was dispersed into 20 mL deionized water ultrasonically. the mixture was transferred into the reactor under the xenon lamp il-
Afterwards, these two miscible solutions were mixed with stirring for lumination. 2 mL liquid sample was taken every 20 min per time. The
20 min. Then, the carbon sphere prepared in advance with certain supernatant dye solution was analyzed by using ultraviolet–visible
amount was added into the precursor solution with magnetic stirring to (UV–vis) spectrophotometer (SHIMADZU UV-1700). The degradation
ensure homogeneous dispersion. Subsequently, the mixed solution was efficiency was defined as C/C0, in which C0 is the initial concentration
transferred into 100 mL Teflon-lined autoclaves, heated up to 100 °C of the MB or RhB solution and C the concentration with specific de-
and had been kept at this temperature for 15 h. After that, the product gradation time after visible-light irradiation.
was collected by centrifugation and washed with alcohol and deionized
water for 3 times. Finally, the composites were prepared after dried off 2.4. Adsorption kinetics study
at about 70 °C for 10 h in air. The samples are named by BVO-0.12C,
BVO-0.18C and BVO-0.24C with 0.12 wt%, 0.18 wt% and 0.24 wt% All the experiments were carried out using batch-adsorption process
content of carbon sphere respectively. The sample named BVO stands in an orbital shaker at 25 °C and 150 rpm in dark to eliminate light
for the pure BiVO4 without carbon sphere, and C represents pure carbon effect. The experiments were performed at pH = 7 with adsorbent do-
sphere. sage of 0.05 g unless stated otherwise. After the completion of the ad-
sorption experiments, the absorbance of the supernatant dye solution
2.2. Samples characterization was analyzed using the UV–vis spectrophotometer. The absorbance of
MB and RhB was measured at the wavelength of 664 nm and 552 nm,
The morphology of the prepared samples was detected with scan- respectively. The amount of dye adsorbed on the samples was calcu-
ning electron microscopy (SEM). The crystalline phase of BVO-C was lated as
analyzed by X-ray powder diffraction (XRD) patterns, which a
(C0−Ct ) V (C −C ) V
Panalytical diffractometer (D/max 40 kv) with Cu Kα radiation qt = qe = 0 e
m m (1)
(λ = 0.1546 nm) was used to measure. The surface chemical analysis of
BVO-C was conducted with X-ray photoelectron spectroscopy (XPS) where qe and qt (mg/g) is the adsorption capacity at equilibrium and t
(VG Multiab-2000) with a PHI Quantum 2000 XPS system with a time respectively, m (g) the mass of samples, V (L) the volume of dye
monochromatic Al Kα source and charge neutralizer. A Micromeritics solution, C0 and Ct (mg·L-1) the initial and t moment concentration of
ASAP2020 nitrogen adsorption apparatus (USA) was used to char- dye solution respectively and Ce the equilibrium concentration.
acterize the Brunauer-Emmett-Teller (BET) specific surface area of the
samples. Raman spectra was detected by using a LabRAMHR Raman 3. Result and discussion
system under Ar+ (532 nm) laser excitation at room temperature.
UV–vis diffuse reflectance spectra (UV–vis DRS) was collected with 3.1. Phase structure and morphology
PerkinElmer Lambda 35 spectrophotometer in the range of 400–800 nm
by using BaSO4 as a reference to represent the absorbancy of the The phase structure of the samples is shown in Fig. 1. The char-
samples. Electrochemical impedance spectroscopy (EIS) was tested with acteristic peaks located at 28.91°, 30.51°, 35.21°, 39.91° and 53.21°
an electrochemical station (PARSTAT 2273, Princeton) in a standard were attributed to (1 2 1), (0 4 0), (0 0 2), (2 1 1) and (1 6 1) for
three-electrode system with a platinum plate as counter electrode, the monoclinic BiVO4 [JCPDS 14-0688], respectively [29,30], which sug-
prepared samples as working electrode and standard Ag/AgCl electrode gests that pure BiVO4 was prepared successfully. With the addition of

