Synthesis and Characterization of Metal Oxide Nano
Synthesis and Characterization of Metal Oxide Nano
Synthesis and Characterization of Metal Oxide Nano
*
Abdullah G ALanazi , Mohamed A Habila , Zeid A ALOthman , Ahmed Yacine Badjah-Hadj-Ahmed
doi: 10.20944/preprints202312.0084.v1
Keywords: hybrid materials; zinc oxide nanoparticles; carbon; iron (III) oxide nanoparticle; adsorption; ki-
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Article
Synthesis and Characterization of Metal Oxide
Nanoparticles Anchored Carbon as Hybrid
Adsorbents for Effective Heavy Metals-Uptake
from Wastewater
Abdullah German Alanazi, Mohamed A. Habila *, Zeid A. ALOthman
and Ahmed-Yacine Badjah-Hadj-Ahmed
Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
* Correspondence: [email protected]; Tel.: +966-1-4674-198; Fax: +966-1-4675-992
Abstract: Hybrid materials derived adsorbents have showed a great applicable efficiency in various fields
including industrial uses and environmental remediation. Herein, the zinc oxide nanoparticles anchored
carbon (ZnO-C) is fabricated and utilized for wastewater treatment by adsorption of Zn(II), Cd(II), Co(II) and
Mn(II). The surface and structural characteristics are examined by TEM, SEM, XRD, FTIR, EDS and BET surface
area. The Kinetics and equilibrium investigations are applied to optimize the adsorptive removal of Zn(II),
Cd(II), Co(II) and Mn(II) onto ZnO-C. Results indicated formation of ZnO-C in crystalline spherical granules
with nano-size between 29.3 and 48.8 nm. In addition, the spherical granules are gathered to form clusters. The
FTIR indicated that the ZnO-C surface is rich with OH groups and ZnO. The adsorption capacity is reported
as 212, 209, 200 and 230 mg/L for Zn(II), Cd(II), Co(II) and Mn(II) respectively. The optimum condition for
maximum adsorption were pH between 5 and 6, contact time of 180 min and adsorbent dose of 0.1 g/L. The
adsorptive removal data modeling for uptake of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C showed
agreement with the assumption of pseudo 2nd order kinetic model and Freundlich isotherm suggesting fast
adsorption rate and multilayer mechanism. The achieved adsorption capacity using the prepared ZnO-C is
more effective compared to ZnO, carbon, Fe3O4 and Fe3O4-C. Real wastewater samples are applied including
valley water, industrial wastewater and rain wastewater and evaluated for applicable uptake of Zn(II), Cd(II),
Co(II) and Mn(II) using ZnO-C and Fe3O4-C with high efficiency.
Keywords: hybrid materials; zinc oxide nanoparticles; carbon; iron (III) oxide nanoparticle; adsorption;
kinetic and equilibrium studies
1. Introduction
The heavy metals polluted effluents are originated from industrial activities and cause serious
environmental hazard [1]. Heavy metals such as manganese, cadmium, cobalt and zinc are naturally
occurring elements. Small amounts of these elements are common in our environment and they are
actually necessary for our health. But large amounts of any of them may cause acute or chronic
toxicity [2]. Heavy metals in human bodies tend to bioaccumulate, which may result in damaged or
reduced mental and central nervous function, and damage to blood composition, lungs, kidneys and
liver. For example, cobalt, one of the common toxic metals affecting the environment, is present in
the waste water of nuclear power plants and many other industries such as mining, metallurgical,
electroplating, paints, pigments and electronic [3]. High levels of cobalt may affect several health
troubles such as paralysis, diarrhea, low blood pressure, lung irritation and bone defects [4].
