Heliyon 6 (2020) e05309

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Heliyon
journal homepage: www.cell.com/heliyon

Research article

Adsorption of lead ions from wastewater using nano silica spheres

synthesized on calcium carbonate templates
Milton Manyangadze a, Nyaradzai M.H. Chikuruwo b, T. Bala Narsaiah c, Ch. Shilpa Chakra c,
Gratitude Charis d, Gwiranai Danha d, Tirivaviri A. Mamvura d, *
a
Chemical and Process Systems Engineering Department, Harare Institute of Technology, Harare, Zimbabwe
b
Industial and Manufacturing Engineering Department, Harare Institute of Technology, Harare, Zimbabwe
c
Institute of Chemical Sciences and Technology, Jawaharlal Nehru Technological University, Hyderabad, India
d
Department of Chemical, Materials and Metallurgical Engineering, College of Engineering and Technology, Botswana International University of Science and Technology,
Plot 10071, Boseja Ward, Private Bag 16 Palapye, Botswana

A R T I C L E I N F O A B S T R A C T

Keywords: Lead is a heavy metal that is bio accumulative and non-biodegradable that poses a threat to our health when it
Chemical engineering exists in excess in our bloodstream. It has found its way into wastewater from mostly chemical industrial pro-
Environmental science cesses. In this article, we investigated the adsorption and hence removal of lead (II) ions from wastewater in order
Physical chemistry
to purify it for re-use in industrial processes or for plant and animal use. We synthesized nano silica hollow
Environmental chemical engineering
Adsorption
spheres (NSHS) and used them as adsorbents to remove lead ions from wastewater. When we characterized the
Surface chemistry NSHS using X-Ray diffraction, the amorphous nature of silica was evident with average crystal size of 39.5 nm.
Environmental pollution Scanning electron microscopy was used to determine the morphology of the adsorbent and the particles were
Nano sodium silicate hollow spheres found to be spherical in shape within a size range of 100–200 nm. Thermogravimetric analysis was used to
Equilibrium studies determine the mass loss of NSHS which was ~2% at 800
C. Our experimental results from adsorption studies
Freundlich isotherm showed that there was a linear relationship between temperature (27–60
C) and adsorption efficiency and an
Langmuir isotherm inverse relationship between initial metal concentration (50–300 mg/L) and adsorption efficiency. At a maximum
Thermodynamic studies
temperature of 60
C and maximum initial metal concentration of 300 mg/L, the adsorption capacity was 200
Wastewater
mg/g and 262 mg/g, respectively while the adsorption efficiency was 99.6% and 87.4%, respectively. Our
Lead ions
equilibrium and thermodynamic results revealed that the process was better modelled by the Langmuir adsorp-
tion isotherm (qmax ¼ 266.89 mg/g and b ¼ 0.89 L/mg). The adsorption process was both endothermic (ΔH ¼ 97
kJ/mol) and spontaneous (ΔG ¼ -22 kJ/mol). We can conclude that we were able to successfully synthesize
NSHS, use them to remove lead (II) ions and the produced NSHS have a capacity that is higher than most other
adsorbents investigated by other researchers.

1. Introduction wastewater. There are four classes of pollutants in wastewater; namely

organic, inorganic, heavy metals and alkaline earth metals, and patho-
One of the socio-economic challenges we face in the present day gens (Huang and Chen, 2009; Singh et al., 2011). Pollution of water
world is access to fresh water for human consumption and industrial bodies from heavy metal and alkaline earth metal ions mainly from
purposes. Our fauna and flora especially in Southern Africa have also chemical industries has also contributed to this challenge of water
succumbed to the diminishing levels of this basic natural resource shortage. Examples of chemical industries that have contributed to heavy
(Sayago et al., 2020). Global warming increase in small and medium metal pollution include tanneries, battery manufacturing, textiles, paints
enterprises (SMEs), absence of child birth policies, persistent droughts and dyes, and metal plating (Badruddoza et al., 2013; Gusain et al., 2019;
and over population (Singh et al., 2013) are amongst many other factors, Hao et al., 2012; Mohammadifard and Amiri, 2017). Heavy metal and
that have contributed to this challenge, mainly in Africa. This is mostly alkaline earth ions like lead and zinc, respectively, have been proven to
due to pollution of water and/or water bodies sometimes from be carcinogenic and cause health disorders in humans and aquatic life.

