ORIGINAL RESEARCH

published: 08 December 2021

doi: 10.3389/fchem.2021.797738

Photocatalytic Removal of Antibiotics

on g-C3N4 Using Amorphous CuO as
Cocatalysts
Yue Zhao 1,2, Amir Zada 3, Yang Yang 4, Jing Pan 2, Yan Wang 5, Zhaoxiong Yan 1*, Zhihua Xu 1*
and Kezhen Qi 1,5*
1
Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education, and Hubei Key Laboratory of
Industrial Fume and Pollution Control, Jianghan University, Wuhan, China, 2College of Life Science, Shenyang Normal University,
Shenyang, China, 3Department of Chemistry, Abdul Wali Khan University Mardan, Mardan, Pakistan, 4College of Physical Science
and Technology, Shenyang Normal University, Shenyang, China, 5Institute of Catalysis for Energy and Environment, College of
Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang, China

Amorphous CuO is considered as an excellent cocatalyst, owing to its large surface area
and superior conductivity compared with its crystalline counterpart. The current work
demonstrates a facile method to prepare amorphous CuO, which is grown on the surface
of graphitic carbon nitride (g-C3N4) and is then applied for the photocatalytic degradation
of tetracycline hydrochloride. The prepared CuO/g-C3N4 composite shows higher
Edited by:
Tingjiang Yan, photocatalytic activities compared with bare g-C3N4. Efficient charge transfer between
Qufu Normal University, China g-C3N4 and CuO is confirmed by the photocurrent response spectra and
Reviewed by: photoluminescence spectra. This work provides a facile approach to prepare low-cost
Xiufang Chen,
Zhejiang Sci-Tech University, China
composites for the photocatalytic degradation of antibiotics to safeguard the environment.
Deli Jiang,
Keywords: amorphous CuO, cocatalysts, photocatalytic degradation, tetracycline hydrochloride, g-C3N4
Jiangsu University, China

*Correspondence:
Zhaoxiong Yan INTRODUCTION
zhaoxiongyan75@163.com
Zhihua Xu
The release of a great deal of different refractory antibiotics applied for the diseases of animal therapy,
xuzhihua78@sina.com
Kezhen Qi
as well as for crop production into the natural water bodies by municipal and pharmaceutical
qkzh2003@aliyun.com industries, is considered to be a concerning issue over the past few years. The incomplete metabolism
of antibiotics results in the excessive accumulation of these compounds in the ground and on the
Specialty section: surface of water bodies to cause strong drug toxicity and reduces the efficiency of life-saving
This article was submitted to medicines. Their long persistence in ground water has led to the generation of serious antibiotic-
Catalysis and Photocatalysis, resistant microbiota, which is a major threat to human existence. Therefore, it is extremely important
a section of the journal to dispose these antibiotics from the bodies of ground water before they cause severe damage to
Frontiers in Chemistry human beings and aquatic animals.
Received: 19 October 2021 Traditional methods used for removing pollutants and antibiotics are no longer effective to ensure
Accepted: 01 November 2021 the safety of water. Photocatalysis (Yan et al., 2020a; Yan et al., 2020b; Zhang H. et al., 2021; Li et al.,
Published: 08 December 2021
2021; Zhu et al., 2021), a green technology has recently shown exceptional performance in the
Citation: photodegradation of a large number of organic pollutants (Khaledian et al., 2019; Liu et al., 2019; Yan
Zhao Y, Zada A, Yang Y, Pan J, et al., 2019; Gholami et al., 2020; Zhang et al., 2020). As a polymeric semiconductor photocatalyst,
Wang Y, Yan Z, Xu Z and Qi K (2021)
graphitic carbon nitride (g-C3N4) has shown outstanding performance and is widely favored due to
Photocatalytic Removal of Antibiotics
on g-C3N4 Using Amorphous CuO
its low toxicity, high chemical and thermal stability, and low-cost precursor materials (Wen et al.,
as Cocatalysts. 2017a; Qi et al., 2020b; Di et al., 2020; Shi et al., 2020; Wu et al., 2020). Its moderate band gap and
Front. Chem. 9:797738. suitable conduction band (CB) and valance band (VB) positions are extremely important to produce
doi: 10.3389/fchem.2021.797738 highly active reactive oxygen species (ROS) under solar light irradiation for the effective removal of

