Journal of Hazardous Materials 389 (2020) 122129

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Journal of Hazardous Materials

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Enhanced photocatalytic degradation of acephate pesticide over MCM-41/ T

Co3O4 nanocomposite synthesized from rice husk silica gel and Peach leaves
Mostafa R. AbuKhadraa,b,*, Aya S. Mohameda,c, Ahmed M. El-Sherbeenyd,**,
Mohammed A. Elmeligye
a
Materials Technologies and their Applications Lab, Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt
b
Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef city, Egypt
c
Department of Environment and Industrial Development, Faculty of Postgraduate Studies for Advanced Sciences, Egypt
d
Industrial Engineering Department, College of Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia
e
Advanced Manufacturing Institute, King Saud University, Riyadh 11421, Saudi Arabia

G R A P H I C A L A B S T R A C T

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

Editor: Danmeng Shuai Novel green nanocomposite from mesoporous MCM-41 and Co3O4 was synthesized from rice husk based silica
Keywords: gel and using the green extract of Peach leaves as reducing reagent. The composite was labeled as RH-MCM-41/
Rice husk Co3O4 and characterized by different techniques as green photocatalyst in the degradation of Acephate pesticide
MCM-41 under visible light illumination. The composite showed well developed spherical MCM-41 particles decorated by
Peach leaves nano Co3O4 nanoparticles with stunning surface area and low bandgap energy (1.51 eV). The composite dis-
Co3O4 played superior photocatalytic activities in the oxidation of Acephate which reflected in a complete degradation
Photocatalyst of different concentrations of it after 40 min (50 mg/L), 60 min (100 mg/L), 100 min (150 mg/L) and 140 min
Acephate pesticide
(200 mg/L) using 0.25 g of the composite. The complete removal of the present TOC for treatment of 100 mg/L
acephate was achieved using 0.25 g after 70 min reflecting the formation of intermediate compounds during the
oxidation steps. The reported intermediate compounds are CH3C(O)NH2, CH3O(CH3S)P(O)NH2, (CH3O)2P(O)
SCH3, CH3OP(O)(OH)2, CH3SS(O)2CH3, and (COOH)2. All the formed intermediate compounds were degraded
under the visible light photocatalytic activity of RH-MCM-41/Co3O4 into NO3−, SO42-, PO43-, and CO2 as final
products.

⁎
Corresponding author at: Materials Technologies and their Applications Lab, Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt.
⁎⁎
Corresponding author at: Industrial Engineering Department, College of Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia.
E-mail addresses: abukhadra89@science.bsu.edu.eg (M.R. AbuKhadra), aelsherbeeny@ksu.edu.sa (A.M. El-Sherbeeny).

