Chemical Engineering Journal 392 (2020) 123767

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Chemical Engineering Journal

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Photocatalytic inactivation of harmful algae and degradation of cyanotoxins T

microcystin-LR using GO-based Z-scheme nanocatalysts under visible light
Gongduan Fana,b,c, , Liang Honga, Jing Luod, Yifan Youa, Jin Zhange, Pei Huaf, Banghao Dua,
⁎

Jiajun Zhana, Rongsheng Ninga, Minchen Baoa

a
College of Civil Engineering, Fuzhou University, 350116 Fujian, China
b
State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, 350002 Fujian, China
c
Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, Fuzhou University, 350002 Fujian, China
d
Fujian Minke Environmental Technology Development Co. Ltd., 350002 Fujian, China
e
Institute of Groundwater and Earth Sciences, Jinan University, 510632 Guangdong, China
f
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental
Theoretical Chemistry, South China Normal University, 510006 Guangdong, China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Three visible-light-driven GO-based Z-

scheme photocatalysts were synthe-
sized.
• Photocatalysts were used to simulta-
neously remove algae and photo-
degrade MC-LR.
• Kinetics, path and mechanisms in the
photodegradation process of MC-LR
were studied.
• Effects and mechanisms of harmful
algae inactivation by Ag CO -GO were
2 3
investigated.

ARTICLE INFO ABSTRACT

Keywords: Three kinds of GO-based Z-scheme photocatalytic materials were synthesized to remove harmful algae and
Z-scheme photocatalysts Microcystins-LR (MC-LR). The physicochemical properties of the photocatalysts were characterized. The in-
Graphene oxide hibitory effects of three photocatalysts on the growth of algae under visible light were compared. The photo-
Microcystis-LR catalytic degradation pathways and mechanism of MC-LR by Ag2CO3-GO were proposed. The results showed
Harmful algae
that the combination modes and morphology size of GO-based Z-scheme photocatalysts had grade effects on the
Photocatalytic degradation
Visible light
degradation of MC-LR. Ag2CO3-GO exhibited the best photocatalytic activity among these GO-based Z-scheme
photocatalysts, which could remove nearly 100% MC-LR (0.3 mg/L) within 1 h under visible light. The de-
gradation rate of MC-LR by Ag2CO3-GO fit well with the pseudo-first-order kinetic model and was significantly
influenced by pH. The degradation of MC-LR by Ag2CO3-GO was also inhibited by the alkalinity, DOM, H2O2,
and the coexistence of algae cells. The experimental results showed that ·OH and O2- played the main role in the
photocatalysis of MC-LR by Ag2CO3-GO, and the Adda side chain and peptide ring in MC-LR were gradually
oxidized, indicating that the biological toxicity of MC-LR was gradually lost during the degradation process.
Besides, 100 mg/L of Ag2CO3-GO could obviously inhibit the growth of harmful algae, which could oxidize and
damage algae cells, and further degrade their released contents under visible light, thus avoiding the secondary

⁎
Corresponding author at: College of Civil Engineering, Fuzhou University, 350116 Fujian, China.
E-mail address: fgdfz@fzu.edu.cn (G. Fan).