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

antibiotics from water (Zada et al., 2020). However, its low

utilization of sunlight and high charge recombination
characteristics are responsible for its low photocatalytic activity
and low removal efficiency of organic pollutants (Hao et al., 2020;
Wang et al., 2021). It is urgently needed to introduce the
photocatalysts with improved photocatalytic activity to address
water pollution.
Transition metal oxides are extremely promising materials for
semiconductor photocatalysts (Zhang G. et al., 2021; Shan et al.,
2021). Especially, CuO is very important due to its high
abundance, low cost, non-toxic property, high intrinsic
thermal safety, and environmental benignity. CuO is a p-type
semiconductor with a narrow band gap between 1.2 and 1.5 eV
(Liu et al., 2014). It has received much attention for its extensive
applications in gas sensors, solar photovoltaics, and as a
heterogeneous catalyst. It is well known that amorphous metal
oxides or metal sulfides are superior to their crystalline
counterparts as they possess the advantage of lower synthesis
temperature, simpler synthesis process, and larger specific area. FIGURE 1 | X-ray diffraction (XRD) patterns of graphitic carbon nitride
Moreover, a number of previous studies have highlighted its (g-C3N4) and CuO/g-C3N4 samples.
excellent hole/electron mobility in comparison to its crystalline
counterpart, such as amorphous MoSx, NiS, Co3O4, etc. (Yuan
et al., 2015; Wen et al., 2017b; Yu et al., 2019). Amorphous vigorous stirring for 30 min. A given mass of Cu(NO3)2·H2O was
materials are considered to possess excellent redox centers in bulk added, and stirring continued for another 30 min. Two milliliters
on the surface to process highly efficient photocatalysis compared of ammonia was added to the mixture, and the mixture was then
with its crystalline form. Although the band gap of amorphous placed in a stainless steel autoclave at 120°C for 4 h. The naturally
CuO is slightly larger than that of the crystalline CuO, its excellent cooled mixture was centrifuged and washed three times with
charge conductivity and superior surface area play an extremely distilled water to remove any impurities. It was then dried at 80°C
positive role in the photocatalytic processes (Huang et al., 2015). in an oven overnight and calcined at 200°C for 1 h. The samples
Thus, it is of much interest to fabricate composite photocatalysts were represented as X%-CuO/g-C3N4 where “X%” stands for the
with amorphous CuO as cocatalyst for improving the percentage of amorphous CuO in the mixture.
performance of photocatalysis.
In this work, a photocatalyst composed of amorphous CuO Characterization
and g-C3N4 was fabricated utilizing a facile method, which The crystal structure of the fabricated samples was examined by
involved heating melamine in a muffle furnace and then x-ray diffraction (XRD) utilizing the Bruker D8 Advance
growing different mass percent ratios of amorphous CuO. The Diffractometer with Cu-Kα radiation. The Fourier transform
fabricated samples showed enhanced photodegradation activities infrared (FT-IR) spectra were obtained utilizing the Nicolet
for the removal of tetracycline hydrochloride antibiotics. The Magna 560 spectrophotometer to investigate the functional
improved photocatalytic performance of CuO/g-C3N4 was groups. ESCALAB MKII x-ray photoelectron spectrometer
attributed to the extended visible light absorption and with Mg-Kα radiation was employed to evaluate the chemical
enhanced charge separation after the growth of amorphous states of the elements, and the binding energies were calibrated
CuO as cocatalysts on the surface of g-C3N4. Finally, a with the binding energy of the adventitious carbon. Transmission
possible photocatalytic mechanism was proposed based on the electron microscopic (TEM) images of the samples were acquired
experimental results. This work provides an effective method for with JEM-2010 apparatus. The ultraviolet-visible diffused
the design of a high-efficiency photocatalyst using amorphous reflectance spectra (UV-vis DRS) were measured with UV-
cocatalysts. 3600, Shimadzu spectrophotometer with an integrating sphere
attachment. The photoelectrochemical study was conducted with
an IVIUM V13806 electrochemical workstation.
EXPERIMENTAL SECTION
Evaluation of Photocatalytic Performance
Synthesis The photocatalytic activities of the different samples were
For the preparation of g-C3N4, 20 g of melamine was ground and evaluated from the photodegradation of tetracycline
transferred to a 100-ml crucible. The crucible was closed and hydrochloride antibiotics. Fifty milligrams of the given
heated in a muffle furnace at 520°C for 4 h at the rate of 2°C/min. antibiotic was dissolved in 1,000 ml of water. Fifty millilters of
The amorphous CuO with different mass percentage ratios was the respective solution was placed into a photochemical reactor
grown on the surface of g-C3N4 by dispersing 0.21 g of g-C3N4 in made of quartz and mixed with 0.2 g photocatalyst. The mixture
20 ml of solvent (10 ml of ethanol and 10 ml of water) under was first stirred in the dark for 30 min to attain adsorption/