* Corresponding author.
E-mail addresses: [email protected], [email protected] (T.A. Mamvura).

https://doi.org/10.1016/j.heliyon.2020.e05309
Received 19 May 2020; Received in revised form 7 August 2020; Accepted 15 October 2020
2405-8440/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Manyangadze et al. Heliyon 6 (2020) e05309

This is because they are highly toxic, bio-accumulative and R2 of 0.9999. Different parameters were optimised and using response
non-biodegradable (Li et al., 2020). The presence of metal ions like lead, surface methodology, they got maximum removal capacity (qmax) of
arsenic and chromium in potable water and/or wastewater, has been 393.53 mg/g at 26
C, initial Cu concentration of 200 mg/L, adsorbent
associated with different cancers like skin cancer, lung cancer, kidney dosage of 0.5 g/L, pH of 5.5 and contact time of 60 min Gusain et al.
cancer among others (Li et al., 2020). Besides being carcinogenic, metals (2019) investigated adsorption of Pb2þ and Cd2þ ions from industrial
like lead and chromium have also been reported as potential teratogens mine wastewater by using hierarchical MoS2/SH-MWCNT nano-
as well as mutagens (Sayago et al., 2020). Lead is also highly toxic and it composite synthesized using a facile hydrothermal method and they
has been linked to various health problems like brain damage, mental observed good results. Optimised parameters for the process were an
disturbances, retardation and reduction in the production of haemoglo- adsorbent dosage of 2 mg/ml, pH of 6, initial metal concentration of 45
bin. It also affects vital internal body parts such as the reproductive mg/L and a temperature of 55
C for both Pb2þ and Cd2þ ions, and
system, nervous system, and is associated with problems of high blood contact time of 60 min for Pb2þ ions and 75 min for Cd2þ ions. Their
pressure and anaemia (Hao et al., 2012). Because of all these prior listed process was better modelled by the Freundlich isotherm model (0.86 
challenges, governments and environmentalists have come up with R2  0.95), and the process was endothermic (ΔH ¼ 8.06 kJ/mol) and
stringent measures aimed at monitoring and reducing heavy metal con- spontaneous (ΔG  -9 kJ/mol). Nano-adsorbents are proving to be su-
centration levels from industrial effluents. This approach has resulted in a perior in terms of separation efficiency and cost as compared to adsor-
lot of research effort being directed towards the development of new and bents like activated carbon (Li et al., 2020). These research findings have
improved technologies that can significantly handle heavy metals and led to nano-adsorbents being considered commercially as an economi-
reduce their concentration to below the stipulated disposal limits. Hence, cally viable, environmentally friendly and sustainable resource option
we elucidate that the novelty aspect in our studies in this manuscript lie during adsorption of heavy metals from wastewater (Gao et al., 2020).
on the ejection of lead ions from wastewater by way of adsorption on Within the sphere of nano adsorbents, silica-based nanomaterials are
silica nano spheres that we synthesized on calcium carbonate templates. finding a lot of application and a lot of attention in water and wastewater
There are many different methods that can be used to remove heavy treatment processes.
metals from wastewater like precipitation, solvent extraction, ion ex- A lot of research has been done on the removal of heavy metal ions
change and membrane separation but only adsorption seems to be an from wastewater using silica nano-particles and their derivatives as ad-
economical option at this stage. The application of adsorption as a unit sorbents because they have been shown to have very good properties like
operation in domestic water and industrial wastewater treatment pro- definite pore size, high surface area, good selectivity and adsorption
cesses has gained a lot of popularity in modern day plants. A lot of capacity. However, silica is employed in its modified form, either func-
research has been done on adsorption of heavy metal ions over the years, tionalized or as a composite (Kegl et al., 2020). Generally, several
but the research is still continuing. Different adsorbents have been pro- different functional groups have been considered. Different researchers
posed and they can be classified into different groups that include employed these functional groups and contributed immensely to the
chemical adsorbents, zeolites, bio adsorbents and nano-adsorbents growing body of knowledge on this subject. Kegl et al. (2020) have
(Mohammadifard and Amiri, 2017). However, most proposed adsor- shown different silica based materials that have been synthesized for