https://doi.org/10.1016/j.cej.2019.123767
Received 15 August 2019; Received in revised form 6 December 2019; Accepted 8 December 2019
Available online 16 December 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
G. Fan, et al.
pollution effectively. In summary, GO-based Z-scheme photocatalysts have a promising future for the in-
activation of harmful cyanobacteria and degradation of MC-LR.
1. Introduction
In recent years, as the eutrophication in aquatic environment has
become more and more prominent, harmful cyanobacteria blooms have
attracted worldwide attention [1]. Among them, Microcystis aeruginosa
is the most representative toxic and harmful algae in natural water
body, and their uncontrolled growth and reproduction in eutrophic
environment have caused adverse impacts on the appearance and smell
of waters [2]. In addition, toxins with hepatotoxicity and neurotoxicity,
as well as some of the algae metabolites that cause the smell and taste of
water, are produced constantly as algae grow, posing a great threat to
the ecological environment and living organisms, including human
beings [3]. Microcystin-LR (MC-LR), as the main metabolite of toxic
and harmful algae [4], has been widely concerned by scholars around
the world because of its wide distribution, strong toxicity, and high
content (46.0–99.8% of the total MC of cyanobacteria bloom [5]. As
issued by World Health Organization (WHO), the provisional limit
concentration of MC-LR for drinking water is 1 μg/L [6]. At present, the
methods for controlling harmful algal blooms in eutrophic water mainly
include physical, chemical, and biological methods. Fan et al. [7,8] has
found that 40 kHz ultrasound at 0.02 W/m can effectively inhibit the
growth of Microcystis aeruginosa. According to Guo et al. [9], Cu2+ can
effectively block the gene expression and transcription of Spirulina
Annulata, thus leading to cell death. Besides, it has been reported by
Yuan et al. [10] that the growth of Scenedesmus could be inhibited by
the genera of bitter algae (e.g., Ceratophyllum and Myriophyllum).
However, the practical applications of these technologies are limited
due to the shortcomings of the above algae removal technologies, such
as low efficiency, high cost, and the potential secondary pollution. In
addition, the molecular structure of MC-LR contains loop structure (D-
Ala-XD-MeAsp-Z-Adda-D-Glu-Mdha) and specific amino acid [11],
which makes MC-LR quite stable in the aquatic environment. Therefore,
traditional water treatment processes such as chlorine dosing [12],
potassium permanganate dosing [13], ultrasonic treatment [14], fil-
tration [15], and adsorption [16] cannot effectively and ideally remove
MC-LR and algae. Therefore, it is urgent to find a novel technology to
remove both algae and MC-LR from algal blooms waters.
Nano-materials are widely applied in environmental treatment be-
cause of their high activity, low cost, and strong adsorption capacity
[17,18]. Recently, nano-silver composites have gained popularity for
the better photoresponse ability and remarkable catalytic capability
[19–21]. Various nano-silver catalysts, such as silver halides (AgX,
X = Cl, Br, I), silver-containing oxides, and salts (Ag3PO4, Ag2CO3,
Ag2CrO4, AgGaO2, Ag2MO3O7, and Ag2O) [19,22,23] are extensively
used in the photocatalytic removal of toxic and harmful substances in
the aquatic environment. According to the physiological properties of
algal cells which are sensitive to Ag+ and Cu2+ and the excellent
photoresponse ability of nano-silver compounds, the removal of algae
blooms and their metabolites (MC-LR) by nano-silver compounds has
been studied. Park et al. [24] found that the inhibitory efficiency of
Microcystis aeruginosa by silver nanoparticles (1 mg/L) could reach
87%. According to Qiang et al. [25], 94.4% MC-LR (5 mg/L) could be
removed efficiently within 10 h by 500 mg/L Ag3PO4/NG/PI compo-
site. However, there are some limitations in the response ability of
silver nanoparticles to visible light. The silver nanoparticles are prone
to photochemical corrosion under visible light irradiation, further
limiting the promotion and recycle of nano-silver catalysts [25,26]. In
order to improve the visible light response of the nano-silver catalysts
and avoid their photochemical corrosion problems, it is feasible to
combine the nano-silver catalysts with a series of semiconductor
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Chemical Engineering Journal 392 (2020) 123767
materials (such as g-C3N4, GO, and RGO et al.) [27–30], which exhibit
good conductivity to form heterojunction, improving the photocatalytic
activity and stability of nano-silver catalysts.
Graphene oxide (GO) is an ideal material for the transfer and re-
ception of photoelectrons due to its large specific surface area (SSA),
good thermochemical stability, and excellent charge transfer ability
[31]. Based on the photocatalysis mechanism of Z-scheme, the nano-
silver composite materials made by combining GO with nano-silver
catalysts have been gradually applied to water treatment. According to
Li et al. [32] study, 86% methyl orange (20 mg/L) could be degraded by
GO (0.5%)/Ag2CO3 within 2 h. Liu et al. [33] found that the de-
gradation efficiency of rhodamine B could reach almost 100% within
100 min with a certain dosage of Ag3PO4@GO (10%) under visible
light. At present, the researches on the application of GO@nano-silver
photocatalysts in water treatment mostly involve the removal of small
molecular pollutants such as dyes and phenols. However, the removal
of harmful algae and their toxic metabolites (MC-LR) in algal blooms
waters are poorly studied. Furthermore, the combination way of GO@
nano-silver photocatalyst, the influence of its structure and morphology
on its photocatalytic performance, the effects and influencing factors of
GO@nano-silver photocatalyst on the removal of algal cells and their
metabolites (such as MC-LR), as well as the degradation kinetic analysis
and mechanism are still unclear.
Consequently, based on the physiological characteristics of algae
which are sensitive to Ag+, three kinds of Z-scheme materials under the
GO system, i.e., Ag2CO3-GO (1%), Ag3PO4-GO (1%) and Ag2CrO4-GO
(1%), were synthesized by a facile precipitation method. The compo-
sition, structure, morphology, combination ways, and photocatalytic
properties of synthesized photocatalysts were characterized by X-ray
diffraction (XRD), scanning electron microscope (SEM), X-ray photo-
electron spectroscopy (XPS), and UV–vis spectra, respectively. The ef-
fects of environmental factors such as dosage of Ag2CO3-GO (1%), in-
itial concentration of MC-LR, alkalinity, types and concentrations of
DOM, pH, content of H2O2, and coexistence of algal cells on MC-LR
degradation were investigated. Moreover, the mechanism of the pho-
tocatalytic inhibition of algae and the photodegradation of MC by
Ag2CO3-GO (1%) were proposed, providing theoretical basis and tech-
nical support for the application of GO system nano-silver photo-
catalysts in the removal of toxic and harmful algae and their metabo-
lites (MC-LR) from aquatic environment.
2. Methods and materials
The types and purity of materials and reagents used in this study can
be found in Text S1.
2.1. Preparation of GO Z-scheme materials
2.1.1. Synthesis of GO
The GO was synthesized via a simple precipitation method ac-
cording to Xu et al.[26]. Briefly, 2.5 g K2S2O8 and 2.5 g P2O5 were
added into 15 mL of concentrated H2SO4 to give solution A. Then, 3 g
graphite were added to solution A followed by heating to 80 °C under
stirring condition for 8 h to obtain solution B. After cooling the solution
B down at room-temperature and diluting with 500 mL of ultra-pure
water, the obtained black composite was filtered by 0.22 µm filtering
membrane and dried under 60 °C. At last, 80 mg of graphite oxide were
dissolved in 80 mL ultra-pure water and then 1.0 mg/mL graphite oxide
solution was obtained after 2 h ultrasonic treatment.
G. Fan, et al.
2.1.2. Synthesis of Ag2CrO4-GO (1 wt%)
Typically, 1.02 g AgNO3 was dissolved in 100 mL of ultra-pure
water to give AgNO3 solution with a concentration of 0.06 mol/L. After
that, 10.06 mL of prepared GO aqueous suspension (1 g/L) was added
into AgNO3 solution and stirred for 12 h to obtain solution C. 100 mL of
0.03 mol/L K2CrO4 was added dropwise into solution C and stirred 1 h.
Finally, being 4 h treating at room-temperature, and after the cen-
trifugation, a brick-red composite was synthesized. Then through
washing the composite by the ultra-pure water for five times, and
drying 6 h at 80 °C, the Ag2CrO4-GO was successfully synthesized.
2.1.3. Synthesis of Ag2CO3-GO (1 wt%)
8.36 mL of GO aqueous suspension (1 g/L) was added into AgNO3
solution (0.006 mol/L) and kept 12 h stirring to obtain solution D. Next,
100 mL of Na2CO3 solution (0.03 mol/L) was added dropwise into so-
lution D and stirred for 1 h. Being 4 h treating at room-temperature, and
after the centrifugation, a light grey composite was synthesized. Then
through washing the composite by the ultra-pure water for five times,
and drying 6 h at 80 °C, the Ag2CO3-GO was synthesized.
2.1.4. Synthesis of Ag3PO4-GO (1 wt%)
8.46 mL of GO aqueous suspension (1 g/L) was added into AgNO3
solution (0.006 mol/L) and kept 12 h stirring to obtain solution E. Next,
100 mL of Na3PO4 solution (0.02 mol/L) was added dropwise into so-
lution E and stirred for 1 h. Being 4 h treating at room-temperature, a
grey composite was synthesized. Then through washing the composite
by the ultra-pure water for five times, and drying 6 h at 80 °C, the
Ag3PO4-GO was synthesized.
2.2. Characterization of GO Z-scheme materials
The XRD patterns was analyzed using X-ray diffraction (Rigaku,
Ultima IV, Japan). The scanned speed was 20°/min and the 2θ ranged
from 5° to 80°. Field-emission scanning electron microscopy (Hitachi, S-
4800, Japan) and Transmission electron microscopy (FEI, TECNAI G2
F20, USA) were used to characterize the morphologies and structure of
samples. Photoluminescence (PL) spectra of the photocatalysts was taken
with Fluorescence Spectrophotometer (HORIBA Jobin Yvon, FluoroMax-
4, France) at room temperature under the excitation wavelength of