Manganese, is naturally occurring metallic element, which may contaminate groundwater as a result
of weathering and the leaching of manganese-bearing rocks into the aquifers. Aquifers in certain
regions of Quebec, other portions of Canada, and other countries contain naturally high quantities of
manganese (including Sweden, Vietnam, Bangladesh, Morocco, and others) [5,6]. Although
manganese is a vital trace element, it may be a strong neurotoxin in excess. The amount of manganese
in drinking water is not regulated in the United States or Canada since it is mostly seen as an aesthetic
problem. Manganese concentrations more than 100 g/L encourage the discoloration of laundry and
hygienic items and provide an unpleasant flavor to drinks [7]. Zinc is extensively present in
environmental components including food and water [8,9]. Zinc is a substance having a
recommendation value of 5.00 mg/L in drinking water, according to the European Commission
Drinking Water Directive, the World Health Organization and its Guidelines for Drinking Water
Quality, and the US Environmental Protection Agency (EPA). The over-dose exposure to zinc leads
to immediate symptoms such as vomiting and nausea and anemia [10]. Cadmium is one of the most
harmful non-essential heavy metals in the environment, and it comes from many sources, including
the wastewater from the metal plating industry, nickel-cadmium batteries, phosphate fertilizer,
mining, pigments, stabilizers, alloys, petroleum refining, welding, and pulp industries, produce
elevated levels of cadmium ions [31,32]. Cadmium toxicity resulted in kidney damage, cancer and
lung dysfunction [11]. The cadmium recommended value for drinking water is 0.005 mg/L [12].
Therefore, many research investigations have been conducted to develop tools for wastewater
purification. The removal of heavy metals pollutants from water can be achieved by many methods
including chemical precipitation, flotation, biosorption, electrolytic recovery, membrane separation,
removal by adsorption onto minerals or activated carbon [13–16]. Usually these methods have been
restricted by many factors, such as processing efficiency, operational method, energy requirements,
and economic benefit. Adsorption is an effective, straightforward, and affordable technique for
removing heavy metals from water [17,18]. An effective sorbent should has a high heavy metal
sorption capacity, low cost, renewable, and durable [19]. Although it is costly and ineffective for
treating water, carbon materials are reported as an efficient adsorbent for heavy metals uptake
[20,21]. The carbon incorporated materials have durability and poses physicochemical stability which
enhance the wastewater treatment applications [22].
Recently, nanostructure-based materials have shown higher efficiencies in wastewater treatment
applications compared to traditional adsorbents [23,24]. Nanostructure adsorbents such as
manganese oxides and titanium oxides, iron oxides and zinc oxides have shown promising results in
removal of heavy metals. Zinc oxide is reported to have been reported as proper adsorbent for organic
and inorganic pollutants, however, the process suffers from many technical problems related to
operating and efficiency [1,25–28]. The combination of metal oxides with carbon produce a hybrid
material with superior properties compared to the single metal oxide oxides or pure carbon. In
addition, the nano-adsorbent such as zinc oxide nanoparticles modified with graphene have showed
an improved tendency to decompose organic pollutants [29]. The researches in this field is still
continuous to improve the efficiency of nano-composite in removal of pollutants, even by adsorption
or by photocatalytic degradation. Due to its outstanding optical, electrical, photonic, and
microbiological capabilities among others, zinc oxide (ZnO) nanoparticles are widely employed in
many new multifunctional materials. The zinc oxide nanoparticles derived materials could be
utilized in various manufacturing sectors like rubber, plastics, cosmetics, pharmaceuticals, paints,
soap, batteries, electrical equipment, optoelectronics, biomedical science, etc., the demand for zinc
oxide is always rising [30,31]. Hybrid materials including carbon and metal oxide nanoparticles have
been reported as novel category of materials with enhanced properties for catalysis, adsorption,
precontraction and medical applications [32–34]. Thus, this work aimed to fabricate zinc oxide
anchored carbon (ZnO-C) as hybrid porous adsorbent using solvothermal process to enhance the
adsorption capacity for heavy metals uptake. In addition to characterized the produced ZnO-C with
SEM, TEM, XRD, surface is and EDS. Furthermore, to compare the achieved adsorption capacity with
other adsorbents including zinc oxide, carbon and Fe3O4-C. Moreover, to purify wastewater samples
using the developed ZnO-C hybrid adsorbent materials.
2. Experimental
2.1. Materials
The materials including zinc acetate, polyethylene glycol, sodium hydroxide, zinc oxide,
hydrochloric acid, zinc nitrate, cobalt nitrate, cadmium nitrate and manganese nitrate are brought
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with analytical grade from Sigma USA. Carbon and Fe3O4-C are obtained from our laboratory as
prepared according our previously published work by Habila et al.
2.3. Optimization of adsorptive removal of Zn(II), Cd(II), Co(II) and Mn(II) for wastewater purification
0.02 g of the metal oxide nanoparticles including ZnO or Fe3O4 or their derived carbon hybrid
materials including ZnO-C or Fe3O4-C was mixed with 20 mL of mixed heavy metals solution
including Zn(II), Cd(II), Co(II) and Mn(II). Then the pH was optimized to pH using phosphate buffer.