https://doi.org/10.1016/j.jhazmat.2020.122129
Received 9 November 2019; Received in revised form 14 January 2020; Accepted 16 January 2020
Available online 17 January 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
M.R. AbuKhadra, et al.
1. Introduction
The organophosphorus pesticides used extensively to inhibit the
activities of acetylcholine esterase; however, they were categorized as
highly toxic organic compounds either for human beings or the mam-
mals (Wang et al., 2019; Moctezuma et al., 2007). The high doses of
such pesticides or the long exposure to them are of toxic and carcino-
genic effects and can cause chromosomal aberration and hypoimmunity
(Sinha and Banda, 2018). The main problem in using such compounds
is their tendency to remain at high chemical stability and biodegradable
resistance in several environments like water, plants, fruits, vegetables,
honey the body of the chicken, animals and the human organisms
through the food chain (Wang et al., 2019; Affum et al., 2018; Mahugija
et al., 2018; Hao et al., 2018; Raju et al., 2019). Additionally, the or-
ganophosphorus pesticides characterize by their high water solubility
and can penetrate deeply into the soil until the groundwater and pol-
luted it (Raju et al., 2019).
Acephate (O, S-dimethyl acetylphosphoramidothioate) is a common
type of organophosphate pesticides that were used on vegetable crops
and fruit as a mild insecticide (Liu et al., 2019; Phugare et al., 2012;
Debnath et al., 2019). Acephate is of lower toxicity and chemical sta-
bility than other organophosphate pesticides, and of biodegradable
properties but the high concentration of it and the accumulation of its
residuals are of poisoning effect in the humans (Debnath et al., 2019).
Therefore, several studies focused on the removal of such types of
pesticides involving biological degradation, adsorption, and advanced
oxidation techniques (Raju et al., 2019; Liu et al., 2019; Phugare et al.,
2012; Ramya et al., 2019). The photocatalytic oxidation techniques
based on semiconducting based materials were addressed widely as low
cost, effective and environmentally techniques (Nomura et al., 2020;
Mohammadi and Sheibani, 2019; Sraw et al., 2018; Pineda et al., 2018).
Cobalt oxide, as well as its based composites, was investigated ex-
tensively as potential materials that can be incorporated in several
advanced applications as electrochromic materials, selective solar ab-
sorbents, gas sensors, lithium-ion batteries, oxygen reduction devices
and as heterogeneous photocatalysts (Xu et al., 2016; Abukhadra et al.,
2019; Zhu et al., 2018). The green synthesis methods for metals and
metal oxides using the extracts of plants, algae, and trees as eco-friendly
reducing reagents were recommended strongly to produce materials of
safe properties in water remediation fields (Abukhadra et al., 2018).
The obtained materials by such methods are of non-toxicity, stunning
surface area, biodegradability, high reactivity, high selectivity, and low
cost. Additionally, the used extracts act as a capping surface for the
formed nanoparticles which minimize the possible agglomeration of
them (Abukhadra et al., 2018; Chen et al., 2019). As reported in the
literature, using metal oxides as photocatalysts in their pure forms is of
several drawbacks. The main reported drawbacks are the difficult re-
covering and reusability properties, low adsorption properties, wide
bandgap energies, and fast recombination rates for the electron/hole
pairs (Chen et al., 2019; Xu et al., 2019). Therefore, supporting of metal
oxides into suitable carrier or substrate of effective adsorption proper-
ties and significant surface area was suggested to enhance the catalytic
performance of the metal oxides and solve the detected drawbacks (Liu
et al., 2018a; Xuea et al., 2018).
Mesoporous silica of MCM-41 structures was assessed extensively as
catalysts carriers or substrates (Xu et al., 2016; Guan et al., 2018). It
displays superb properties of highly ordered nanoporous morphology,
tunable pore size, high pore volume, stunning surface area, low toxicity,
and high uptake properties (Xu et al., 2016; Guan et al., 2018; Rabie
et al., 2019). Additionally, the structure of mesoporous silica is of vital
effect in inhibiting the possible agglomeration of the supported metal
oxides by creating bonds between them and the surficial silicon hy-
droxyl bridges of MCM-41 (Du et al., 2018; Seliem et al., 2016).
However, the used silica raw materials of silicon alkoxides and sodium
silicate reduce the probabilities of producing such materials on a
commercial scale for the very expensive cost of the used precursors
2
Journal of Hazardous Materials 389 (2020) 122129
(Rabie et al., 2019). Therefore, in the later periods, several studies have
been performed to produce mesoporous silica from low-cost raw ma-
terials like silica fume, coal fly ash, iron ore tailing, rice husk ash, and
clay minerals (Rabie et al., 2019; Shaban et al., 2017).
Rice husk is a common by-products for rice milling processes and
chemically mainly composed of cellulose (about 50 %), lignin (25 % to
30 %) and silica (15 % to 20 %) while the silica content in the ash of the
rice husk within a range from 90 % to 98 % (Daifullah et al., 2003).
There are about 100 million tons of rice husk produced annually as
agricultural solid wastes in the developing countries which can act as a
significant reserve for reactive silica in the synthesis of MCM-41
(Soliman et al., 2019). Therefore, this focuses on the synthesis of a well-
developed MCM-41 mesoporous structure from silica gel extracted
chemically from rice husk. The synthetic MCM-41 was used as a carrier
for green fabricated cobalt oxide nanoparticles using Peach leaves as
novel nano-composite of high photocatalytic performance in the de-
gradation of acephate pesticide in water. The photocatalytic degrada-
tion tests were conducted under visible light considering different
parameters and the operating mechanism was discussed in the manu-
script in detail.
2. Experimental work
2.1. Materials
Rice husk byproducts were obtained from some local rice produc-
tion mills in Sharqea Governorate, Egypt. Sodium hydroxide pellets of
97 % purity and sulfuric acid of 99.9 % purity were applied in the
extraction processes of silica (Sigma-Aldrich). Ammonium solution
(Sigma-Aldrich (20 % NH3)), ethanol ((95 %) Sigma-Aldrich), and or-
ganic surfactant of Cetyltrimethylammonium bromide (CTAB) ((99 %)
Sigma-Aldrich) are the main chemical and the production of MCM-41.
Peach leaves and cobalt nitrate hexahydrate ((> 98 %) Sigma Aldrich)
were used in the decoration of MCM-41 by green synthesized Co3O4
nanoparticles. The Peach leaves were collected from local Peach farm in
the Fayum city, Egypt. Acephate pesticide of an analytical standard