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X. Wang et al. Applied Surface Science 453 (2018) 394–404

Fig. 3. Raman spectra for pure BVO, BVO-C and carbon sphere.
Fig. 1. XRD patterns for BVO, BVO-0.12C, BVO-0.18C and BVO-0.24C.

against to combine with BVO.


carbon sphere, there was no peak assigned to carbon for the composites,
which may be due to the reason that the amount of the carbon sphere
was too little or the prepared carbon sphere was amorphous as shown in
3.2. Raman spectroscopy
the Fig. S1 [31]. The presence of carbon sphere can be identified by
Raman spectroscopy, which will be introduced in the follow section.
Raman spectroscopy is a sensitive tool for the investigation of
SEM images in Fig. 2 revealed the morphology of the pure BiVO4
structural information. Raman spectra of the different samples are
and the composite of BVO-0.18C with 0.18 wt% carbon sphere. Those
shown in Fig. 3. Raman bands at around 210, 324, 366, 640 and
for the samples with other contents of carbon sphere are shown in Fig.
826 cm−1 were observed as the typical vibrational ones for BiVO4 in all
S2. It is found that dumbbell like BVO was prepared with the mean
samples. Among them, the band located at 210 cm−1 was the external
length and width of about 2.5 μm and 1 μm respectively. As seen from
mode of BiVO4, while those at 324 and 366 cm−1 was assigned to the
the SEM images, carbon spheres and BVO were attached to each other.
asymmetric and symmetric deformation modes of VO43− tetrahedron
However, the carbon spheres were unevenly distributed on the surface
respectively. The one at 826 cm−1 corresponded to the stretching
of BVO and the ends were more likely to be covered. The main reason of
modes of VeO bonds [33–35]. Notably, there was only one type of
this phenomenon was probably owing to the much rough ends of BVO
stretching vibrational band observed in the samples, suggesting that
and the uneven distribution of the stress on the surface [32]. With the
stretching mode of the VeO bond was present in all samples. The
increase of the carbon spheres, more carbon spheres were attached. But,
Raman spectrum of the pure carbon sphere is also presented in the
too many carbon spheres were easily to form large clusters, which was
insert of Fig. 3, in which D band (∼1350 cm−1) and G band

Fig. 2. SEM images of BVO (a and b) and BVO-0.18C (c and d).

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X. Wang et al. Applied Surface Science 453 (2018) 394–404

Fig. 4. High resolution XPS spectra of Bi 4f, V 2p, O 1s and C 1s in BVO, BVO-0.18C and carbon sphere.