330 nm and 430 nm. The UV–vis diffuse reflectance spectra were re-
corded using a UV–vis spectrophotometer (Perkin-Elmer, Lambda950,
USA). XPS spectra and maximum valence band of catalysts were ob-
tained using an X-ray photoelectron spectrometer (Thermo-VG Scientific,
ESCALAB 250 and 250XL, USA). The Zeta potential was explored with
laser particle size analyzer (Zetasizer Nano ZS, Malvern, UK).
2.3. Photocatalytic experiments
2.3.1. Photocatalytic degradation of MC-LR
As shown in Fig. S1, the photodegradation experiments were con-
ducted with a photochemical reactor according to our previous study
[21]. In this experiment, a 50 mL sandwich beaker was used as the reactor
and an amount of photocatalysts were added to 20 mL of MC-LR aqueous
solution with a certain concentration. At the given time intervals, 1 mL of
sample was withdrawn and filtered using 0.22 μm PTFE syringe filter to
remove the excess catalyst. The control group was conducted under the
same condition without the catalyst. High-performance liquid chroma-
tography (HPLC) (Shimadzu, LC-2030, Japan) equipped with an Eclipse
XDB-C18 column (250 mm × 4.6 mm, 5.0 μm particle size) was em-
ployed to determine the content of MC-LR. Detection wavelength was set
at 238 nm and the temperature was maintained at 30 °C. The mobile
phase consisted of 650 mL of methanol and 350 mL of water contained
0.05% tallow fatty acid (TFA). The flow rate was set to 0.6 mL·min−1 and
the injection volume was 20 μL [34]. The identification of MC-LR and its
intermediates was carried out in positive ion model using HPLC-QTOF-MS
(Agilent, G6520B, USA) under the above conditions.
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Chemical Engineering Journal 392 (2020) 123767
The effects of Z-scheme GO photocatalyst for MC-LR photo-
degradation were studied by one-factor-at-a-time approach. Take the
experiment of MC-LR degradation by Ag2CO3-GO as an example.
Firstly, 0.3 mg/L of MC-LR was adopted to investigate the effect of
dosages of photocatalyst (0–250 mg/L). Secondly, the effect of MC-LR
initial concentration (0.1–0.4 mg/L) was studied under optimum MC-
LR dosage. Finally, experiments on the effect of pH (3–11), DOM type
and concentration (0–10 mg/L), alkalinity (Na2CO3 initial concentra-
tion: 0–10 mg/L), H2O2 concentration (0–1 mg/L), and the coexistence
of algae were conducted with optimum MC-LR dosage and MC-LR in-
itial concentration. The effect of different types of Z-scheme-GO pho-
tocatalysts on MC-LR degradation was also studied under the same
condition to find out the optimum catalyst.
2.3.2. Photocatalytic inhibition of algal cells
In this experiment, a 250 mL sandwich beaker was used as the re-
actor and 100 mg/L of catalyst was added to 100 mL of algae suspen-
sion. The samples were withdrawn at the pre-set time intervals. The
physiological properties of algae cells were analyzed using UV–vis (T6,
New Century, China), laser particle size analyzer, and fluorescence
spectrum scanning (EEM, FS5, Edinburgh, UK).
2.4. Algal cells culture and index detection
The absorbance of algae cells suspension at 680 nm (OD680) was
regarded as one of the important indicators to determine the growth of
algae cells [35]. In this study, the OD680 value was 0.932 which was
analyzed by using UV–visible spectrophotometer (T6, New Century,
China).
2.4.1. Algae cultivation
Microcystis aeruginosa (FACHB-905) was obtained from the
Freshwater Algae Culture Collection at the Institute of Hydrobiology
(FACHB). The algae were cultivated in BG-11 media (Blue-Green
Medium, pH = 7.0) at 30 ± 1 °C under incandescent lamp.
Illumination intensity was about 2000 lx with light/dark cycle of 12 h/
12 h[36].
2.4.2. Determination of chlorophyll a content
Chlorophyll a content was obtained according to Fan et al. [37]
method. Briefly, 8 mL of sample was withdrawn at 0, 1, 2, 3, 4, 5, 6, 7,
8, 9 h for suction filtration with 0.7 μm cellulose acetate membranes.
After using filter paper to remove excess water, the cellulose acetate
membrane with filtered algal cells was placed in 10 mL centrifuge tube.
These samples were frozen at −20 °C for 1 h and thawed at room
temperature for 1 h with repeated three times. Then, 8 mL of 90%
acetone was added in the centrifuge tube and centrifuged at 3500 r/min
for 15 min, the obtained supernatant was analyzed by using UV–visible
spectrophotometer to measure OD630, OD647, OD664, and OD750. The
chlorophyll a content was calculated by Eq. (1):
Chlorphll a
[11.85(OD664 OD750) 1.54(OD647 OD750) 0.08(OD630 OD750 )] V1
(mg/L) =
2V2 L (1)
where V1 represents the volume of the extract (mL), V2 is the volume of
the water sample (mL), and L is the cuvette optical path (cm).
2.4.3. Detection of zeta potential
In this experiment, 1 mL of sample was withdrawn at 0, 1, 2, 3, 4, 5,
6, 7, 8, 9 h. The zeta potential of the algae suspension was determined
by laser particle size analyzer (Zetasizer Nano ZS, Malvern, UK).
2.4.4. Determination of extracellular organic matter (EOM)
10 mL of algae suspension was withdrawn at 0, 1, 2, 3, 4, 5, 6, 7, 8,
9 h and centrifuged under 4 °C immediately (4500 r/min, 10 min).
Then, the obtained supernatant was filtered using 0.45 μm filter
G. Fan, et al.
membrane. 3 mL of algae suspension was withdrawn for the determi-
nation of extracellular organic matter (EOM) using fluorescence spec-
trum scanning (EEM, FS5, Edinburgh, UK) with xenon lamp as excita-
tion light source. The detection parameters for EOM of algal suspension
were consistent with our previous study [38].
Fig. 1. X-ray diffraction patterns of (a) Ag2CrO4-GO, Ag3PO4-GO and Ag2CO3-GO, (b) Ag2CO3-GO, Ag2CO3 and GO, (c) UV–vis spectra of Ag2CrO4-GO, Ag3PO4-GO
and Ag2CO3-GO, (d) Ag2CO3-GO, Ag2CO3 and GO.
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Chemical Engineering Journal 392 (2020) 123767
2.4.5. Determination of intracellular organic matter (IOM)
The precipitation of algal suspension was collected during the EOM
detection process and centrifuged three times followed by washing with
ultra-pure water. After being added with 10 mL of ultra-pure water,
these samples were frozen at −20 °C and thawed at 4 °C with repeated
three times. Subsequently, ultrasonic cell disrupter (VCX130, Sonics &
G. Fan, et al.
Materials Inc, USA) was employed for the release of intracellular or-
ganic matter (IOM). The supernatant was collected by centrifugation
(5000 r/min, 20 min) and then filtrated by 0.45 μm filter membrane.
Finally, 3 mL of algae suspension was withdrawn for the determination
of IOM using fluorescence spectrum scanning (EEM, FS5, Edinburgh,
UK). The detection parameters for IOM of algal suspension were con-
sistent with our previous study[38].
Fig. 2. SEM images of (a) Ag2CO3, (b) Ag2CO3-GO, (c) Ag2CrO4, (d) Ag2CrO4-GO, (e) Ag3PO4 and (f) Ag3PO4-GO.
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Chemical Engineering Journal 392 (2020) 123767
3. Results and discussion
3.1. Characteristics of the photocatalysts
The XRD patterns of Ag2CO3-GO and its components were showed
in Fig. 1(b). Ag2CO3-GO showed distinct peaks at 18.61°, 20.66°,
32.76°, 33.76°, 37.09°, 39.75°, 41.91°, and 44.45°, which were ascribed
G. Fan, et al.
to the (0 2 0), (1 1 0), (−1 0 1), (−1 3 0), (2 0 0), (0 3 1), (2 2 0), and
(1 3 1) crystal face of Ag2CO3, respectively [32]. Typical XRD patterns
of Ag2CO3-GO, Ag2CrO4-GO and Ag3PO4-GO were presented in
Fig. 1(a). All the characteristic peaks could be corresponded to phase of
Ag2CrO4 (JCPDS No. 26-0952) [26]. The main peaks of Ag3PO4-GO
could be related to the (1 1 0), (2 0 0), (2 1 0), (2 1 1), (2 2 0), (3 1 0),
(2 2 2), (3 2 0), (3 2 1), (4 0 0), (3 3 0), and (4 2 1) planes of the body-
centered cubic structure Ag3PO4 (PDF#06-0505), respectively [33].
Besides, the diffraction peak of all samples at 2θ = 26.7° was corre-
sponding to the GO, indicating the successful synthesis of Ag2CO3-GO,
Ag2CrO4-GO, and Ag3PO4-GO.
To further understand the photocatalytic activity of different Z-
scheme photocatalysts, UV–vis spectra and PL spectra were in-
vestigated. It can be observed from Fig. 1(c), all the GO-catalysts ex-
hibited different absorbance in the visible-light region. Ag2CrO4-GO
showed a wider absorption band in 380–600 nm while the absorption
intensities significantly decreased after 600 nm. Compared with
Ag2CrO4-GO, Ag2CO3-GO and Ag3PO4-GO exhibited a relatively stable
response to the visible light. Ag2CO3-GO showed a more significant
photoexcitation performance than Ag3PO4-GO. This may due to the
photon excitation on Ag2CO3 which required less energy than Ag3PO4
(hνAg3PO4 = 2.420, hνAg2CO3 = 2.300) [39,40]. Fig. 1(d) showed the
Fig. 2. (continued)
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Chemical Engineering Journal 392 (2020) 123767
photocatalytic activity trend as follows: Ag2CO3-GO >
Ag2CO3 > GO. Besides, Ag2CO3-GO exhibited a broader absorption
band during 300–780 nm. Thus, the photocatalytic activity of Ag2CO3
could be remarkably enhanced with the suitable content of GO in the
visible-light region. The PL measurement was carried out to study the
situation of the recombination of photo-generated electron - hole pairs.
Basically, the weaker fluorescence intensity corresponded to the lower
charge recombination rate. As shown in Fig. 1(e), the fluorescence in-
tensity of the different components of Ag2CO3-GO
(Ag2CO3 > GO > Ag2CO3-GO) indicated that the heterojunction
between GO and Ag2CO3 could significantly decrease the recombina-
tion of electron - hole pairs.
The morphological characteristics of all obtained photocatalysts
were evaluated through SEM and TEM as presented in Fig. 2. According
to Fig. S2, it was obvious that GO showed a regular layered distribution
and could provide a large number of sites for Ag salt attachment as a
carrier. The Ag2CO3 displayed a relatively dispersed distribution
(Fig. 2(a)) while dense agglomeration and accumulation could be found
in Ag2CrO4 (Fig. 2(b)) and Ag3PO4 (Fig. 2(c)). Besides, compared with
Ag2CrO4, both Ag2CO3 and Ag3PO4 exhibited a clearer crystal structure
and higher crystallinity. As can be seen from Fig. 2(b–f), Ag salt par-
ticles were distributed on graphite oxide and the gap of GO sheets,
G. Fan, et al. Chemical Engineering Journal 392 (2020) 123767