purity was delivered from Sigma-Aldrich Company for photocatalytic
degradation tests.
2.2. Methods
2.2.1. Extraction of silica gel
The collected rice husk was purified from the attached impurities by
extensive washing with distilled water and then was dried for 24 h at 70
°C. After that, the dried rice husk was ground to fine fraction with size
range from 25 μm to 100 μm using a home blender. 250 g of the ground
rice husk was carbonized for 4 h at 500 °C forming rice husk ash (RHA)
and then produced ash was mixed with 250 mL of NaOH solution (1 M)
under stirring for 4 h at a reaction temperature of 150 °C. In this stage,
the present silica in the ash was dissolved forming soluble sodium si-
licate. Finally, the sodium silica solution was separated by centrifuga-
tion and precipitated as silica gel by the addition of sulfuric acid to it
(Fig. 1).
2.2.2. Synthesis of MCM-41 rice husk ash-based silica gel (RH-MCM-41)
The production of MCM-41 was conducted utilizing the extracted
silica gel from rice husk as a precursor and according to the procedures
of Seliem et al., (Shaban et al., 2017). Firstly, 0.51 g of the surfactant
(CTAB) was dissolved in about 25 mL of distilled water with continuous
stirring for 15 min. Then, 16.34 mL of ammonium solution was mixed
with a surfactant solution by stirring for 15 min. This followed by the
addition of 0.75 g of the extracted silica gel to ammonia/surfactant
mixture under very rapid stirring (1000 rpm) for 30 min and then the
all mixture was transferred into Teflon autoclave sealed with stainless
for hydrothermal treatment at 100 °C for 24 h. After that, the synthetic
solid materials were separated by centrifugation and then washed by
M.R. AbuKhadra, et al.
Fig. 1. Schematic diagram for the synthesis of rice husk silica based MCM-41 decorated by green Co3O4 nanoparticles using Peach leaves. For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
ethanol and distilled water five times. Finally, the fabricated materials
were dried for 12 h at 70 °C and then were heated for 5 h at 450 °C to
confirm the complete removal of the used CTAB template (Fig. 1).
2.2.3. Green decoration of RH-MCM-41 by nano Co3O4 (Co3O4/RH-MCM-
41)
The decoration of the produced RHA MCM-41 by green cobalt oxide
nanoparticles was accomplished after washing and drying the Peach
leaves at 70 °C for 12 h. The dried leaves were then ground by home
blender and 5 g of the ground leaves were boiled with 100 mL of dis-
tilled water for 5 min to prepare Peach leaves extract. After that, 2 g
RHA MCM-41 was dispersed in 50 mL of distilled water under complex
mixing system of stirring (500 rpm) and ultrasonic irradiation (80 %
power) and this followed by addition of 2.5 g cobalt of nitrate hex-
ahydrate under the same mixing system for 60 min. This followed by
the sudden addition of the Peach leaves extract (50 mL) to the mixture
under the effect of magnetic stirring and ultrasonic irradiation for 24 h.
Finally, the prepared composite was isolated by filtration using
Whitman filter paper, washed and dried at 70 °C for 12 h.
2.3. Analytical techniques
The crystalline properties and the dominant oxide phases were ex-
amined considering the resulted XRD patterns for the samples from X-
ray diffractometer (PANalytical-Empyrean). The morphology and the
internal features of the composite were recognized considering the re-
sults of th Scanning-Electron Microscope (Gemini, Zeiss-Ultra 55) and
Transmission Electron Microscope (JEOL-JEM2100) investigation, re-
spectively. The chemical significations were estimated considering the
elemental analysis and the main functional groups using energy dis-
persive X-ray (EDX) and FT-IR Raman spectrometer (Vertex 70). The
optical studies were conducted to measure the bandgap of the compo-
site as compared to the individual components based on the UV–vis
spectra within the area 200 nm–800 nm by UV–vis spectrophotometer
(Shimadzu-M160 PC). The surface areas and pore size distributions of
the produced MCM-41 and the composite were determined by
Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH)
methods, respectively.
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Journal of Hazardous Materials 389 (2020) 122129
2.4. Photocatalytic degradation of acephate pesticide
The photocatalytic degradation of acephate was accomplished
within the photocatalytic reactor of cylindrical Pyrex glass of 15 cm
length and 3.5 cm diameter in the existence of artificial visible light
source. The incorporated light source is an artificial Metal halide lamp
(250 W) with 490 nm as the main wavelength and 18.7 mW/cm2 as the
intensity of the incident light photons in the used reactor. The proce-
dures of the degradation tests involved homogenous mixing of certain
amounts of the studied catalyst with acephate solution in dark for 24 h
to attend the realistic adsorption/desorption equilibrium and avoid the
effect of adsorption in the process. After that, the activity of the syn-
thetic RHA silica gel base Co3O4/RH-MCM-41 composite as photo-
catalyst in the degradation acephate was evaluated considering several
experimental parameters (the catalyst dosage (0.05 g to 0.25 g), the
acephate concentration (50 mg/L to 250 mg/L), the solution pH (from
pH 3 to pH 10), and the irradiation time (10 min–140 min)) after ad-
justing acephate volume at 50 mL and the temperature at about 30 °C.
By the end of each degradation experiment, the Co3O4/RH-MCM-41
fractions were isolated by centrifugation to measure the remaining
acephate pesticide after treatment.
The degradation percentages in the accomplished tests were calcu-
lated based on the obtained concentrations of the remaining acephate
by the HPLC system (Merck/Hitachi). Also, the degradation efficiency
was evaluated based on the remaining total organic carbon (TOC) in the
treated solutions using TOC-VCPH (Shimadzu, Japan). Moreover, the
present inorganic anions in the solution after the degradation processes
were measured using ICS-2100 ion chromatograph. The produced in-
termediate organic compound during the photocatalytic oxidation
process were identified using an Agilent-7890A Series gas-chromato-
graph system connected with a flame ionization detector, a split/split-
less injection system in addition to capillary column ((DB WAX) 30 m
× 0.25 m × 0.25 μm). The injector and the detector operating tem-
perature was adjusted at 280 °C. The oven starting temperature ad-
justed at 120 °C and then increased systematically by 10 °C min for
about 50 min until attained 260 °C. The results are average values for
triplicate tests with standard deviations of 4.6 %, 5.2 %, and 3.8 % for
the HPLC results, the TOC, and ion chromatography results, respec-
tively.
M.R. AbuKhadra, et al. Journal of Hazardous Materials 389 (2020) 122129