(∼1596 cm−1) were clearly observed. As we all known, the D band O 1s spectra for the samples of carbon sphere, pure BVO and BVO-
represents the crystal defect of carbon atoms while the G band stands 0.18C, are shown in Fig. 4c. The asymmetric peak centered at 530 eV
for the expansion vibration of sp2 orbital hybridization [36]. With the was decomposed into two components at the binding energy of
increase of carbon sphere amount, the D band and G band were clearly 529.4 eV and 531.2 eV for the pure BiVO4, which was due to the surface
shown in the samples of BVO-0.12C, BVO-0.18C and BVO-0.24C, which lattice oxygen and the adsorbed oxygen species respectively [41,42]. As
suggests that the carbon spheres were present in the composites. In for the broad peak in the sample of pure carbon sphere, it was the result
addition, the external mode of the bond around 210 cm−1 for BVO- of a variety of carbon-oxygen bindings [37,43–44]. With the addition of
0.12C, BVO-0.18C and BVO-0.24C shifted to lower wavelength com- carbon sphere, the peaks of oxygen were complex and shifted to lower
pared to that for pure BVO, which indicates that the external mode binding energy, which indicates that the intricate oxygenous groups
changed after the carbon sphere was combined with BVO [33]. were included in the composites and the electron cloud density around
O decreased because of the addition of carbon sphere with lower
electronegativity [41]. In Fig. 4d, there were XPS spectra of C 1s peak
3.3. XPS analysis
for pure carbon sphere, pure BVO and BVO-0.18C. In the spectrum of C
1s in pure carbon sphere, there was only one peak at 284.3 eV, which
The chemical states of pure carbon sphere, pure BVO and BVO-
was ascribed to the sp2 bonded carbon (C]C) [37,45]. The C 1s peaks
0.18C were investigated by XPS analysis, and the results are shown in
at around 284.6 and 288.3 eV were attributed to the carbon signal from
Fig. 4. Fig. 4a displayed the Bi element in both pure BVO and BVO-
carbon in the instrument for calibration and the adsorbed CO2 on the
0.18C. Thereinto, two strong peaks in the spectra at 164.4 and 159.0 eV
surface of pure BVO respectively [21,38,46–49]. It is worth noting that
were assigned to Bi 4f5/2 and Bi 4f7/2, respectively, which suggests that
there was a new peak at 286.2 eV for BVO-0.18C, which could be as-
the bismuth specie in BVO and BVO-0.18C was Bi3+ cations [37,38].
cribed to the formation of CeOeC (the O atoms in BVO) between BVO
With the addition of carbon sphere, no apparent change was observed,
and carbon sphere [44,48–49]. The above result displays that most of
which reveals that the chemical states of Bi species were not changed.
carbon atoms in BVO-0.18C were sp2 hybridized and there were oxy-
The chemical states of V species are presented in Fig. 4b, in which the
genous functional groups like CeO or C]O and CeOeC in BVO-C
characteristic spin-orbit splitting of V 2p1/2 and V 2p3/2 signals was
system, indicating that the strong interaction between BVO and carbon
observed at approximately 524.0 and 516.3 eV, respectively, corre-
sphere was formed during the solvothermal reaction process [50]. This
sponding to V4+ in BiVO4, which is consistent with the former reports
phenomenon is well consistent with the result of Raman spectra. The
about BiVO4 [37–40].

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Fig. 6. N2 adsorption–desorption isotherms and pore size distribution curves


Fig. 5. FTIR spectra of BVO, BVO-0.18C and carbon sphere. (the inset) of BVO, BVO-0.18C and carbon sphere.

new CeOeC binding was not found in the spectra of O 1s due to the
overlap of other broad peaks nearby.

3.4. FT-IR spectrum

FT-IR spectrum is an informative and important technique to de-


termine the change of organic groups in materials. The FT-IR spectra of
BVO, BVO-0.18C and carbon sphere are shown in Fig. 5. The peaks at
1709, 1621 and 1326 cm−1 were assigned to C]O, C]C and CeOH
vibrations, respectively [50], in which the one at 1621 cm−1 was re-
sulted from the bond vibration of un-oxidized graphitic or the re-
maining sp2 carbon character of graphite [36]. The peak located at
1498 cm−1 in BVO-0.18C was attributed to the bond of CeOeC, which
was not present in carbon sphere or pure BVO. It suggests that the
strong interaction was formed between the carbon sphere and BVO.
Fig. 7. Zeta potential for BVO, BVO-0.12C, BVO-0.18C and BVO-0.24C.
Besides, the peak located nearby 1500 cm−1 was weaker in the sample
of BVO-0.18C, which was due to the change of the electronic en-
vironment of carbon atom [51]. This phenomenon is consistent with the analysis. The zeta potential of BVO-0.18C was −63.8 mV. With the
result of XPS spectra, indicating that the strong interaction was formed further increase of the content of carbon sphere, the zeta potential of
between BVO and carbon sphere. In addition, the peak at 748 cm−1 in BVO-0.24C was more positive than that of BVO-0.18C, which may be
BVO and BVO-0.18C was assigned to the stretching vibrations of VeO the result of the agglomeration of excess carbon sphere and the de-
bonds [52]. creased binding between BVO and carbon sphere.