indicating the successful synthesis of Ag2CO3-GO, Ag2CrO4-GO, and attributed to the effect of GO on Ag2CO3. The peaks at 531.0 eV in Fig.
Ag3PO4-GO. Apparently, Ag2CO3 was evenly distributed on the surface S11(h) were in accordance with the feature peaks of oxygen in Ag2CO3
of the GO and increased the SSA of the catalyst, which made it easier to [42]. The new peaks of O1s were found at 530.9 and 531.4 eV in
contact with reactants. In comparison, the dense agglomerations of Ag2CO3-GO (Fig. S11(d)) may be related to the existence of GO. The
Ag2CrO4 and Ag3PO4 on the surface of GO resulted in the uneven dis- above results further indicated the successful synthesis of Ag2CO3-GO.
tribution, which may increase the SSA of the photocatalyst. While the
photo-response performance was affected due to the agglomeration,
3.2. Photocatalytic degradation of MC-LR
leading to the decrease in the photocatalytic performance. Through
comparing with the TEM images from Fig. 2(g–j), it could be clearly
As can be seen in Fig. 3(a), the content of MC-LR remained almost
observed that Ag2CO3 was successfully deposited on the surface of GO,
unchanged within 7 h without photocatalysts, indicating that visible
indicating the formation of heterostructure between GO and Ag2CO3.
light irradiation had no significant effect on the degradation of MC-LR.
This structure may provide good potential for carrier transport, which
All three kinds of photocatalysts exhibited high degradation efficiency
further guaranteed the photocatalytic performance of Ag2CO3-GO.
of MC-LR in the early stage during the treatment process. Subsequently,
XPS measurements were carried out to elucidate the surface elec-
the degradation efficiency was decreased, which was mainly due to the
tronic states of the as-prepared Ag2CO3 samples. According to the
less active sites caused by the MC-LR intermediates during the de-
survey scan (Fig. S11(a) and Fig. S11(e)), it was obvious that Ag2CO3-
gradation process. The degradation efficiency of MC-LR using Ag2CrO4-
GO and Ag2CO3 all contain Ag, C and, O elements. The peaks of C1s
GO and Ag3PO4-GO could achieve at 100% and 55% within 3 h under
located at 284.7 and 288.7 eV were relevant to carbon in Ag2CO3 (Fig.
visible light, respectively. In contrast, Ag2CO3-GO could completely
S11(f)) [41]. The new peaks of C1s were found at 286.8 eV in Ag2CO3-
degrade MC-LR within 1 h, exhibiting a distinctively effective photo-
GO composite (Fig. S11(b)), which was ascribed to graphene sp2 epoxy/
catalytic performance. The photocatalytic degradation ability of these
hydroxyl (C–O) [39], further indicating the formation of hetero-
photocatalysts was in the following order: Ag2CO3-GO > Ag2CrO4-
structure between GO and Ag2CO3. Besides, around 367.9 and
GO > Ag3PO4-GO. The HPLC chromatogram of the photocatalytic
373.9 eV, the Ag 3d3/2 and Ag 3d5/2 could also be investigated (Fig.
degradation of MC-LR was shown in Fig. 3(b–d). The peak intensities of
S11(g)), demonstrating the existence of Ag+ in Ag2CO3. The shift of
MC-LR were decreased with the extension of retention time (RT), in-
characteristic peaks of Ag3d spectrum for Ag2CO3-GO (Fig. S11(c)) may
dicating that intermediate by-products were generated during