Fig. 2. Low angle XRD pattern of RHA silica gel based MCM-41 (A), XRD pattern of the used rice husk (B.1), high angle XRD patterns of RHA silica gel based MCM-
41(RH-MCM-41) (B.2), green synthesized Co3O4/RH-MCM-41 nanocomposite (B.3), EDX investigation of green synthesized Co3O4/RH-MCM-41 nanocomposite (C),
and FT-IR spectra of the used rice husk (D.1), MCM-41 (D.2), green synthesized Co3O4 (D.3), and Co3O4/RH-MCM-41 nanocomposite (D.4) (D). For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

3. Results and discussion 3.1.2. Chemical properties

3.1. Characterization
3.1.1. Structural properties
The crystalline belongings of RHA silica gel-based MCM-41 (RH-
MCM-41) and the green synthesized Co3O4/RH-MCM-41 nanocompo-
site were studied based on their XRD patterns (Fig. 2). The obtained low
angle XRD pattern of RHA silica gel-based MCM-41 reflected the ex-
istence of a strong peak at 2.4° as a 2Theta angle and another two re-
duced peaks at 3.65° and 4.5° (Fig. 2A). The recognized peaks signify
the (100), (110) and (200) crystallographic planes that characterize
MCM-41of highly order hexagonal mesoporous structure (JCPDS 00-
049-1712) (Feng et al., 2019; Zhang et al., 2019).
The obtained high angle XRD patterns of RHA, RH-MCM-41, and
green synthesized Co3O4/MCM-41 were presented in Fig. 2B. The XRD
patterns of RHA and RH-MCM-41 showed broad peaks centered around
2Theta angle of about 22.6° that distinguish the amorphous silica
(Fig. 2B.1 and 2B.2) (Shaban et al., 2017). The synthesis of Co3O4/RH-
MCM-41 as green nanocomposite was confirmed by the detection of the
characteristic spinel Co3O4 peaks at about 18.89°, 31.15°, 36.76°,
45.37°, 59.32° and 65.22° as 2 Theta angles (Fig. 2B.3). All the detected
peaks related to (111), (220), (311), (400), (511) and (440) as lattice
planes, respectively (JCPDS no. 73-1701; JCPDS no. 42-1467). The
calculated crystallite size of the green synthesized cobalt oxide con-
sidering the Scherer equation is 25.6 nm (Soliemanzadeh and Fekri,
2017).
The EDX results for the green synthesized Co3O4/RH-MCM-41 nano-
composite for confirmed the formation of the composite by the dom-
inance of Si, O, and Co as the structural elements (Fig. 2C). The in-
tegration of RH-MCM-41 as silica dominant structure cobalt oxide was
reflected also in functional groups that were evaluated based on the FT-
IR spectra (Fig. 2D). The spectrum of starting rice husk precursor re-
vealed the presence of OeH stretching (3400 cm−1), aliphatic asym-
metrical eCH2 (2900 cm−1), aliphatic symmetrical eCH2 (2800
cm−1), CC or CO bonding (1640 cm]]−1), C–H bending (1458 cm−1
and 1376 cm−1), and SiOe (bands from 570 cm−1 to 1071 cm−1)
(Fig. 2D.1).
For the synthesized RH-MCM-41, the bending vibration of Si-O-
groups that signify the mesoporous structures of hexagonal porous
properties were recognized by the FT-IR band at about 451 cm−1
(Fig. 2D.2) (Sikarwar et al., 2018). The identified bands within the
region from 1080 cm−1 to about 805 cm−1 are the characteristic bands
of the asymmetric and the symmetric stretching of Si-O-Si (Fig. 2D.2)
(Vardast et al., 2019; Wu et al., 2019). Finally, the recognized bands at
1637 cm−1 and 3426 cm−1 were signified to the adsorbed H2O mole-
cules and the silanols groups, respectively (Fig. 2D.2) (Xu et al., 2015).
The obtained spectrum of green synthesized Co3O4 phase demon-
strated two main bands related to OB3 (B = octahedral Co3+) and ABO
(A = tetrahedral Co2+) vibrations of the spinel crystal lattice which
were recognized at about 574 cm−1 and 661 cm−1, respectively
(Fig. 2D.3) (Abu-Zied et al., 2015). The detection of band related to the
C]C groups at about 1120 cm−1 might be related to the possible
capping of the synthetic nanoparticles by the components of the Peach

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M.R. AbuKhadra, et al. Journal of Hazardous Materials 389 (2020) 122129

Fig. 3. SEM images of RHA silica gel based MCM-41 (A), focus SEM image on RH-MCM-41particles (B, C), SEM image of RH-MCM-41 decorated by green cobalt oxide
nanoparticles (D), TEM image of RH- MCM-41 (E), and TEM image of RH-MCM-41 decorated by cobalt oxide nanoparticles (F). For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

leaves extract (Fig. 2D.3) (Fariasa et al., 2018). The resulted spectra of
green synthesized Co3O4/RH-MCM-41 nano-composite nanoparticles
showed the same bands of pure RH-MCM-41 with a small deviation
from their positions in addition to the existence of the significant bands
of Co3O4 (Fig. 2D.4).

3.1.3. Morphological properties

The morphological properties were studied based on the SEM and
TEM images of RHA silica gel-based MCM-41 and green synthesized
Co3O4/RH-MCM-4 nanocomposite (Fig. 3). The synthetic RH-MCM-41
reflected its formation as a network structure from interlocked wormy
(Fig. 3A and B). The interlocked particles commonly aggregated in
flower-like shapes with interstitial secondary pores of Nano-scale dia-
meters (Fig. 3C). After the loading of green cobalt oxide, the RH-MCM-
41 particles appeared to be coated by nanoparticles of nearly spherical
or elliptical shape (Fig. 3C).
The previous morphological investigation was supported by the
obtained TEM images (Fig. 3E and F). The synthetic RH-MCM-41 using Fig. 4. Nitrogen adsorption/desorption isotherm curves of glass based MCM-41
the extracted silica gel from rice husk ash displayed well developed (A), and Co3O4/MCM-41 (B).
spherical particles that recognized widely for highly ordered porous
structures of MCM-41 (Fig. 3D). The green decoration of RH-MCM-41 attributed to the predicted partial blocking of MCM-41 pores with
by Co3O4 nanoparticles was confirmed by the appearance of the me- during the green supporting of cobalt oxide nanoparticles into it
soporous silica as spherical grains coated by nano-grains with good (Fig. 4). The measured surface area, average pore diameter, pore-vo-
preservation for the main morphological properties. lume, and wall thickness are 735 m2/g, 6.52 nm, 0.77 cm3/g, and 2.34
nm, respectively. However, the measured values of green Co3O4/ MCM-
3.1.4. Textural properties 41 nanocomposite are 608 m2/g, 4.72 nm, 0.51 cm3/g, and 2.57 nm, for
The obtained isotherm curves of nitrogen adsorption/desorption surface area, average pore diameter, pore-volume, and wall thickness,
results for both RH-MCM-41 and green synthesized Co3O4/RH-MCM-41 respectively.
nano-composite demonstrated IV type isotherm curves that can be
formed by mesoporous structures of uniform cylindrical mesopores as
that characterize MCM-41 (Fig. 4) (Sikarwar et al., 2018; Farhadi et al., 3.1.5. Optical properties
2013). The identified hysteresis lops in the plotted curves can be clas- The obtained UV–vis spectra of RH-MCM-41, green Co3O4 nano-
sified as H1 type which assigned mainly to synthetic solid materials of particles and green synthesized Co3O4/RH-MCM-41 nanocomposite
internal cylindrical channels or synthetic agglomerated particles of were presented in Fig. S1. The pure MCM-41 exhibit UV–vis spectra of
spheroidal forms (Farhadi et al., 2013). The detected declination in the no characteristic absorption bands (Fig. S1.A). The UV–vis spectrum of
adsorbed nitrogen intensity of the green Co3O4/RH-MCM-41 nano- green Co3O4 nanoparticles as well as the synthetic Co3O4/RH-MCM-41
composite as compared to RH-MCM-41 as a pure phase might be nanocomposite showed the presence of two main broad absorption