3.5. BET and zeta potential


3.6. Electrochemistry property
The BET and the pore structure of the prepared samples are shown
The electrochemical properties including the transient photocurrent
in Fig. 6, which were detected via nitrogen adsorption-desorption
response and EIS spectra of the samples were investigated to explore
measurement. As we can see, the isotherm for the BVO, BVO-0.18C and
photocatalytic mechanism and the data are shown in Fig. 8a and b
carbon sphere belonged to the type IV according to Brunauer–De-
respectively. It can be found from Fig. 8a. that all of the samples of
ming–Teller classification [53]. The N2 adsorption ability of BiVO4 was
BVO, BVO-0.12C, BVO-0.18C and BVO-0.24C belonged to p-type
improved after it was hybridized with the carbon sphere in the range of
semiconductor, which suggests that the main charge carriers were
medium pressure zone (from 0.45 to 0.85 P/P0). The pore size dis-
holes. The photocurrents exhibited good reproducibility after four cy-
tribution is shown in the inset of Fig. 6, which indicates that the major
cles, which indicates that the samples had good stability. The transient
pore sizes were concentrated upon the range from 2 to10 nm, belonging
photocurrents were obviously enhanced with the presence of carbon
to mesopore scope. The specific surface area of BVO, BVO-0.18C and
sphere in the samples, suggesting that the separation efficiency of
carbon sphere was 4.811, 8.334 and 11.272 m2/g, respectively, which
photo-generated electrons and holes was improved via carbon sphere,
displays that the relationship between the adsorption performance and
which may lead to the enhancement of photocatalytic performance. In
the specific surface area of composites was not very distinct. It is ne-
Fig. 8b, EIS spectra of the samples BVO, BVO-0.12C, BVO-0.18C and
cessary to test the zeta potentials of the samples in this case.
BVO-0.24C are presented. It is found that the sample of BVO-0.12C
Zeta potentials were measured for the BVO, BVO-0.12C, BVO-0.18C
displayed the smallest arc radius in Nyquist plots but all of the com-
and BVO-0.24C in aqueous solution under neutral environment and the
posites showed smaller arc radius than pure bismuth vanadate, which
data are presented in Fig. 7, which reveals the variation of surface
reveals that the charge carriers were easier to transport in the samples
charges. As we can see, the zeta potentials became more negative after
after combined with the carbon sphere. This result will strongly support
BVO was combined with carbon sphere. The reason of this phenomenon
the photocatalytic phenomenon.
was mainly due to the generation of new binding mentioned in the XPS

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Fig. 8. (a) Transient photocurrent response and (b) EIS spectra of pure BVO and different BVO-C.

3.7. Uv–vis diffuse reflectance spectra 3.8. Photoluminescence (PL) spectra

Fig. 9a shows the UV–vis diffuse reflectance (DRS) spectra of BVO, The PL spectrum is often used to explore the recombination rate of
BVO-0.12C, BVO-0.18C and BVO-0.24C. It can be seen that the visible- photogenerated electrons and holes for a photocatalyst. The smaller the
light absorption ability for the samples was improved in the range of spectral intensity is, the lower the recombination rate of the photo-
500–800 nm after BVO was combined with carbon sphere. Whereas generated electrons and holes. The PL spectra of BVO/C composites are
there was no shift of the absorption edge, which suggests that there was shown in Fig. 10. There was a broad peak at 525 nm, which originated
no band energy change for BVO even after its hybridization with carbon from the recombination of the hole formed from the hybrid orbitals of
sphere. It displays that the improvement of photocatalytic performance Bi 6 s and O 2p (valence band) and the electron generated from V 3d
is not related to the band structure of the different composites. orbitals (conduction band) [55]. Moreover, the spectral intensity for the
In addition, the bandgap of the semiconductor can be calculated composites decreased after the samples were combined with carbon
according to the formula: sphere, which suggests that the recombination rate of photogenerated
electrons and holes was reduced. This result reveals that the carbon
αhv = A (hv−Eg )n/2 sphere could facilitate the transfer of photogenerated electrons due to
its good electronic conductivity and thus help to enhance the photo-
where α , h , v , A and Eg represents absorption coefficient, Planck con- catalytic performance, which is consistent with previous studies [56].
stant, light frequency, a constant and band gap, respectively. Besides, n
is decided by the type of semiconductor. When the semiconductor is
3.9. Photocatalytic activity
direct transition, n = 1. And n = 4 when it is indirect transition. n value
for BiVO4 is 1 [28]. The bandgaps of the samples were calculated by the
In order to test the photocatalytic property, MB and RhB were
plot of (αhv )2 versus energy (hv ) as shown in Fig. 9b. The value for BVO
chosen as the target pollutants. To study the MB and RhB degradation
and BVO-0.18C was 2.42 and 2.35 eV respectively, which means that
kinetics in the presence of BVO-C, the apparent reaction rate constant
the bandgap for the sample was slightly lower than that of pure bismuth
(−k) is calculated by using the following first-order reaction model:
vanadate after it was combined with carbon sphere. The narrowing of
the bandgap was ascribed to the chemical binding between BiVO4 and C
carbon sphere. It suggested that the composite can generate more ln ⎛ ⎞ = −kt
⎜ ⎟