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

FIGURE 2 | Ultraviolet-visible diffused reflectance spectra (UV-Vis DRS) of g-C3N4 and 7%-CuO/g-C3N4 samples.

desorption equilibrium between the adsorbed and unadsorbed the surface of g-C3N4, the light absorption was slightly
antibiotic molecules. It was then illuminated with a 500-W Xe increased, and the absorption wavelength was shifted slightly
lamp for 2 h at a wavelength of over 365 nm. After every interval toward the higher wavelength side. Compared with g-C3N4, the
of 20 min, 5 ml of the liquid portion was centrifuged, and the absorption edge of 7%-CuO/g-C3N4 was shifted to 479 nm at
concentration of the antibiotics was examined with a UV-Vis 2.59 eV. The red shift results from the mixing of the electron
spectrophotometer (UV-3600, Shimadzu) at 357-nm wavelength. orbitals of CuO and g-C3N4. The 7%-CuO/g-C3N4 sample shows
The photoluminescence (PL) spectra were obtained by a Varian a broad shoulder peak ranging from 600 to 800 nm because of the
Cary Eclipse spectrometer. d-d transition between the energy levels of Cu2p orbital (Qi et al.,
2020c). The above result concludes that CuO has been
successfully loaded on the surface of g-C3N4. The light
RESULTS AND DISCUSSION absorption property of g-C3N4 has been increased after the
loading of CuO. Thus, more visible light photons can be
X-Ray Diffraction Analysis utilized by CuO/g-C3N4 for enhanced photoactivity.
The XRD patterns of the as-prepared samples are given in
Figure 1. The g-C3N4 has two characteristic diffraction peaks, Transmission Electron Microscopy Analysis
one at 13.02° and the other at 27.3°, which agrees well with the TEM measurement is an effective method to study the structural
standard pattern of g-C3N4 (JCPDS87-1,526) (Yang et al., 2013). properties of 7%-CuO/g-C3N4. Figure 3A presents the TEM
The peak at 13.02° is due to the inter-planar staking units of the image of 7%-CuO/g-C3N4 with thin multilayered structures.
aromatic system in conjugation, and the peak at 27.3° is due to the When CuO was grown on its surface, the layered structure of
inter-layer structural packing units (Qi et al., 2019d; Qi et al., g-C3N4 still persisted, and its morphology showed no detectable
2020a). These peaks are indexed to (100) and (002) crystal planes changes due to a low synthesis temperature approach
corresponding to a distance of 0.675 and 0.324 nm, respectively (Figure 3B). The absence of the lattice fringes of CuO in the
(Li et al., 2014; Qi et al., 2019c). After growing CuO on g-C3N4, no composite is an indication that CuO is amorphous. The elemental
obvious peak of CuO was detected, indicating its amorphous mapping of the sample suggests the presence of C, N, O, and Cu
nature. The intensity of the inter-planar staking peak of g-C3N4 in the composite. The distribution of both Cu and O shows that
has been reduced slightly, which shows the uniform distribution these elements are uniformly and homogeneously grown on the
of amorphous CuO on the surface of g-C3N4. surface of g-C3N4, as shown in Figures 3C–G. EDS spectrum
(Figure 4) demonstrates that C, N, Cu, and O elements are evenly
distributed on the 7%-CuO/g-C3N4 sample. Additionally, the
Ultraviolet-Visible Diffused Reflectance existence of CuO was further verified with EDS spectra.
Spectra Analysis
The light absorption properties of the samples were investigated Fourier Transform-Infrared Analysis
by UV-Vis DRS (Figure 2). The g-C3N4 absorbs the light photons The FT-IR spectra were obtained to investigate the functional
with a wavelength of 470 nm and gives a direct band gap of groups in the fabricated samples, and the results are shown in
2.64 eV, which is consistent with the previous report (Ong et al., Figure 5. The peak at 802 cm−1 is attributed to the breathing
2015; Qi et al., 2021). CuO has a narrow band gap of lower than mode of triazine rings of g-C3N4 (Zhu et al., 2017; Huo et al.,
1.5 eV, which means a strong visible light absorption ability 2019). The FT-IR peaks between 1,231 and 1,620 cm−1 are
(Verma et al., 2019). When amorphous CuO was grown on accredited to the C-N stretching mode of the aromatic ring,

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

FIGURE 3 | (A) Transmission electron microscopy (TEM) and (B) HRTEM images of 7-%CuO/g-C3N4, and (C–G) corresponding elemental mapping showing the
distribution of C, N, Cu, and O.