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M.R. AbuKhadra, et al. Journal of Hazardous Materials 389 (2020) 122129

bands within the area from 240 nm to about 350 nm and from 630 nm
to about 780 nm (Fig. S1.A). The observed bands were formed as a
result of the predicted charge transfer of O2−→Co2+ and O2−→Co3+
forming the first band and the second band, respectively (Huang et al.,
2015; Vennela et al., 2019; Hai et al., 2016; Li et al., 2018). The ab-
sorption intensity of Co3O4/RH-MCM-41 nanocomposite spectrum is
higher than that pure Co3O4 revealing a considerable improvement in
the optical properties of Co3O4 after supporting it into MCM-41.
The calculated bandgap energies of both Co3O4 and green Co3O4/
RH-MCM-41 nano-composite were obtained considering the Tauc's
formula and the resulted values are 2.01 eV and 1.51 eV, respectively
(Fig. S1.B). The obtained bandgap for the green synthesized Co3O4 is
very close to the values which were reported in the literature (Huang
et al., 2015; Vennela et al., 2019; Hai et al., 2016; Li et al., 2018). Such
reducing in the value of the band gap energy after loading of cobalt
oxide nanoparticles into the synthetic RH-MCM-41 porous structure
reflected the role of such porous substrates in providing the loaded
photocatalysts high exposed properties for the incident photons by the
regular orientation of them into its structure and by preventing them
from the agglomeration (Soliemanzadeh and Fekri, 2017).
3.2. Photocatalytic removal of acephate pesticide
3.2.1. Effect of pH
As the solution pH is a vital factor in all water treatment systems as
it controls the surface charges of the prepared Co3O4/RH-MCM-41
nano-composite in addition to the ionization degrees. Moreover, it is
the main controlling parameter which is of a direct impact on the
speciation of organic and inorganic dissolved ions (Han et al., 2009).
Thus, the influence of acephate solution pH on controlling the perfor-
mance of Co3O4/RH-MCM-41 photocatalytic activity was addressed
within an experimental range from about pH 3 to pH 10 and at fixed
parameters (100 mg/L concentration, 50 mL volume, 60 min time and
at 30 °C as temperature) (Fig. 5A). The recognized oxidation results
verified significant improvement in the percentages from about 14.7 %
to 69 % with the systematic raising in the acephate solution pH from pH
3 to pH 10. i.e., the oxidation of acephate using Co3O4/RH-MCM-
41photocatalyst is preferable to be done in the alkaline environments.
This recognized behavior was elucidated to be a normal result for
the expected de-protonation of Co3O4/RH-MCM-41functional groups
with testing acephate solutions of higher pH values. This, in turn, re-
sulted in saturation of the green composite by negative charges that are
of a strong repulsion forces with the dissolved acephate ions that are of
positive charges (Fu et al., 2018; Juang and Chen, 2014; Mohamed
et al., 2018). Additionally, such surficial properties that are of strong
impacts on increasing the quantities of the uptake acephate molecules
and this is of critical value in achieving effective photocatalytic oxi-
dation results (Alalm et al., 2015).
3.2.2. Effect of catalyst dosage at different time intervals
The influence of performing the oxidation experiments of acephate
at different illumination intervals using different quantities of Co3O4/
RH-MCM-41 was exemplified graphically in Fig. 5B at fixed conditions
of 100 mg/L as concentration, 50 mL as volume, 30 °C as temperature,
and pH 8. The main trends of the curves for all the applied Co3O4/RH-
MCM-41 masses demonstrated consistent intensification in the achieved
oxidation percentages with a reliable increase in the tested illumination
intervals showing a slight reduction in the experimental oxidation rates.
This oxidation behavior was clarified to be associated results for the
enrichment of Co3O4/RH-MCM-41 by numerous uptake receptors and
the high availability of the present oxidizing species at the initial stages
of the test which promotes the degradation rate of acephate (Alalm
et al., 2015). The predicted decrease in main affecting radicals with the
continuous consumption of them with expanding the reaction time
causes observable declination in the degradation rate at the final stages
of the reaction until achieving equilibrium state (Alalm et al., 2015;
Shaban et al., 2018).
Moreover, incorporation of higher quantities of Co3O4/RH-MCM-41
resulted in a noticeable improvement in the activity of Co3O4/RH-
MCM-41 of photocatalyst during the visible light oxidation of acephate.

Fig. 5. Effect of the main factors on the degradation of acephate using Co3O4/RH-MCM-41 as photocatalyst (100 mg/L concentration, 50 mL volume, pH 8 and room
temperature); (A) pH, (B) illumination time for different studied dosages, (C) acephate concentrations, and (D) reusability of Co3O4/RH-MCM-41 green nano-
composite, (E) TOC concentrations in the treated solutions, and (F) the main inorganic anions that were detected after the degradation process (The error bars refer to
the statistical differences for the results of triplicate tests with standard deviations of 4.6 %, 5.2 %, and 3.8 % for the degradation results, the TOC results, and the
inorganic anions results, respectively). For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