⎝ C0 ⎠ (2)
electrons and holes under visible-light irradiation, resulting in its higher
photocatalytic performance [54]. where C0 and C is the concentration of MB or RhB at time 0 and t min

Fig. 9. (a) UV–vis absorption spectra of different samples and (b) plot of Kubelka-Munk transformation of BVO and BVO-0.18C.

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X. Wang et al. Applied Surface Science 453 (2018) 394–404

photocatalytic performance, which was mainly because of the prefer-


able adsorption performance and good electrochemical property men-
tioned above. With the excess addition of carbon sphere, many active
sites were covered and the binding between BVO and carbon sphere
decreased, leading to the declined performance. These results were in
accordance with the DRS result shown in Fig. 9a that the light ab-
sorption ability was the lowest for BVO-0.24C, which suggests that too
many carbon spheres would reduce light utilization for BVO. Besides,
the total organic carbon (TOC) was tested when the BVO and BVO-
0.18C were used to degrade MB as shown in Fig. S3, which suggests that
organic carbon in the dye was effectively removed. These two results
can reach a solid conclusion that BVO-0.18C shows much better pho-
tocatalytic performance than pure BVO.
In order to distinguish the prepared composite from the BVO and
carbon sphere mixture prepared by mechanical blend, the performance
comparison for the two different samples was tested as shown in Fig.
S4. Substantially, the sample BVO-0.18C displayed better photo-
catalytic performance. So, BVO-0.18C was not just the mechanical
Fig. 10. PL spectra for BVO, BVO-0.12C, BVO-0.18C and BVO-0.24C. mixture of pure BVO and carbon sphere.
Phenol was chosen to be another target pollutant to test the per-
formance of the samples in order to exclude dye sensitization effect
respectively [57]. The normalized reaction rate constant was calculated
under visible-light irradiation. The samples of BVO and BVO-0.18C
by normalizing k with the total mass of catalysts. The photodegradation
were used to photodegrade the phenol with the initial concentration of
result of MB and RhB is shown in Fig. 11. As we can see, the sample of
5 mg/L. Phenol concentrations were measured by high performance
BVO-0.18C showed the best performance for both MB and RhB photo-
liquid chromatography (HPLC). The results are shown in Fig. S5. The
degradation. Fig. 11b displays the apparent reaction rate constant (−k)
concentration of phenol decreased by 27.05% and 50.13% under
for MB photodegradation, which showed the value of −k for BVO-
visible-light irradiation for 5 h over the photocatalyst of BVO and BVO-
0.18C was 11.56 times higher than that for pure BVO. Moreover, the
0.18C respectively. The photodegradation efficiency of BVO-0.18C was
specific value was 4.42 times higher for RhB as shown in Fig. 11d. Thus,
almost 2 times as high as that of BVO, which suggests that the BVO-
with the presence of carbon sphere, the composites showed the better
0.18C indeed had the better photocatalytic performance than BVO.