Fig. 3. (a) Photocatalytic degradation of MC-LR under visible light by Ag2CO3-GO, Ag2CrO4-GO and Ag3PO4-GO, and HPLC chromatograms of the MC-LR de-
gradation over time (b) Ag2CO3-GO, (c) Ag2CrO4-GO, (d) Ag3PO4-GO.

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G. Fan, et al. Chemical Engineering Journal 392 (2020) 123767

photocatalytic degradation. Some peak sites which represented dif-
ferent by-products were observed: RT = 3.1, 3.3, 5.1 and 5.8 min
(Fig. 3(b)), RT = 4.8, 5.2, and 6.9 min (Fig. 3(c)), RT = 4.1, 6.2, 6.9,
and 7.2 min (Fig. 3(d)). The reduction of peak intensities showed that
intermediates were further degraded, which corresponded to the de-
crease in the degradation efficiency of MC-LR in the later stage of
treatment. The speculation that MC-LR competed for the active sites
between MC-LR and its intermediates was also confirmed.
3.3. Effect of environmental factors on MC-LR degradation by Ag2CO3-GO
3.3.1. Photocatalytic performance
The photocatalytic degradation of MC-LR by Ag2CO3-GO and its
components under visible light are shown in Fig. 4(a). Without the
addition of Ag2CO3-GO, visible light irradiation had no significant ef-
fect on MC-LR degradation. The degradation efficiency of Ag2CO3-GO
reached up to 100% within 10 min, which was 76% and 55% higher
than that of Ag2CO3 and GO, respectively. However, Ag2CO3 resulted in

Fig. 4. Photocatalytic degradation of MC-LR under visible light by Ag2CO3-GO (a) by different materials, (b) at various catalyst dosages, (c) at various pH, (d) the
change of Zeta potential for MC-LR and Ag2CO3-GO, (e) at various initial MC-LR concentration, (f) at various initial HA concentration, (g) at various initial FA
concentration, (h) at various initial Na2CO3 concentration, (i) at various initial H2O2 concentration, (j) in the presence of algae.