6
M.R. AbuKhadra, et al.
The described improvement in the oxidation removal results were il-
lustrated in the literature to be related to the predicted rise in the
Co3O4/RH-MCM-41 surface area, the exposed catalytic sites to the light
irradiation, and adsorbed quantities of acephate molecules
(Soliemanzadeh and Fekri, 2017; Huang et al., 2008). This also asso-
ciated with enrichment in the generated oxidizing species which ac-
celerate the degradation rate of the studied organic compounds even
within short illumination periods (Daifullah et al., 2003; Zheng et al.,
2016). Therefore, the studied acephate concentration (100 mg/L) was
completely degraded after 140 min, 90 min, 70 min, and 60 min using
0.1 g, 0.15 g, 0.2 g, and 0.25 g of Co3O4/RH-MCM-41 green nano-
composite, respectively.
3.2.3. Effect of acephate concentration
The applicability of degrading higher concentrations of acephate
using Co3O4/RH-MCM-41 catalyst was evaluated within a range from
50 mg/L to about 250 mg/L. The test was conducted after fixing the
Co3O4/RH-MCM-41 dose at 0.25 g, the acephate volume at 50 mL, pH 8
and at 30 °C as temperature (Fig. 5C). The achieved results verified
complete oxidation of 50 mg/L, and 100 mg/L, 150 mg/L, 200 mg/L of
acephate after 40 min, 60 min, 100 min, and 140 min, respectively.
Therefore, the synthetic Co3O4/RH-MCM-41 is promising photocatalyst
that can be applied effectively in the degradation of acephate pesticide
in the presence of visible light at short oxidation intervals. During the
degradation tests, the oxidation rate and the oxidation percentages
emphasized recognizable decrease with testing the higher concentra-
tions of acephate pesticide. This might be credited to the over adsorp-
tion of acephate molecules on the surface of Co3O4/RH-MCM-41 by
increasing its concentration in the aqueous solutions which can make
capping cover for catalyst surface from the direct interaction with the
incident light and reduce the produced oxidizing species (Alalm et al.,
2015; Huang et al., 2008).
3.2.4. Reusability
The reusability property of Co3O4/RH-MCM-41 to be used effec-
tively in several degradation tests of acephate is essential to assess the
suitability of the catalyst to be used in the realistic and the commercial
scale. The reusability tests of Co3O4/RH-MCM-41 were repeated form
eight runs considering the acephate concentration at 100 mg/L, the
catalyst dosage at 0.25 g, the acephate volume at 50 mL, pH 8, 30 °C as
temperature, and the visible light illumination time at 60 min (Fig. 5D).
The prepared Co3O4/RH-MCM-41 nanocomposite exhibited high sta-
bility and was reused in several degradation runs at high removal
percentages. The accomplished degradation percentages are 100 %
(Run1), 100 % (Run2), 98.4 % (Run3), 96.6 % (Run4), 95.2 % (Run5),
92.4 % (Run6), 89.3 % (Run7), and 85.7 % (Run8). Additionally, the
results can be enhanced greatly by increasing both the incorporated
Co3O4/RH-MCM-41 quantities and the visible light illumination periods
to be used in other reusing runs.
3.2.5. Changes in the TOC content during the degradation process
The oxidation of organophosphorus pesticides as organic com-
pounds resulted in the consistent conversion of them into CO2 as final
products in addition to inorganic anions from the present heteroatom
that remains common in the treated solutions (Jing et al., 2019). The
detection of the existing TOC in the treated solutions after using dif-
ferent masses Co3O4/RH-MCM-41 doses (0.05 g to 0.25 g) within ex-
periment irradiation intervals from 10 min to 140 min was performed
as the main indicators for the photocatalytic mineralization of acephate
after fixing the concentration at 100 mg/L, the temperature at 30 °C,
the volume at 50 mL and the pH at pH 8 (Fig. 5E). The TOC content
exhibited a continuous reduction in its content with increasing either
the applied Co3O4/RH-MCM-41 masses or the visible light irradiation
period. The calculated removal percentages of TOC are of considerably
lower values than that obtained for the removal of acephate confirming
the formation of intermediate compounds during the degradation
7
Journal of Hazardous Materials 389 (2020) 122129
process. The best oxidation results for acephate into CO2 without TOC
residuals in the treated solutions were obtained after incorporation of
0.15 g, 0.2 g, and 0.25 g of Co3O4/RH-MCM-41 as photocatalyst doses
for 90 min, 80 min and 70 min of visible light irradiation, respectively.
This can be attributed to the high availability of the oxidation radicals
by incorporation of high doses of the composite which provide more
chances to degrade the original acephate pesticide as well as its deri-
vatives intermediate compounds with time. The formation of such in-
termediate compounds can explain the degradation mechanism of
acephate in the Co3O4/RH-MCM-41 photocatalytic system.
3.2.6. Oxidation intermediate compounds and inorganic anions
The possible formation of an intermediate organic compound, as
well as the inorganic anions during the oxidation of acephate pesticide,
was followed to predict the pathway of the photocatalytic degradation
mechanism of it using Co3O4/RH-MCM-41 under the visible light
source considering the concentration at 50 mg/L and the other condi-
tion at fixed values of 50 mL as volume, pH at pH8, temperature at 30
°C. The analytical results verified the existence of SO42−, NO3-, and
PO43- as principal mineralization byproducts during the oxidation
process using 0.25 g of the green nanocomposite for different de-
gradation periods (Fig. 5F). The content of the present inorganic anions
displayed a noticeable increment with raising the oxidation time in-
terval. The presence of NO3- might be related to the expected cleavage
of PeO bond and the existence of SO42− as well as PO43- was assigned
mainly to the continuous oxidation of the sulfur-bearing compounds
(Jing et al., 2019).
The principal organic intermediate compounds which were re-
cognized GC–MS during the photocatalytic oxidation of acephate over
Co3O4/G-MCM-41 were listed in Table 1. The identified compounds are
common identified intermediate compounds and support greatly the
observed trends for the reduction in the TOC in the treated solutions.
The main intermediate compounds are acetamide, phosphorothioic
acid, O, O’, S-dimethyl ester, phosphoramidothioic acid, O, S-dimethyl