The mixture was kept under shaking condition at room temperature for 180 min. Then the aqueous
solution was separated by centrifuge. The change in the heavy metal ions concentration was detected
by ICP-MS. The adsorptive removal- capacity was evaluated from Equation 1
qe = (C0−Cf). V/M, (1)
where qe is the adsorptive removal-capacity (mg/g) for Zn(II), Cd(II), Co(II) or Mn(II) onto the metal
oxide nanoparticles including ZnO or Fe3O4 or their derived carbon hybrid materials including ZnO-
C or Fe3O4-C
C0, the initial concentration of Zn(II), Cd(II), Co(II) or Mn(II)
Cf is the final concentration of Zn(II), Cd(II), Co(II) or Mn(II) after adsorption.
V is the volume of the solution of whole adsorption mixture.
M is the mass of the metal oxide nanoparticles including ZnO or Fe3O4 or their derived carbon
hybrid materials including ZnO-C or Fe3O4-C
The previously described steps for adsorptive removal were operated several times to assess the
effects of pH of adsorption medium, time, dose of metal oxide nanoparticles including ZnO or Fe3O4
or their derived carbon hybrid materials including ZnO-C or Fe3O4-C, as well as the influence of the
concentration of Zn(II), Cd(II), Co(II) or Mn(II). The Kinetic models and the equilibrium-isotherms
were investigated to study the adsorption rate and predict the adsorption behavior. In addition,
wastewater samples were collected from Saudi Arabia, filtered and applied for adsorption evaluation
using optimized conditions for uptake of Zn(II), Cd(II), Co(II) or Mn(II) onto including ZnO-C or
Fe3O4-C.
Figure 1. SEM characterization of ZnO-C at magnification of (A) 250 and (B) 100000.
Figure 2. TEM characterization of ZnO-C at scale of (A) 200 nm and (B) 100 nm.
The developed ZnO-C is characterized by FTIR (Figure 3) which indicated main peaks between
3300 and 3700 cm–1 due to stretching vibration of the O-H groups. Peaks around 2900 cm–1, which
attributed to the aliphatic C-H. While the peak at around 1600 cm-1 is due to carbonyl groups (C═O).
The peak between 1400 and 1500 is attributed to O-H binding. The peak between 400 and 470 cm–1 is
attributed to the stretching vibration of Zn-O bond. The XRD analysis confirmed the crystalline
nature of the formed ZnO-C due to appearance of peaks at 2 thetas of around 31°, 34°, 36°, 47°, 56°,
62° and 69° which are attributed to the planes of (100), (002), (101), (102), (110), (103), and (112),
respectively. In addition, the detected high intensity peaks indicated the purity of formed hexagonal
structure of ZnO (JPCDS number: 36-1451) [37]. The successful fabrication of pure zinc oxide
nanoparticles anchored carbon is expected to improve the formed hybrid materials application for
adsorption of heavy metals. Rodríguez et al., developed zinc oxide/graphene nanocomposite and
indicated that the removal efficiency of Al and Cu were 19.9 mg/g and 33.5 mg/g, respectively, owing
that the decoration of graphene with ZnO nanoparticles enhanced the adsorption capacity [38].
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removal of heavy metals due to synergic effect. In addition, the developed ZnO-C exhibited the
higher adsorption capacity as 212, 209, 200 and 230 mg/L for Zn(II), Cd(II), Co(II) and Mn(II)
respectively, compared to Fe3O4-C which possess adsorption capacity of 177, 173, 165 and 167 for
Zn(II), Cd(II), Co(II) and Mn(II), respectively. These results agree with finding indicated by Hadadian
et al., who reported that combination of zinc oxide nanoparticles with graphene improve the
adsorption capacity for nickel removal [39].
Figure 5. investigating the adsorption capacity of varios adsorbent s for removal of Zn(II), Cd(II),
Co(II) and Mn(II), pH 6, time 180 min and adsorbent dose 0.15 g/L.
Figure 6. influence of pH on the removal of Zn(II), Cd(II), Co(II) and Mn(II) using ZnO-C, (time 180
min and adsorbent dose 0.15 g/L).