FIGURE 4 | EDS spectrum of 7-%CuO/g-C3N4.

and these originate from C≡N stretching modes (Dai et al., 2014; ring (Cao et al., 2017; Qi et al., 2020d). These peaks are slightly
Li et al., 2017). A broader peak at 3,121 cm−1 is attributed to the reduced in their intensities when amorphous CuO was grown on
stretching vibrational mode of the –NH group of the aromatic g-C3N4. The FT-IR results indicate that the structure of g-C3N4

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

55% for 7%-CuO/g-C3N4. The apparent reaction rate constant (k) is

calculated in the photocatalytic degradation of tetracycline
hydrochloride (Figure 7B). The kinetic constant of 7%-CuO/
g-C3N4 (0.014 min−1) is almost three times higher than that of
g-C3N4 (0.005 min−1). The improved photocatalytic activity is
related to the extended visible light absorption and improved
charge separation due to the introduction of amorphous CuO
on the surface of g-C3N4. Another important role of CuO is
acting as an oxidation cocatalyst, which promotes the
separation and transport of holes and improves the oxidation
ability of the photocatalyst.

Electrochemical Analysis
The measurement of transient photocurrent against time during
photoelectrochemical measurement was used to study the charge
separation for photocatalysis. The photocatalysts were deposited
on the surface of indium-doped tin oxide glass and were used as
FIGURE 5 | Fourier transform-infrared (FT-IR) spectra of g-C3N4 and the working electrode, while Ag/AgCl and platinum were used as
7%-CuO/g-C3N4 samples. the reference electrode and counter electrode, respectively. The
electrolyte solution was composed of 0.1 M KCl. The greatly
improved photocatalytic activity of the optimized 7%-CuO/
remained unchanged after the loading of CuO. This means that g-C3N4 sample was attributed to the excellent charge
CuO has been well combined with g-C3N4, which is consistent separation in the given composite. The photocurrent response
with the XRD result. spectra were obtained, as shown in Figure 8. The 7%-CuO/
The surface chemical states of the elements in the g-C3N4 shows enhanced photocurrent compared with pure
composite were determined by XPS measurement. The XPS g-C3N4, which suggests that charge recombination has been
results demonstrate that the 7%-CuO/g-C3N4 sample contains quenched in the given sample to impart excellent
C, N, Cu, and O elements as shown in Figure 6A. High- photocatalytic activity. The photocurrent response spectra
resolution XPS spectrum of carbon is shown in Figure 6B. show that the interface of amorphous CuO and g-C3N4 favors
Carbon shows two binding energy peaks at 284.6 and the charge transfer and separation in the composite, indicating its
287.6 eV, which are attributed to the sp2-hybridized important role in the photocatalytic process.
C-atom bonded to the N-atom of the aromatic ring and
NH2 group, respectively (Hayat et al., 2019; Wu et al., Photoluminescence Analysis
2015). The binding energy peaks of the N-atom are located In order to show the enhanced charge separation in the
at 398.2, 400.1, and 403.8 eV (Figure 6C). The former two fabricated CuO/g-C3N4 composite, PL spectra were obtained,
peaks are due to the CN-C and N-(C)3 , respectively, while as shown in Figure 9. As can be observed, an emission peak of
the last peak is attributed to the π–π* satellite (Lin et al., 2015; g-C3N4 is located at 460 nm, which agrees with the previous
Qi et al., 2019a). The binding energy peak at 932.6 eV with a results (Liu and Ma, 2020; Zhang M. et al., 2021). The intensity
satellite peak at 942.8 eV is attributed to the Cu2p3/2 , and the of PL peak is high in case of g-C3N4, which shows poor charge
peak at 952.6 eV with a satellite peak at 962.8 eV is due to the separation. However, when amorphous CuO was grown over
Cu2p1/2 of Cu2p (Figure 6D) (Shen et al., 2018). The XPS g-C3N4, the PL intensity was significantly reduced. Since the PL
peaks of the O-atom are located at 530.4, 531.3, and 532.4 eV peak is low, charge separation is high (Lu et al., 2017; Qi et al.,
(Figure 6E), which are attributed to the O-atom of the crystal 2019b). The lower PL signal shown by the 7%-CuO/g-C3N4
lattice of CuO and O-atom of adsorbed water molecules, composite is due to the adsorption of amorphous CuO on
respectively (Qi et al., 2018). The obtained XPS data g-C3N4 surface that extends the internal charge
indicate that CuO has been effectively coupled with g-C3N4 . transformation and decreases the charge recombination
between the excited e– and h+. This has increased the lifetime
Photocatalytic Activity of working charges to result in increased reaction time. It is
The photocatalytic activities of the as-prepared CuO/g-C3N4 concluded that the optimized composite is suitable for
composites were evaluated by selecting tetracycline hydrochloride enhancing the photocatalytic degradation of antibiotics due
antibiotic for degradation under the irradiation from simulated to an enhanced charge separation.
solar light (λ > 365 nm). From Figure 7A, the photocatalytic
activity of g-C3N4 is very low due to poor charge separation. Photocatalytic Mechanism
When amorphous CuO was grown on the surface of g-C3N4, the The photocatalytic degradation of antibiotics over amorphous
photocatalytic activities were improved, and the degradation efficiency CuO-coupled g-C3N4 has been discussed in detail. The charge
increased as the amount of CuO increased. After reaction for 60 min, separation and transformation are illustrated in Figure 10. When
the degradation of tetracycline hydrochloride is 24% for g-C3N4 and irradiated with light, the electrons are promoted to the CB of