Fig. 11. (a) and (b) Photodegradation of MB over different samples under visible light (λ > 420 nm); (c) and (d) photodegradation of RhB over different samples
under visible light (λ > 420 nm).

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Fig. 12. (a) Plots of active species trapped in the system of MB photodegradation over BVO-0.18C under visible light (λ > 420 nm) and (b) histogram of MB removal
efficiency.

The photogenerated electrons and holes have strong reduction and cycles respectively. It is mainly due to the reason that the dye molecules
oxidation capacities. The main active species of different photocatalysts adsorbed on the surface of the sample was not able to be removed
may vary due to their different energy band structure. CCl4, EDTA-2Na, completely in the cycle, resulted from the excellent adsorption perfor-
tert-butyl alcohol (TBA) and 1,4-benzoquinone (BQ) was used in this mance of the sample.
study as electron (e-), hole (h+), hydroxyl radical (%OH) and superoxide
radical (%O2−) scavenger, respectively [50,58–59]. The controlled ex- 3.10. Adsorption kinetics
periments for the photocatalytic degradation of MB over BVO-0.18C
with different scavengers under visible-light irradiation were performed Adsorption kinetics is often used to describe the adsorption rate and
and the results are shown in Fig. 12a. It can be found that the MB provide important information for adsorption mechanism. As we all
photodegradation was inhibited obviously with the presence of EDTA- know, the adsorption mechanism depends on the characteristics of
2Na (h+), which suggests that the holes were the main active species. adsorbent and mass transport process [61]. A couple of adsorption ki-
The photodegradation was also restrained when the TBA (%OH) and BQ netic models are employed to investigate the adsorption mechanism of
(%O2−) were added into the system, which indicates that %OH and %O2− MB over BVO-C and they are the pseudo-first-order and pseudo-second-
were also active species but not as active as the holes and thus they also order model, which are based on the difference in equilibrium ad-
played roles in the photodegradation system. In addition, the perfor- sorption capacity and adsorbed amount, and the assumption that rate-
mance was slightly enhanced with the addition of CCl4, which is elec- limiting step involves chemisorption, respectively [26,62]. The pseudo-
tron scavenger and can capture the photoelectrons. So, electron was not first-order and pseudo-second-order models are shown in Eqs. (3) and
responsible for the dye photodegradation. In conclusion, the holes were (4).
the main active species and the hydroxyl and superoxide radical con-
tributed to the dye photodegradation. This result is in agreement with ln(qe−qt ) = lnqe−k1 t (3)
previous studies. [43,60].
The recycle experiments were performed to evaluate the repeat- t 1 1
= + ∙t
ability and stability of BVO-0.18C under visible light irradiation for four qt k2 qe2 qe (4)
cycles. The results are shown in Fig. S6 with the target pollutants of MB −1
and RhB. As we can see, the MB and RhB photodegradation perfor- In these two equations, qe (mg·g ) means equilibrium adsorption
mance over BVO-0.18C decreased by 22.57% and 13.29% after four capacity, qt (mg·g−1) the adsorption capacity at t moment, k1 (min−1)
and k2 (min−1) the rate constant for pseudo-first-order kinetic model

Fig. 13. (a) Adsorption kinetic curves of MB onto BVO-C with different amount of carbon sphere (C0 is 20 mg/L MB solution; adsorbent concentration is 0.5 g/L), (b)
fitting curves by the pseudo-second-order model for MB adsorption onto BVO-C.