Figure 7. influence of ZnO-C dose on the removal of Zn(II), Cd(II), Co(II) and Mn(II) using ZnO-C
(pH 6, time 180 min).
Figure 8. influence of contact-time on the removal of Zn(II), Cd(II), Co(II) and Mn(II) using ZnO-C
(pH 6 and adsorbent dose 0.15 g/L).
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Table 1. kinetics and equilibrium equation for the applied as pseudo 1st order, pseudo 2nd order,
Langmuir isotherm and Freundlich isotherm.
intensity parameter.
The pseudo 1st order kinetic model (Figure 9) (Table 2) reveal a calculated adsorption capacity
of 227.1, 233.1, 191.7 and 258.4 mg/g for Zn(II), Cd(II), Co(II) and Mn(II), respectively, which
significantly different from the experimental capacity (183, 180, 163 and 196 mg/L for Zn(II), Cd(II),
Co(II) and Mn(II), respectively) mg/L for Zn(II), Cd(II), Co(II) and Mn(II), respectively. The pseudo
2nd order kinetic model (Figure 9) (Table 2) reveal a calculated adsorption capacity of 196.1, 188.7,
181.8 and 200.0 mg/g for Zn(II), Cd(II), Co(II) and Mn(II), respectively, which are near from the
experimental capacity (183, 180, 163 and 196 mg/L for Zn(II), Cd(II), Co(II) and Mn(II), respectively).
Therefore, the pseudo 2nd order model is the suitable model to describe the adsorption process. These
results indicated that the adsorption process onto the developed ZnO-C occur over three steps
(migration of Zn(II), Cd(II), Co(II) and Mn(II) in the adsorption solution, arrangement at the ZnO-C
surfaces, and migration through the pores)[43]. By applying the Langmuir isotherms plot (Figure 11)
for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C, the calculated constant (Table 3) and
the related correlation coeffcienct indicated that the isnot applicable for describing the adsorption
process. While plotting the Freundlich isotherm (Figure 12), the calculated constants (Table 3)
indicated strong correlation which confirm the multilayer adsorption and heterogenous surfaces
according to Freundlich assumptions.
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Figure 9. the pseudo 1st order plot for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C (pH
6 and adsorbent dose 0.15 g/L).
Figure 10. the pseudo 2nd order plot for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C
(pH 6 and adsorbent dose 0.15 g/L).
Table 2. the pseudo 1st order and pseudo 2nd order constants for adsorption of Zn(II), Cd(II), Co(II)
and Mn(II) onto ZnO-C (pH 6 and adsorbent dose 0.15 g/L).
Pseudo-First-Order Pseudo-Second-Order
qe,exp
K1(min−1) qe,cal(mg/g) R2 k2(g/mg.min) qe,cal(mg/g) R2
(mg/g)
10
Figure 11. the Langmuir plot for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C (pH 6, 25
C˚ and co time 180 min).
Figure 12. the Freundlich plot for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C (pH 6,
25 C˚ and co time 180 min).
Table 3. Equillibrium isothers constants for adsorption of Zn(II), Cd(II), Co(II) and Mn(II) onto ZnO-C.
11
wastewater treatment in real field with high added value. By comparing the obtained results with
literature [46–68] (Table 5), most of applied materials exhibited the maximum adsorption capacity in
the in the pH range of low acidic medium and neutral medium. In addition, the performance
efficiency of the evaluated hybrid martials in this work including ZnO-C and Fe3O4 are superior
compared to most of tabulated adsorbents from the literature. However, few adsorbents materials
exhibited higher adsorption capacity such as f the ZnO nanoparticles [54], hydroxyapatite/pectin
hybrid material [64] and Zinc oxide/ graphene oxide composite (ZnO/GO) [68].
Table 4. utilization of ZnO-C and Fe3O4-C hybrid materials for real wastewater purification.
Table 5. comparing adsoprion performance of ZnO-C and Fe3O4-C hybrid materials with materials
from literature.