ester, monomethyl phosphate, methyl methanethiosulfonate, and
ethanedioic acid. The phosphorothioic acid, O, O’, S-dimethyl ester and
phosphoramidothioic acid, O, S-dimethyl ester were formed by the
breaking of PeO bonds Fu et al., 2018). The other detected inter-
mediate organic compounds were formed by the cleavage of the present
Table 1
The formed organic intermediate compounds during the degradation acephate
pesticide by Co3O4/RH-MCM-41.
Name Structure Structural CAS
Formula
O,S-Dimethyl acetyl C4H10NO3PS 30560-19-1
phosphoramidothioate
(Acephate)
Acetamide CH3C(O)NH2 60-35-5
Phosphoramidothioic acid,O,S- CH3O(CH3S)P 10265-92-6
dimethyl ester (O)NH2
Phosphorothioic acid,O,O’,S- (CH3O)2P(O) 152-20-5
dimethyl ester SCH3
Monomethyl phosphate CH3OP(O) 812-00-0
(OH)2
Methyl methanethiosulfonate CH3SS(O)2CH3 2449-92-0
Ethanedioic acid (COOH)2 144-62-7
M.R. AbuKhadra, et al.
Fig. 6. The adsorption and photocatalytic removal of acephate using RH-MCM-
41, Co3O4, and Co3O4/RH-MCM-4 nanocomposite (The error bars refer to the
statistical differences for the results of triplicate tests with standard deviations
of 4.6 %).
PeS bonds.
3.3. Effect of the integration process
To study the influence of the combination of RH-MCM-41 and
Co3O4 green nanoparticles in new hybrid nanocomposite on the ad-
sorption and photocatalytic performances, the adsorption of acephate
as well as its photocatalytic oxidation properties using the composite
were compared with RH-MCM-41 and green Co3O4 as separated com-
ponents (Fig. 6). The test was conducted by incorporation of Co3O4/RH-
MCM-41 catalyst (0.25 g) with 50 mL of acephate solution (100 mg/L)
for 60 min at pH 8 and in the dark as the studied adsorption test and in
the presence of the light source as the photocatalytic test. The ad-
sorption removal of acephate Co3O4, RH-MCM-41, and Co3O4/RH-
MCM-41 was recorded at percentages of 1.3 %, 2.4 %, and 5.6 %, re-
spectively considering the time at 60 min (Fig. 6). The results verified
enhancement in the properties of Co3O4/RH-MCM-41 by 76.8 % and
57.14 % higher than Co3O4 and RH-MCM-41, respectively.
Using RH-MCM-41 as photocatalyst is of no effect in removal per-
centages of acephate pesticide i.e., it is of not photocatalytic properties.
Incorporation of Co3O4 in the presence of visible light resulted in higher
removal percentage to be 18.8 % confirming strong photocatalytic ac-
tivity for it in the oxidation of acephate. Loading of Co3O4 onto RH-
MCM-41 (Co3O4/RH-MCM-41) resulted in stunning photocatalytic ac-
tivity achieving 100 % oxidation result with enhancing the value of
81.2 % higher than the achieved value using Co3O4 as a separate phase.
The reported improvement either in the adsorption removal of
acephate or the visible light photocatalytic oxidation by Co3O4/RH-
MCM-41as compared to their components might be attributed to (a) the
stunning surface area and the adsorption which was reported com-
monly to RH-MCM-41, (b) the formation of the composite associated
with exposing of different groups which in turns provide more receptor
sites that can adsorb high quantities of acephate molecules, and (c) the
distribution of the synthetic Co3O4 nanoparticles on RH-MCM-41 in
homogenous manner without agglomeration reflected a noticeable in-
crease in the exposed surface area of such particles providing high
chances for effective interactions between them and the incident light
(Wang et al., 2019; Chen et al., 2019; Prabhu et al., 2018; Sun et al.,
2019).
3.4. Degradation mechanism
3.4.1. The kinetic behavior
The kinetic studies of the acephate degradation system using
Co3O4/RH-MCM-4 were assessed considering the fitting results of the
8
Journal of Hazardous Materials 389 (2020) 122129
oxidation data with the theoretical first-order as well as second-order
models and their repetitive equations are Eqs. 1 and 2, respectively
(Chen et al., 2019):
Ct = C0 e−k1 t (1)
1 1
= + k2t
Ct C0 (2)
The obtained regression coefficient values verified best fitting for
the degradation of acephate at studied concentrations lower than 250
mg/L with the first-order model achieving R2 values higher than 0.9
(Fig. S2; Table S1)). This suggested the predicted controlling of the
oxidation process by one of the operating factors and reflected the
possible removal of acephate by adsorption in a parallel process with
photocatalytic degradation (Alalm et al., 2015). Additionally, the re-
duction in the values of kinetic rate constant with the oxidization of
higher acephate concentrations is of high agreement with the achieved
experimental results. The kinetic behavior with applying different
masses of Co3O4/RH-MCM-4 also displayed the best fitting with the
First-order model with a noticeable increase in the rate kinetic constant
revealing the improvement of the photocatalytic performance with the
incorporation of higher masses (Fig. S2; Table S1).
3.4.2. Effective oxidizing radicals
The identification of the main effective oxidizing species during the
oxidation of acephate by Co3O4/RH-MCM-41 is of valuable contribu-
tions in the recognition of the photocatalytic mechanisms. The oxi-
dizing radicals in the studied system were identified considering the
results of effective species capturing experiments. The accomplished
procedures of the trapping tests involved addition of Co3O4/RH-MCM-
41 (0.25 g) to 50 mL of acephate solutions containing 1 mmol of cap-
turing reagents including Isopropanol (IP) (for hydroxyl radicals),
EDTA-2Na (for electron/hole pairs) and 1–4 benzoquinone (BQ) (for
superoxide radicals) for 60 min in the existence of visible light source.
The recognized oxidation percentage demonstrated a reduction in the
value to 8.55 %, 92.4 %, and 74.7 % with the mixing of IP, EDTA-2Na,
and BQ, respectively. i.e., the hydroxyl radicals are the dominant oxi-
dizing species during the degradation of acephate utilizing Co3O4/RH-
MCM-41.
The photoluminescence (PL) technique was applied to confirm the
previous results about the dominance of hydroxyl radicals as the main
oxidizing radicals during the degradation of acephate pesticide over
Co3O4/RH-MCM-41. This was conducted in the presence of terephthalic
acid (TA) as the incorporated probe molecule and the detection of hy-
droxyl radicals can be evaluated according to the increase in the in-