401
X. Wang et al. Applied Surface Science 453 (2018) 394–404

and pseudo-second order kinetic model respectively [63,64]. adsorption capacity [46]. Besides, it’s worth noting that BVO-0.18C
The adsorption kinetic curve of MB onto pure BVO, BVO-0.12C, showed a slightly better adsorption capacity than carbon sphere, which
BVO-0.18C, BVO-0.24C and carbon sphere are shown in Fig. 13a. The was mainly due to the binding between the BVO and carbon sphere
adsorption condition was that 0.05 g sample was dispersed in 100 mL mentioned above and the negative charges on the surface based on zeta
20 mg/L MB solution at room temperature. It can be found that the potential measurement. Both MB and RhB have positive charges, which
samples showed a fast adsorption in the first ten minutes and the ad- are beneficial for the adsorption onto the surface of the samples with
sorption rate gradually decreased with time, until reaching adsorption negative charges.
equilibrium after 100 min. The equilibrium adsorption capacity (qe,exp) The equilibrium adsorption capacity of BVO-0.18C and carbon
for pure BVO was quite low but that for the samples showed good ad- sphere with the same amount for RhB is shown in Fig. S9. The detailed
sorption property after hybridized with carbon sphere. It is worth data are shown in Table S1. It is found that the adsorption ability of
noting that BVO-0.18C had a superior adsorbability even than carbon BVO-0.18C for RhB was obviously weaker than that of carbon sphere.
sphere, which suggests that the binding between BVO and carbon This was mainly due to the reason that MB and RhB with different
sphere effectively enhanced the adsorbability. With the increase of molecular structure and surface functional groups led to the different
carbon sphere, BVO-0.24C showed weaker adsorbability than BVO- adsorption behavior. MB is easier to be adsorbed onto the samples
0.18C, which was mainly due to the agglomeration of excess carbon owing to its smaller molecular structure and more positive charges
sphere and the decreased binding between BVO and carbon sphere. [53].
Therefore, BVO-0.18C had the best ratio of BVO and carbon sphere,
which showed the best photocatalytic performance and adsorption 3.11. Mechanism
ability.
The adsorption data were fitted according to the pseudo-first-order The proposed mechanism is shown in Fig. 15. As we can see, the
and pseudo-second-order models as shown in Fig. S7 and Fig. 13b re- photocatalyst is consisted of BVO and carbon sphere. The electrons and
spectively. Fig. S7 displays the relationship between ln(qe-qt) versus holes were generated when the composite was illuminated under visible
time based on the pseudo-first-order, in which the slope means −k1 light. Carbon sphere has good electrical conductivity, which is bene-
(minus of rate constant) and the intercept the lnqe. The rate constant k1 ficial for the separation of photo-generated electrons and holes to
and qe,cal can be calculated based on the slope and intercept. While prolong the lifetime of carriers and thus improve photocatalytic per-
Fig. 13b shows the relationship between t/qt versus time based on the formance. Additionally, carbon sphere has excellent adsorption per-
pseudo-second-order, in which the slope stands for 1/qe and the inter- formance as well, which is conducive to pollutant adsorption onto the
cept 1/(k2qe2). The rate constant k2 and qe,cal can be calculated. The surface of the photocatalyst. This will facilitate the photodegradation of
detailed data are shown in Table 1. As we can see, the correlation the pollutants. Synergistic effect of photocatalysis and adsorption to
coefficients (R2) for all samples obtained from the pseudo-second-order remove the pollutants is distinctly shown for the case of the composite
model were closer to 1 than those from the pseudo-first-order model. BVO-C.
The qe,cal values obtained from the pseudo-second-order model perfectly
agreed with the experimental values of qe,exp, while those from the 4. Conclusion
pseudo-first-order model were much smaller than the qe,exp values. So,
the pseudo-second-order model was more suitable to describe the ad- A series of BVO-C composites are successfully synthesized by a facile
sorption behavior of the dyes onto the samples than the pseudo-first- hydrothermal method, which affords the photocatalysts with intimate
order model. The adsorption of MB onto the samples belonged to contact between BVO and carbon sphere. It is found that BVO-0.18C
physical adsorption. shows the best photocatalytic performance and good adsorption ability.
Furthermore, the effect of different initial concentration of MB on On one hand, carbon sphere has good adsorption property and elec-
the adsorption of MB onto BVO-0.18C and carbon sphere was tested and trical conductivity, which is conducive to the adsorption of pollutants
the data are shown in Fig. 14a and b respectively. It can be seen from and beneficial for the separation of photogenerated electrons and holes.
Fig. 14a that the adsorption rate of MB was high during the initial stage, On the other hand, BVO has photocatalytic performance under visible
then decreased, and finally equilibrium arrived after 100 min. During light. The combination of BVO and carbon sphere shows excellent or-
the adsorption process, the dye molecules rapidly reached the boundary ganic pollutant degradation performance with complementary ad-
layer by mass transfer, and then they slowly diffused from the boundary vantages, and the best sample BVO-0.18C far surpasses pure BVO by
layer to adsorbent surface, and finally diffused into the porous structure 11.56 times for MB degradation and by 4.42 times for RhB under
of the photocatalysts [62]. The detail data are shown in Table 2. Be- visible-light irradiation. Synergistic effect of photocatalysis and ad-
sides, the fitting plots by pseudo-first-order model and pseudo-second- sorption for organic pollutant removal is demonstrated for the case of
order model are shown in Fig. S8 for MB adsorption onto carbon sphere BVO-C. This study will provide a novel and facile way to treat organic
and BVO-0.18C. The equilibrium adsorption (qe) capacity increased pollutants by the combination of photocatalysis and adsorption.
with the increase of MB initial concentration for both BVO-0.18C and
carbon sphere. When the initial concentration of MB increased, the
Acknowledgments
driving force for mass transfer became strong and the interaction be-
tween MB and the adsorbent was enhanced, which resulted in a higher
This work was supported by the National Natural Science