8
G. Fan, et al.
Fig. 4. (continued)
the worst photocatalytic performance because it could not respond
significantly to visible light. The greatest photocatalytic performance of
Ag2CO3-GO may be attributed to the superior visible light absorption
performance of GO [43]. The doping of GO increased the SSA and
porosity of the composite photocatalyst, thus providing more active
sites. Besides, GO and Ag2CO3 formed a homogeneous system, which
could inhibit the recombination of photo-generated electrons and holes
[44]. These findings showed that Ag2CO3 can effectively remove MC-LR
from water bodies, indicating its excellent visible light catalytic per-
formance.
3.3.2. Ag2CO3-GO dosage
The degradation efficiency of MC-LR under different dosages of
Ag2CO3-GO is presented in Fig. 4(b). The content of MC-LR stabilized
within 7 h without photocatalyst in the system. In the contrast, there
was significant decrease of MC-LR concentration after degrading by
Ag2CO3-GO. The degradation efficiency of MC-LR increased with higher
catalyst dosage in the range from 0 to 200 mg/L. However, a decrease
of the degradation efficiency was observed when the dosage increased
to 250 mg/L, which could be explained by the fact that the scattering
effect would affect the light absorption of the catalyst and lead to the
flocculation and precipitation with excessive photocatalyst [21].
3.3.3. pH value
Fig. 4(c) shows the results of MC-LR degradation over time under
various pH values with initial MC-LR concentration of 0.2 mg/L and
100 mg/L of Ag2CO3-GO. Ag2CO3-GO was most effective to degrade
MC-LR at pH 5 (i.e., MC-LR was 100% degraded at 1.25 min). Although
complete degradation of MC-LR was also reached at 1.25 min under pH
9
Chemical Engineering Journal 392 (2020) 123767
3, the degradation efficiency was not as high as pH 5. As the pH in-
creased further, the degradation efficiency of MC-LR decreased. How-
ever, MC-LR removal efficiency could reach 100% after 15 min under
different pH values. Besides, the higher removal efficiency was ob-
served under acidic conditions compared with alkaline conditions,
which may be due to the reason that the solution pH could affect the
hydrophobic of MC-LR [45]. According to previous study, MC-LR pre-
ferentially moved to the surface of Ag2CO3-GO as the result of hydro-
phobicity effect in the solution, and the hydrophobicity effect was
found to be weaken under alkaline conditions [45], causing the de-
crease of contact time between MC-LR and the photocatalyst. Mean-
while, the excess OH− could cause Ag+ to rapidly form Ag0, which
would deposit on the surface of the catalyst in the formation of nano-
Ag, resulting in a reduction of the catalytic active sites. In addition, the
CO32− dissociated by Ag2CO3-GO in water played a role in scavenging
of hydroxyl radical (%OH). The HCO3− (8.5 × 106 M−1 s−1), which
formed in acidic condition, had lower effect on the removal of ·OH than
CO3− (3.9 × 108 M−1 s−1), which existed in alkaline condition [15].
This could also explain why the catalyst exhibited better visible light
photocatalytic activity under acidic conditions. Furthermore, the
pseudo-first-order kinetic model of the degradation process of MC-LR
under visible light and the variation of the zeta potential of catalyst and
MC-LR at different pH values are shown in Figs. S4 and 4(d), respec-
tively. The best apparent reaction rate constant was 2.46436 min−1 at
pH 5. The apparent reaction rate constant slightly decreased to
2.03781 min−1 at pH 3, the possible reason was that Ag2CO3 could be
partially dissolved in the acid solution, leading to the destruction of the
structure of photocatalyst [46]. As shown in Fig. 4(d), the zeta potential
of Ag2CO3-GO was positive while MC-LR was negative at pH 3.
G. Fan, et al.
Therefore, MC-LR could be adsorbed on the surface of the photocatalyst
through electrostatic interaction. In addition, the zeta potential of
Ag2CO3-GO turned to negative when pH ≥ 5 and the negative charge
increased with the increase of pH, leading stronger electrostatic re-
pulsion between MC-LR and photocatalyst. This phenomenon may also
explain why the poor degradation of Ag2CO3-GO under alkaline con-
ditions.
3.3.4. Initial concentration of MC-LR
The effect of different initial MC-LR concentrations on the photo-
catalytic degradation process is shown in Fig. 4(e). The MC-LR was
degraded rapidly within 5 min at the initial stage of the experiment,
which may be due to the rich active sites on the surface of the photo-
catalyst. The degradation efficiency of MC-LR decreased when the in-
itial concentration was less than 0.3 mg/L. When the initial con-
centration increased to 0.4 mg/L, the degradation efficiency of MC-LR
was basically the same as that of 0.3 mg/L and could reach 100%
within 45 min. Fig. S3 shows the effect of the initial MC-LR con-
centration on the photocatalytic degradation efficiency over Ag2CO3-
GO catalyst. As shown in Eq. (2), the Langmuir-Hinshelwood model was
applied for fitting kinetics process.
Ct
ln = kt
C0 (2)
where C0 (mg/L) is the initial concentration of MC-LR, Ct (mg/L) is the
concentration of MC-LR at time t (min), k (min−1) is the apparent re-
action rate.
The square of correlation coefficient R2 was 0.968, 0.965, and 0.995
for the initial MC-LR concentrations of 0.2, 0.3 and, 0.4 mg/L, re-
spectively. The MC-LR degradation process confirmed to fit well the
pseudo-first-order kinetic equation [34]. As the initial concentration of
MC-LR increased from 0.1 mg/L to 0.4 mg/L, the reaction efficiency
decreased from 0.45644 min−1 to 0.09291 min−1 and varied obviously
in the range of 0.1–0.3 mg/L. When the initial concentration of MC-LR
was more than 0.3 mg/L, there was no significant decrease for the re-
action efficiency. This may be due to the Ag2CO3-GO active site was
saturated for a long time by excessive MC-LR, leading to the lower
degradation efficiency.
3.3.5. Natural organic matter (NOM)
The main composition of natural organic matter (NOM) in surface
water mainly included humic acids (HA), fulvic acids (FA), poly-
saccharides, and proteins, and etc [47]. Therefore, HA and FA were
selected as representative natural organic compounds for exploring the
influence of NOM on the photocatalytic degradation of MC-LR by
Ag2CO3-GO. The experimental results are shown in Fig. 4(f and g).
Compared with control group, MC-LR degraded dramatically in the
presence of FA and HA, and the inhibitory effect of FA was more sig-
nificant in contrast to HA. The degradation of MC-LR showed a sig-
nificant downward trend as the dosage of HA and FA increased. The
photocatalytic degradation efficiency reached 100% at 2 h and 1 h with
the addition of 5 mg/L of HA and FA, respectively. As the dosage of HA
and FA increased to 10 mg/L, the degradation efficiency of MC-LR
achieved to 20% and 25% at 4 h, respectively. It was confirmed that the
photocatalytic degradation of organic pollutants could be inhibited in
the water body when the NOM content reached a certain concentration
due to HA, FA, and MC-LR co-competing catalyst surface active sites
and active substance [48,49]. Besides, dissolved HA and FA could act as
an incident light screen, reducing the visible light transmittance to a
certain extent [50]. At the same time, as the reactive oxygen species
(ROS) radical scavenger, HA and FA can effectively remove the active
substance produced by photocatalyst [51].
3.3.6. Alkalinity
In this study, the solution alkalinity was adjusted by adding Na2CO3.
10
Chemical Engineering Journal 392 (2020) 123767
The effect of alkalinity on the photocatalytic degradation efficiency of
Ag2CO3-GO by MC-LR is shown in Fig. 4(h). The degradation efficiency
of MC-LR reached 100% at 20, 60, and 120 min with the initial Na2CO3
concentrations of 0, 5, and 10 mg/L, respectively. The results proved
that the alkalinity had a negative effect on the photocatalytic de-
gradation of MC-LR by Ag2CO3-GO. This may be explained by the fact
that carbonate (e.g., CO32− and HCO3−) may compete with MC-LR for
%OH since %OH (E0 = 2.3 V) is more likely to react with CO32− and
HCO3− to form CO32− (E0 = 1.78 V) with lower oxidation activity, as
shown in Eqs. (3) and (4) [15,52]. Moreover, CO32− is not conducive to
the progress of MC-LR degradation for its alkalinity in solution.
CO23 + ·OH OH +·CO3 (3)
HCO3 + ·OH ·CO3 + H2 O (4)
3.3.7. H2O2 dosage
The impact of H2O2 at different concentrations on MC-LR photo-
catalytic degradation by Ag2CO3-GO is shown in Fig. 4(i). In the control
group, MC-LR was completely degraded by Ag2CO3-GO within 20 min.
However, the MC-LR degradation rate was decreased when a small
amount of H2O2 was added. The degradation efficiency of MC-LR was
55% and 42% with 0.5 mg/L and 1 mg/L H2O2 within 4 h, respectively.
The results showed that the addition of H2O2 could inhibit the de-
gradation of MC-LR. This negative effect may due to the reaction be-
tween ·OH and H2O2, resulting in a decrease in the ROS content in the
solution, as shown in Eqs. (5) and (6) [53,54]. In addition, the possible
reason was that a higher concentration of H2O2 could absorb or at-
tenuate incident light, inhibiting the photocatalytic activity of Ag2CO3-
GO [55].
H2 O2 + h + HO2 · + H + (5)
H2 O2 + ·OH HO2 · + H2 O (6)
3.3.8. Effect of algal cells coexisting on degradation of MC-LR
Harmful algal cells would release the toxins into the surrounding
aquatic environment once rupture. In this study, through adding MC-LR
(0.2 mg/L) to high-density algae suspension to simulating the state of
MC-LR leakage under high-density algae oxidative damage condition.
In the presence of Microcystis aeruginosa cells, the degradation of MC-LR
by the photocatalyst is shown in Fig. 4(j). MC-LR content in the control
group remained unchanged within 9 h, indicating no significant influ-
ence on MC-LR degradation under visible light. In the experimental
groups, MC-LR concentration reduced from 0.178 to 0.067 mg/L (i.e.,
62.4% degradation efficiency). Compared with the degradation process
without adding algal cells, the removal efficiency of MC-LR by Ag2CO3-
GO was inhibited in the presence of algae cells. This may be due to the
more competitive catalyst active sites and substances of algae cells for
their greater SSA and coarse surface texture compared with MC-LR. The
removal of algae under visible light by Ag2CO3-GO in presence of MC-
LR was provided in Fig. S5. In the control group, the content of