12
pH = 5
Natural phosphate(NP) Cd(II) 26mg/g ]52[
straw biochar
pH = 6
(WSB)and acid treated WSB= 31.65 mg/g
Cd(II) contact time (5–180 ]53[
wheat straw biochar AWSB= 74.63 mg/g
min)
(AWSB)
Zn(II) 357 mg/g for Zn(II)
pH = 5.5
ZnO nanoparticles Cd(II) 387 mg/g for Cd(II) ]54[
Hg(II) 714 mg/g for Hg(II)
pH = 8
TiO2 nanoparticles Pb, Cd, Cu, Ni, Zn - [55]
Polyaniline/sawdust Mn(II) pH = 10
58.824 mg/g ]60[
composite contact time= 30 min
Poly (sodium acrylate)- Mn(II)
Mn(II) :
graphene oxide (PSA- pH = 6
165.5 mg/g ]61[
GO) double network Cd(II)
Cd(II): 238.3mg/g
hydrogel
pH = 4.04-8.05
Surfactant Modified Mn(II)
Contact time= 30 min 2.04 mg/g [62]
Alumina (SMA)
Mn(II)
Activated carbon Mn(II) pH = 5-6
=23.4 mg/g ]63[
from bean pods waste As (III) Contact time: 30 min
As (III)=1.01 mg/g
hydroxyapatite/pectin Zn(II) pH = 5
330.4 mg/g [64]
hybrid material
Polyaniline
Zn(II) pH = 3
Nanocomposite Coated 24.3 mg/g ]65[
Contact time: 20 min
on Rice Husk(PAn/RH)
Dendrimer-conjugated Zn(II)
pH= 7 24.3 mg/g [66]
magnetic nanoparticles
Zinc oxide
pH = 3-7
nanoparticles Cr3+ 88.547 mg/g ]67[
Contact time:20 min
(ZnO-NPs)
Zinc oxide/ graphene
pH = 5
oxide composite Pb(II) 909.09 mg/g ]68[
Contact time:160 min
(ZnO/GO)
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13
4. Conclusion
The zinc oxide nanoparticles anchored carbon (ZnO-C) hybrid materials have been prepared
with crystalline structure and spherical granules in nanoscale size of 29.3 - 48.8 nm. The prepared
porous structure of ZnO-C poses surface area of 24.84 m²/g. The optimized conditions for Zn(II),
Cd(II), Co(II) and Mn(II) uptake were at pH between 5 and 6, contact time 180 min and the ZnO-C
dose of 0.1 g/L. For comparison, various adsorbents materials including ZnO, Fe3O4, carbon, ZnO-C
and Fe3O4-C were utilized for wastewater treatment by adsorption of Zn(II), Cd(II), Co(II) and Mn(II).
However, the ZnO-C exhibited the superior adsorption capacity. Real wastewater sample including
valley-water, industrial wastewater and rain-water are successfully treated by adsorption of Zn(II),
Cd(II), Co(II) and Mn(II) onto ZnO-C and Fe3O4-C indicating high removal efficiency (more than 91%)
for evaluated samples. The results achieved in this work lead to further future investigations to
develop novel transition metal oxide nanoparticles decorated carbon as hybrid porous materials for
enhanced wastewater treatment applications. In addition, the investigated materials in this work
could be investigated for additional applications such photocatalytic degradation of organic
pollutants and/or removal of various pollutant’s categories such as radioactive waste or greenhouse
gases.
Author Contributions: Conceptualization, Mohamed Habila and Zeid ALOthman; Formal analysis,
Mohamed Habila, Zeid ALOthman and Ahmed Badjah-Hadj-Ahmed; Investigation, Abdullah ALanazi,
Mohamed Habila and Ahmed Badjah-Hadj-Ahmed; Methodology, Abdullah ALanazi, Mohamed Habila and
Ahmed Badjah-Hadj-Ahmed; Resources, Zeid ALOthman; Supervision, Zeid ALOthman and Ahmed Badjah-
Hadj-Ahmed; Validation, Mohamed Habila, Zeid ALOthman and Ahmed Badjah-Hadj-Ahmed; Writing –
original draft, Abdullah ALanazi; Writing – review & editing, Mohamed Habila and Ahmed Badjah-Hadj-
Ahmed.
Funding: This project was funded by the National Plan for Science, Technology, and Innovation (MAARIFAH),
King Abdul Aziz City for Science and Technology, Kingdom of Saudi Arabia, award No. 13-ENV1186-02.
Acknowledgments: The author acknowledges the National Plan for Science, Technology, and Innovation
(MAARIFAH), King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia for its grant with
award number 13-ENV1186-02.
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