Table 1
Pseudo-first-order and pseudo-second-order kinetic parameters for MB adsorption onto BVO, BVO-C and carbon sphere.
Pseudo-first-order model Pseudo-second-order model

-1 2
qe,exp (mg/g) qe,cal (mg/g) k1 (min ) R qe,cal (mg/g) k2 (min-1) R2

BVO 16.5428 0.9328 0.0168 0.7793 16.6417 0.1624 0.9999


BVO-0.12C 25.8125 3.6844 0.0246 0.9537 25.7865 0.0364 0.9997
BVO-0.18C 28.5954 7.5030 0.0416 0.9099 28.7356 0.0216 0.9994
BVO-0.24C 22.5431 2.3736 0.0252 0.7763 22.4316 0.0605 0.9996
C 26.8793 7.3483 0.0354 0.9606 27.1150 0.0180 0.9991

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X. Wang et al. Applied Surface Science 453 (2018) 394–404

Fig. 14. (a) Adsorption capacity of BVO-0.18C and (b) carbon sphere in MB solution with different concentration. (Adsorbent concentration is 0.5 g/L and tem-
perature is 298 K).

Table 2
Pseudo-first-order and pseudo-second-order kinetic parameters for the adsorption of MB with different concentration onto BVO-0.18C and carbon sphere.
Pseudo-first-order model Pseudo-second-order model

CMB (mg/L) qe,exp (mg/g) qe,cal (mg/g) k1 (min-1) R2 qe,cal (mg/g) k2 (min−1) R2

BVO-0.18C 10 19.7170 7.1622 0.0346 0.9042 19.5351 0.0112 0.9965


20 29.7776 8.8729 0.0306 0.7634 30.0391 0.0164 0.9994
30 38.0862 6.2564 0.0322 0.7603 38.0807 0.0183 0.9997
40 49.5841 8.0830 0.0332 0.7690 49.3827 0.0145 0.9994

C 10 15.1093 4.5071 0.0244 0.9752 15.2346 0.0246 0.9979


20 24.2576 4.9042 0.0276 0.9794 24.3368 0.0269 0.9995
30 36.0393 5.8576 0.0309 0.9907 36.3504 0.0209 0.9995
40 44.7833 6.5445 0.0288 0.9305 44.9640 0.0198 0.9996

Fig. 15. Photodegradation and adsorption mechanism of MB and RhB on the surface of BVO-C composite.

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