chlorophyll a remained basically unchanged within 9 h, implying that
visible light irradiation contributed insignificantly to algae cells in-
activation. When only Ag2CO3-GO was added, the content of chlor-
ophyll a of the algae cells in the experimental group was close to zero,
which meant nearly 100% algae cells were removed by photocatalyst.
The removal efficiency of algal cells was 80% with the addition of MC-
LR, suggesting MC-LR exhibited insignificant inhibition to the photo-
catalytic degradation of algae cells by Ag2CO3-GO. The above results
further confirmed that Ag2CO3-GO could achieve the synergistic re-
moval of algal and MC-LR to a certain extent.
G. Fan, et al.
3.4. Photocatalytic inhibition of algal cells by Ag2CO3-GO
3.4.1. Cell chromaticity and chlorophyll a content
The concentration of chlorophyll a could indicate the amount of
algal cells since the function relationship between chlorophyll a content
and the growth state of algae cells [56]. Fig. S6(a-b) presents the algae
cells suspension and the color change of chlorophyll a in the control and
experiment groups, respectively. Comparison for chlorophyll a content
changes of samples in two groups is shown in Fig. S6(c). It was obvious
that visible light irradiation did not play a role in the photocatalytic
degradation of Microcystis aeruginosa without Ag2CO3-GO, since no
significant color change was found in the control group (Fig. S6(a)).
Besides, only a slight decrease in chlorophyll a in the first hour was
found in the control group. In the experiment group, the color of the
algae suspension was brown at most of the time and did not sig-
nificantly change within 9 h except that the color turned green to
brown in the first hour, which was presumably caused by the chroma of
the catalyst and the oxidative damage of the algae cells. The chlor-
ophyll a underwent a continuous reduction in the presence of Ag2CO3-
GO and the suspension was basically colorless after 6 h. The removal
efficiency of chlorophyll a at the same time was approximately 80%.
With the photocatalysis time extended to 9 h, the removal efficiency of
chlorophyll a by catalyst increased to 100%. Therefore, the dosage of
100 mg/L Ag2CO3-GO was efficient in oxidizing and damaging high-
concentration algal cells (OD680 = 0.932).
Fig. 5. Integration of fluorescence regions of algal cells EOM and IOM during photocatalytic treatment (a) the change of algal EOM for control groups, (b) the change
of algal EOM for experimental groups, (c) the change of algal IOM for control groups, (d) the change of algal IOM for experimental groups.
11
Chemical Engineering Journal 392 (2020) 123767
3.4.2. Zeta potential
The effect of Ag2CO3-GO on the zeta potential of algal cells is shown
in Fig. S7. The algal cells were negatively charged in the solution and
stabilized within 9 h with only a small decrease in the absolute value of
the zeta potential. Ag2CO3-GO was negatively charged with a zeta po-
tential of −13.8 mV at the beginning. The absolute zeta potential value
of Ag2CO3-GO was much smaller than that of algae cells. The zeta po-
tential of the Ag2CO3-GO was highly stable during the experiment, in-
dicating its excellent stability in water. Besides, the absolute value of
zeta potential in the experimental group decreased continuously over
time (e.g., from 45.2 mV to 31.0 mV) and stabilized after 7 h reaction. It
was consistent with that of section 3.4.1. The continuous decrease of
zeta potential may be partly due to the oxidation damage by Ag2CO3-
GO which changed the membrane structure of algal cells, resulting in
the release of cell contents. Hence, Ag2CO3-GO could reduce the zeta
potential and stability of algal cells, presumably contributing to the
aggregation and sedimentation of damaged cells thereafter [57].
3.4.3. Eom and IOM
The fluorescence spectrum of EOM and IOM during the photo-
catalysis process is presented in Figs. S8 and S9. The EOM fluorescence
spectrum of algae solution included peak A, λex/λem = 280/325 nm;
peak C, λex/λem = 255/455 nm; and peak D, λex/λem = 345/425 nm,
which represented protein-like, fulvic acid-like, and humic-like sub-
stances, respectively [58] (Fig. S8). The fluorescence intensity of the
G. Fan, et al.
control group basically showed an enhancement in V region which was
assigned to humic acid-like and fulvic acid-like substances within 2–5 h
and then tended to stabilize after 5 h, suggesting that algal cells suffered
stress response and gradually adapted to the visible light irradiation.
The fluorescence intensities and areas of peaks A, D, and C decreased
over time, presumably due to the removal of intracellular substances
released from cells during the photocatalyst oxidation process. The IOM
fluorescence spectrum for algal cells is depicted in Fig. S9. Peak A at
λex/λem of 275/320 represented microbial soluble metabolites, aro-
matic proteins, and phenolic substances; peak B at λex/λem of 225/325
indicated tyrosine-like and tryptophan-like substances; peak C at λex/
λem of 275/450 was corresponding to fulvic acid-like substances, and
peak D at λex/λem of 450/350 conformed to humic acid-like substances
[59]. In the control group, the fluorescence peaks intensities of IOM
basically unchanged within 9 h except for the insignificant decrease of
peak B in the first hour. It was possibly due to the adaptation of algae to
visible light irradiation in the initial stage. The fluorescence intensity of
all treated samples decreased dramatically in comparison to the un-
treated samples. Peaks A and B showed the most significant decrease
among them. With the increase of the photocatalysis time, the peak in
fluorescence from fulvic acid-like and humic acid-like substances were
increased initially and decreased afterward. The results indicated that
Ag2CO3-GO not only led to the oxidative stress of algal cells but also
oxidized the inclusions released from the damaged cells.
To further verify the variations of IOM and EOM content in algal
cells during the photocatalysis process, FRI partition method was used
to quantitatively divide the fluorescence regions [60]. The FRI parti-
tioning method and typical representative substances are shown in
Table S1. The quantitative integration results of the EOM and IOM
fluorescence regions of algae cells are shown in Fig. 5. As depicted in
Fig. 5(a) and (c), the integration of fluorescence regions in the control
group maintained at high level during photocatalytic treatment and
IOM content was higher than that of EOM. Besides, a great increase in V
region was observed, which was commonly associated with the increase
of humic acid-like substances. This increase may due to the stress re-
sponse of algae cells to visible light irradiation, resulting in the release
of humic acid-like substances from the algae cells. As shown in Fig. 5(b)
and (d), EOM and IOM content increased first and then decreased in the
experimental group. The I + II regions of IOM which presented tryp-
tophan and tyrosine were increased, possibly ascribing to the protease
formed during the treatment process. Moreover, the subsequent re-
duction may explain that algal cells were completely inactivated, and
the photocatalyst further oxidized to remove the inclusions.
Fig. 6. (a) The species of active substances and (b) contributions of different active substances.
12
Chemical Engineering Journal 392 (2020) 123767
3.5. Photocatalytic stability and reusability
The specific operation steps of the Ag2CO3-GO stability in water
body, the measurement of chemical stability of Ag2CO3-GO, and cir-
culation experiment are shown in Text S2 and Text S3. The experi-
mental results are shown in Fig. S10. After five consecutive cycles of
visible light photocatalytic degradation of methyl orange, its degrada-
tion efficiency could still reach about 80% with only 17% reduction
compared with the first cycle, indicating that Ag2CO3-GO exhibited
significant reusability performance. The XRD patterns and SEM images
of Ag2CO3-GO before and after the recycling experiment are shown in
Fig. S10(b), (c), and (d). The recovered Ag2CO3-GO in each recycle
experiment all kept the characteristic peak of the original Ag2CO3-GO,
and no other diffraction peaks were observed. Only the intensity of the
diffraction peaks at different sites declined to some extent. Meanwhile,
the results of SEM images also showed that the morphology of Ag2CO3-
GO did not change significantly, only a few of Ag2CO3 exfoliations from
GO after five cycles experiments could be observed. The results showed
that the content of Ag+ decreased with the cycle experiments in the
experiment group compared with the control group as depicted in Fig.
S10(e), which indicated that the degree of detachment of Ag2CO3 in-
creased with the cycle experiments. However, the detachment rate of
Ag2CO3 from GO decreased with the cycle experiments after the second
run. By the end of the fifth cycle, the degree of detachment of Ag2CO3
was only about 14.1%. The above experimental results indicated that
Ag2CO3-GO exhibited excellent stability and had a promising prospect
to apply in the aquatic environment.
3.6. Mechanism of photocatalytic degradation of MC-LR by Ag2CO3-GO
3.6.1. Reactive species
The quenching experiments were performed for exploring the pos-
sible photocatalytic degradation mechanism of the MC-LR by Ag2CO3-
GO. In order to trap the superoxide radical (%O2−),·OH, and holes (h+),
1 mM of p-benzoquinone (BQ), isopropanol (IPA), and sodium oxalate
(SO) were added, respectively [61]. In addition to the use of scavengers,
all the experiment procedures of the quenching experiments were
consistent with the photocatalytic experiments. As presented in Fig. 6,
MC-LR was completely degraded in 20 min without scavenger in the
control group. However, the MC-LR degradation efficiency was 50%,
18%, and 8% with the addition of IPA (1 mM), IPA (1 mM) and BQ
(1 mM), IPA (1 mM) and SO (1 mM) and BQ (1 mM), respectively. The
results indicated that %OH and %O2− were the primary reactive species,
which contributed 50% and 32% for the MC-LR degradation,
G. Fan, et al.
respectively. While only 10% of the degradation was attributed to h+
and the remaining 8% of MC-LR degradation may due to other reactive
species (e.g., %CO3−).
3.6.2. MC-LR intermediates and potential pathways
The reaction intermediates of MC-LR were analyzed by HPLC-
QTOF-MS. The possible types of intermediates, oxidative destructible