tensity of the PL spectrum of 2-hydroxyterephthalic acid which pro-
duced by the interaction between the hydroxyl radicals and
terephthalic acid. The PL spectra were estimated at a wavelength of 425
nm and principal determination steps involved homogeneous mixing of
0.25 g of Co3O4/RH-MCM-41, 20 mL of TA (5 × 10−4 M) and sodium
hydroxide solution (2 × 10-3 M). The light source was set at 10 cm as
the vertical distance from the mixture and provided with a 420 nm
cutoff filter. By the end of the selected illumination intervals, the
treated solutions were separated by filtration to and the PL-spectrum of
each solution was measured at a wavelength of 425 nm and an ex-
citation wavelength of 315 nm. The recognized spectra in Fig. S3
confirmed no photocatalytic activity for the composite in the dark
which emphasized in the straight–line PL curve in the absence of the
used light source. Under the illumination effect, the PL-spectra showed
a systematic increment in the intensity of the observed PL band con-
firming increasing in the quantity of the captured hydroxyl radicals
during the excitation of Co3O4/RH-MCM-41 with increasing the illu-
mination period. i.e., the quantities of the photo-created hydroxyl ra-
dicals over the synthetic Co3O4/RH-MCM-41 nanocomposite increase
with time (Fig. S3).
M.R. AbuKhadra, et al.
Fig. 7. Schematic diagram for the suggested photocatalytic degradation of acephate by Co3O4/RH-MCM-41 green nanocomposite. For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this article.)
3.4.3. The degradation pathway
As documented in the literature, the photocatalytic oxidation of any
dissolved organic materials can be performed within three mains steps.
At the initiative of the process, the dissolved organic molecules should
be adsorbed on the surface of Co3O4/RH-MCM-41 nanocomposite and
then the incident visible light photons should be absorbed by the
composite causing significant excitation of the external electrons to the
conducting band. The excitation process associated with the charge
transfer process and formation of oxidizing radicals (hydroxyl radicals,
electron holes, and superoxide radicals) that are the main components
in the degradation of the investigated organic molecules (Chen et al.,
2019; Liu et al., 2018b) (Fig. 7). The descriptive equations of the pre-
dicted oxidation mechanisms of acephate using Co3O4/RH-MCM-41
were signified by Eqs. 3–9:
Co/ MCM + hv→ Co/MCM (e−CB , h+VB )
Co/MCM(e−) + O2 → Co/ MCM+ O•2−
(Co/MCM)e− + AS. P→ (Co/MCM ) e− + AC. P+ •
AC. P+ • + O2• − → Degraded products
Co/MCM (h+) + H2 O → Co/ MCM+ H+ + OH•
Co/MCM (h+) + AC. P+ •→Degraded Product
AC. P+ • + OH• → Degraded products
The degradation of acephate first involved broken for the NeC bond
followed by the PeN and CCe bonds (Jing et al., 2019). The non-de-
tection of Methamidophos that is of higher stability than acephate and
the reported increase in the PO43− concentration reflected poor
chances for the breaking of NeC bond during the initial stages of the
reaction. Similar behavior was observed by Negishi et al., (Negishi
et al., 2012) and Zheng et al., (Jing et al., 2019); and the predicted
mechanism was suggested to involve initial oxidation of the acetyl
functional group in acephate pesticide followed by the oxidation of the
formed CH3C(O)NH2 and CH3O(CH3S)P(O)OH (Fig. 8). The CH3O
(CH3S)P(O)OH is an unstable compound that commonly converts into
(CH3O)2P(O)SCH3 by oxidation which in turn can be oxidized to CH3OP
(O)(OH)2. The C atom of CH3O(OH)2P(O) might be eliminated by either
the H-abstraction or under the interaction effect of hydroxyl radicals
(Vorontsov et al., 2002). Also, the P atom affected by oxidation and
reduction reactions forming H3PO4 and H3PO3 as end byproducts. The
remaining intermediate organic compounds under the extensive effect
of the photocatalytic system converted into NO3-, SO42-, and PO43-
(Fig. 8).
Journal of Hazardous Materials 389 (2020) 122129
4. Conclusion
The Co3O4/MCM-41 green nanocomposite was synthesized from
rice husk based silica gel and using the green extract of Peach leaves as
reducing reagent for cobalt salt. The composite was as green photo-
catalyst in the degradation of Acephate pesticide under visible light
illumination. It achieved complete removal for different concentrations
of acephate after 40 min (50 mg/L), 60 min (100 mg/L), 100 min (150
mg/L) and 140 min (200 mg/L) reveling promising photocatalytic ac-
tivity. The degradation steps involved the formation of the intermediate
compound before their complete oxidation into NO3−, SO42-, and PO43-
over Co3O4/MCM-41 after 70 min of irradiation. The hydroxyl radicals
were identified as the principal oxidizing species during the degrada-
tion pathway of acephate pesticide over Co3O4/MCM-41.
(3) Recommendation
(4) Further studies will be conducted to investigate the adsorption
properties of RH-MCM-41 and Co3O4/RH-MCM-41 nanocomposite; and
(5) the main controlling mechanism. Additionally, further work will be
accomplished to investigate the photocatalytic performance of Co3O4/
(6) RH-MCM-41 as photocatalyst under different reaction temperature.
(7) Credit statement
(8) Dr. Mostafa R. Abukhadra, the corresponding authors of the
manuscript declare that the inserted descriptions accurate and the
manuscript were submitted after the acceptance of all the authors. Dr.
(9)
Mostafa R. Abukhadra synthesized the material, characterized the
products, share the degradation tests, interpretation of the results and
writing the manuscript. Mrs. Aya made the degradation tests, con-
ducted the analysis and share in the interpretation of the results. Dr.
Ahmed M. El-Sherbeeny share in the synthesis of the materials, char-
acterize the products, interpretation of the results and writing the
manuscript. Dr. Mohammed A. Elmeligy made the analysis of the
treated solutions, interpret the degradation results, and share in writing
the manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors extend their appreciation to the Deanship of Scientific
Research at King Saud University for funding this work through
9
M.R. AbuKhadra, et al.
Fig. 8. The predicted degradation mechanisms of Acephate pesticide and generated intermediate compounds.
research group number RG-1440-047.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122129.
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