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

FIGURE 6 | X-ray photoelectron spectroscopy (XPS) spectra of 7%-CuO/g-C3N4: survey scan (A), C1s (B), N1s (C), Cu2p (D), and O1s (E).

FIGURE 7 | Photoactivities for the decomposition of tetracycline hydrochloride using g-C3N4 and CuO/g-C3N4 as photocatalysts.

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

FIGURE 10 | Schematic representation of charge generation and

separation in CuO/g-C3N4 for the degradation of tetracycline hydrochloride.

FIGURE 8 | Photocurrent response signals of 7%-CuO/g-C3N4.

CONCLUSION
In conclusion, the amorphous CuO with excellent charge
conductivity was loaded on the surface of g-C3N4 to form a
composite and then applied for the photodegradation of
tetracycline hydrochloride antibiotic. The prepared CuO/g-C3N4
composites show enhanced photocatalytic activities compared with
the bare g-C3N4. It has been found that the g-C3N4 loaded with
CuO shows the considerably positive effect for charge transfer in
the composites. This work provides a facile and feasible approach
for the preparation of low-cost composites for the photocatalytic
degradation of antibiotics to safeguard our environment.

DATA AVAILABILITY STATEMENT

The original contributions presented in the study are included in
the article/supplementary material. Further inquiries can be
directed to the corresponding authors.

FIGURE 9 | Photoluminescense (PL) spectra of g-C3N4 and 7%-CuO/

g-C3N4 samples. AUTHOR CONTRIBUTIONS
YZ conducted the catalysts preparation. AZ performed the activity
test. YY, JP, and YW discussed the mechanism part. ZY, ZX, and
g-C3N4, leaving positive holes in the VB. The generated electrons KQ conceived the project and co-wrote the manuscript.
in the CB easily transfer to the g-C3N4 surface, in which the
electrons can reduce the adsorbed O2 molecules to form super
oxide anions (•O2−), which either directly reacts with antibiotic FUNDING
molecules. At the side of the VB, when p-type semiconductor
CuO was closely attached on the n-type semiconductor of This work was supported by the Opening Project of Key
g-C3N4, the p–n junction was formed at the interface of CuO Laboratory of Optoelectronic Chemical Materials and Devices
and g-C3N4 (Belaissa et al., 2016; Hua et al., 2019). Thus, the inner of Ministry of Education, Jianghan University (JDGD-202022),
electric field in the p–n junction promotes the transfer of holes National Natural Science Foundation of China (21871111,
from the VB of g-C3N4 to CuO, and these holes oxidize the water 22075186, 21975164) and Excellent Youth Foundation of
to produce hydroxyl radicals (•OH) to degrade the antibiotics. Hubei Province of China (2019CFA078). Education Office of
Thus, the CuO/g-C3N4 composite shows an improved Liaoning Province (LJKZ0997), Liaoning Revitalization Talents
photocatalytic performance for the decomposition of organic Program (XLYC1807238), Liaoning BaiQianWan Talents
pollutants. Program (2020921111).

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Zhao et al. Amorphous CuO Modified g-C3N4 Photococatalysts

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