groups, and bond energy sites were studied. During the degradation
procedure, twenty compounds m/z 995.6, 1029.5, 1009.6, 1011.6,
1015.6, 1027.5, 1063.5, 233.2, 283.2, 795.4, 743.4, 193.2, 274.2,
346.3, 318.3, 362.3, 835.2, 745.2, 652.2, 525.3 were detected and their
Fig. 7. The possible three degradation pathway of MC-LR by Ag2CO3-GO during the photocatalytic process (A) the first possible degradation process, (B) the second
possible degradation process, (C) the third possible degradation process.
13
Chemical Engineering Journal 392 (2020) 123767
molecular structures are shown in Fig. S12. Based on the above results,
three possible degradation pathways of MC-LR by Ag2CO3-GO in the
photocatalytic procedure were proposed.
The first possible MC-LR degradation pathway is shown in Fig. 7(A).
The products with m/z 995.6 were assigned to MC-LR. Firstly, the
conjugated double bond of the Adda moiety and the unsaturated double
bond of the Mdha moiety in the molecular structure of MC-LR were
attacked by reactive species such as ·OH, forming four dihydroxylated
isomers with m/z 1029.5 (a, b, c, d). Then, electrophilic free radical
(e.g.,%OH) was added to the unsaturated double bond in the dihy-
droxylated intermediate (a) with m/z 1029.5, generating three kinds of
G. Fan, et al.
Fig. 7. (continued)
tetrahydroxylated isomers (g, e, f) with m/z 1063.5 [62]. The inter-
mediates (g, e) were oxidized to cleave at the diene structure forming
intermediate products with m/z 233.2, 283.2, and 193.2, removing the
Adda moiety. The intermediate (h) was formed by further oxidation of
Adda and Mdha moieties in the MC-LR peptide chain. Finally, the
amino group of m/z 743.4 was hydrolyzed to small molecule de-
gradation products with m/z 274.3. The hydroxylated carbon-carbon
single bond in the m/z 1029.5 was cleaved under %OH oxidation, which
was proved by the generation of intermediates (o) with m/z 835.2
(ketone-like) and (j) with m/z 193.2 (aldehyde-like). Further photo-
catalytic process led to the opening of the peptide ring, which was
confirmed by the product (p) with m/z 745.2. This could be explained
by oxidation of the Mdha, Arginine, as well as partial structures in
Alanino. The observation of the intermediate (q) with m/z 652.2 in-
dicated that the gradual decarbonated and decarboxylation progress of
the intermediate (p) with m/z 745.2. Similarly, the intermediate (r)
with m/z 525.3 was the result of the continued decarboxylation of the
residual Adda and Glu in the intermediate (q) with m/z 652.2, which
was caused by the photogenerated h+ [63]. Besides, the
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Chemical Engineering Journal 392 (2020) 123767
bishydroxylated intermediate (c) with m/z 1029.5 was oxidized to form
the intermediate (n) with m/z 795.4 and intermediate (m) with m/z
233.2.
According to the second proposed pathway (Fig. 7(B)), the methoxy
group on the MC-LR structure formed a formic acid-MC-LR-lipid deri-
vative intermediate (s) with m/z 1009.6 under the attack of ·OH[62].
Subsequently, the amino and carbonyl group in Adda of the inter-
mediate (s) was hydrolyzed into the m/z 346.3 (t) of which the lipid
structure was then further hydrolyzed into the m/z 318.3 (v). Ad-
ditionally, the benzene ring structure on MC-LR was prone to be at-
tacked by electrophiles leading electrophilic substitution. Combined
with oxygen molecules, %OH substituted hydrogen atoms from benzene
ring and the intermediate (u) with m/z 362.3 was formed.
The third possible pathway is presented in Fig. 7(C). When attacked
by %OH and %O− 2 , the C]C in Mdha could temporarily be oxidized to
form C]O and generate the intermediate (w) with m/z 1011.6 [64].
Similarly, the carbon at the unsaturated C]C in Adda was easily oxi-
dized to C]O, generating the isomer of the m/z 1011.6 which was
indicated by intermediate (x). Subsequently, the amido bond in Mdha
G. Fan, et al.
Fig. 7. (continued)
was further hydrolyzed and the intermediate (y) with m/z 1015.6 was
formed by cleaving the peptides. The intermediate (z) with m/z 1027.5
was formed at the same time as the C]C in the Mdha was temporarily
oxidized to C]O. Then, intermediate (h) with m/z 743.4 was generated
accompanied by the exfoliation of the Adda and Mdha. Finally, the
amino group of the residual Adda in intermediate (h) was hydrolyzed to
form intermediate (i) with m/z 274.2.
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Chemical Engineering Journal 392 (2020) 123767
According to the above three possible MC-LR photocatalytic degrada-
tion pathways, we inferred that four sites including benzene ring, methoxy
group, conjugated double bond in Adda, and the unsaturated part in Mdha
in MC-LR were most vulnerable to suffer from oxidation [65,66]. Fur-
thermore, with the further oxidation by Ag2CO3-GO, MC-LR was gradually
oxidized and destroyed with the destruction of conjugated double bond in
the Adda and Mdha, Alanine, and Arginine in peptide [67].
G. Fan, et al.
Fig. 8. Photocatalytic mechanism diagram of the Ag2CO3-GO samples.
3.7. Photocatalysis mechanism of algae removal and MC-LR degradation by
Ag2CO3-GO
The maximal valence band value of GO was acquired by the VB-XPS
spectra of GO (Fig. 1(f)). The calculation process and results of valence -
conduction band position of Ag2CO3, as well as GO are shown in Text
S4 and Table S2, respectively. Based on the accurate band structure of
Ag2CO3 and GO, the Z-scheme interfacial charge transfer pathway of
Ag2CO3-GO was mainly confirmed as followed reasons. Firstly, the
formation of heterojunction between GO and Ag2CO3 was confirmed by
the characteristic results. In the Z-scheme pathway, the e− in the CB of
GO and h+ in the VB of Ag2CO3 were preserved. In this case, the re-
action of H2O/%OH and O2/%O2− occurred theoretically for the VB
potential of Ag2CO3 and the CB potential of GO were higher than the
redox potential of H2O/%OH (ca. 2.380 eV) and O2/%O2− (ca.
−0.330 eV)[68,69]. This was consisted with the results of quenching
experiments that %OH and %O2− were the primary reactive species. In
the type II pathway, the e− and h+ would be accumulated in the CB of
Ag2CO3 and the VB of GO, respectively. While in this case, the reaction
of H2O/%OH and O2/%O2− cannot occur theoretically. The details of the
interfacial charge transfer mechanism were shown in Fig. S13. Sec-
ondly, the different Fermi level (EF) between the two semiconductors is
a prerequisite for inducing charge redistribution and internal electric
field formation, and this significant difference affects the process of
photogenerated charge carrier separation and transfer [70,71]. The
Fermi level of GO ranged from ca. 1.4 to 1.6 eV [72], which varied with
the oxygen content on GO. The EF of Ag2CO3 was basically above 2 eV
[73,74]. Ag2CO3 has a higher EF compared with GO. Once GO con-
tacted with Ag2CO3, the free electrons in the CB of Ag2CO3 would
transfer to the VB of GO until their fermi levels are equilibrated [75],
resulting in the formation of internal electric field inside the Ag2CO3
and GO. The factors (e.g., internal electric field, the extra potential
barrier induced from band bending, and coulomb repulsion) hinder the
e- transfer from CB of GO to CB of Ag2CO3, as well as h+ transfer [75].
The details of mechanism analysis were shown in Fig. S14.
Based on the above analysis results, a photocatalytic mechanism for
the inactivation of harmful algae as well as MC-LR degradation by
16
Chemical Engineering Journal 392 (2020) 123767
Ag2CO3-GO was proposed (Fig. 8). Ag2CO3 and GO were activated to
generate electron-hole pairs under visible-light irradiation. The photo-
generated electrons (e−) of Ag2CO3 migrated from the VB to the CB to
form h+. Then, the e− tended to transfer and recombine with h+ in the
VB of GO. Hence, large quantities of h+ and e− were accumulated in
the VB and CB, respectively. The photogenerated h+ accumulated in
the VB would combine with H2O to generate ·OH. The e− accumulated
in the CB could react with the absorbed O2 to form O2-. Finally, the
generated ROS directly reacted with algae cells and MC-LR to achieve
algae cells growth inhibition and MC-LR degradation. In summary, the
Z-scheme photocatalyst significantly enhanced the photocatalytic ac-
tivity by inhibiting the recombination of electron-hole pairs.
4. Conclusion
Ag2CO3-GO exhibited the best efficiency in MC-LR degradation
compared with Ag2CrO4-GO and Ag3PO4-GO. The removal efficiency of
MC-LR by three photocatalysts was in the following order: Ag2CO3-
GO > Ag2CrO4-GO > Ag3PO4-GO. The optimum parameters for MC-
LR degradation were found to be as follows: the dosage of Ag2CO3-GO
was 100 mg/L, the initial content of MC-LR was 0.2 mg/L, and pH value
was about 5. Besides, the photocatalytic degradation rate of MC-LR was
in accordance with the pseudo-first-order kinetic model with the best
apparent rate constant (2.46436 min−1). The alkalinity, H2O2, DOM,
and the coexistence of algal cells could also affect the photocatalytic
degradation process of MC-LR by Ag2CO3-GO. Based on the fore-men-
tioned mechanism analysis, %OH and %O2− radical groups were the
main active radicals during the photocatalytic degradation process of
MC-LR and the inhibition process of Microcystis aeruginosa. The possible
photocatalytic degradation pathways of MC-LR demonstrated that Adda
and the peptides were easier to be broke due to the effect of %OH and
O2−. It would result in the loss of the toxicity of MC-LR. Besides, the
cycle experiments showed that Ag2CO3-GO demonstrated excellent
stability and reusability and remained excellent photocatalytic activity
after five consecutive cycles. In conclusion, by synthesizing the nano-
photocatalyst Ag2CO3-GO, this study provides a new insight for the
removal of toxic and harmful algae cells and their metabolites in the
G. Fan, et al.
aquatic environment under visible light.
Acknowledgments
The authors would like to gratefully acknowledge the financial
support from the National Natural Science Foundation of China (No.
51778146), the Outstanding Youth Fund of Fujian Province in China
(No. 2018J06013), and the Open Project Program of National
Engineering Research Center for Environmental Photocatalysis (No.
NERCEP-201901).
Declaration of Competing Interest
None.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.123767.
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