bents have not been economical due to separation and regeneration, and adsorption studies: (a) silica functionalized nanomaterials (NMs), see
so research still continues to find the ideal adsorbent for heavy metal ion their Figure 3; (b) silica/polymer nano compounds (NCs), see their
removal. El-Naggar et al. (2019) investigated the adsorption of Pb2þ ions Figure 4; (c) functionalized silica/compounds NCs, see their Figure 5 and
from wastewater using Kaolinite/Smectite natural composite adsorbents (d) silica core@shell nanoparticles (NPs), see their Figure 6. All of these
and observed positive results at pH of 2, a linear relationship between silicas based materials are also summarised in Table 1 in their paper. Kegl
adsorption rate and temperature from 30 to 75
C, and a linear rela- et al. (2019) investigated adsorption of dysprosium (Dy3þ) ions, a critical
tionship up to 100 mg/L then an inverse relationship from 100 to 500 rare earth element, using novel γ-Fe2O3–NH4OH@SiO2(APTMS) nano-
mg/L with adsorption capacity, and their adsorption process followed particles and the process showed very good results that fit the Temkin
Freundlich isotherm (R2 ¼ 1). Higher pH led to Hþ ions adsorption isotherm, and the process was endothermic and spontaneous. Li et al.
instead of Pb2þ ions. Mustapha et al. (2019) investigated adsorption of (2020) prepared thiol-functionalized cobalt ferrite magnetic mesoporous
metal ions (Pb2þ, Cd2þ, Zn2þ, Cu2þ) from aqueous solutions using silica composite (SH-mSiO2@CoFe2O4) using the modified St€ ober
powdered adsorbent made from Albizia lebbeck pods. They varied method and used the composite to remove Hg2þ ions from aqueous so-
different parameters and found optimum parameters of pH of 10, contact lutions. The magnetic composite was separated using its magnetic
time of 30 min, lower initial metal concentration of 10 mg/L, high properties after adsorption within 1 min. The composite showed very
adsorbent dosage of 1.4 g and high temperature of 80
C. The adsorption good adsorption capability with a maximum adsorption of 258 mg/g at
process was best modelled by the Langmuir isotherm model (R2 > 0.94). room temperature when the initial concentration of Hg2þ ions was 8
The process was endothermic and non-spontaneous at low temperatures, mg/L. The optimum conditions were initial metal concentration of 30
but it was spontaneous at higher temperatures. mg/L, contact time of 20 min, lower temperature of 15
C within a pH
Currently, there is a growing trend in interest and demand for nano- range of 2–6.
adsorption technologies in wastewater treatment processes. Nano- When considering adsorption of metal ions from wastewater, the
materials have gained popularity in water treatment because of their most important property that we consider is a high adsorption ability,
large surface area to volume ratio, and surface multi-functionality that which is linked to a large surface area to volume ratio (Kegl et al., 2019).
makes them to easily react chemically and bind/adsorb a specific target This gave us the platform to look at silica-based nano spheres supported
metal ion(s) on their surfaces (Kegl et al., 2020; Mohammadifard and on CaCO3 as adsorbents to remove Pb2þ ions from wastewater. CaCO3 is
Amiri, 2017). These nano-adsorbents are employed to remove various one of the most abundant materials found in nature (Mohammadifard
types of pollutants from industrial wastewater. The nanomaterials can be and Amiri, 2017) and this justified its use as a support for silica-based
magnetic or non-magnetic, magnetic nanomaterials can be separated nano spheres in our study. To the best of our knowledge, there is no
using permanent magnets at the end of the adsorption process, while research that has been done on nano silica spheres supported on calcium
non-magnetic nanomaterials will require different means of separation carbonate as an adsorbent for removing Pb2þ ions from wastewater. In
(Kegl et al., 2019). In this study we employed non-magnetic nano- this article, we focussed on the synthesis and characterization of
materials. Mohammadifard and Amiri (2017) investigated the removal of non-metallic nano silica spheres (NSHS) with calcium carbonate (CaCO3)
Cu2þ ions from aqueous solutions using novel synthesized CaCO3 nano- as a template, for application in the removal of Pb2þ ions from industrial
particles prepared in a colloidal gas aphron. The adsorption process was wastewater.
best modelled by the Langmuir isotherm based on correlation coefficient,

2
M. Manyangadze et al. Heliyon 6 (2020) e05309

Table 1. Statistical analysis using t-test on three parameters.

Parameter Equilibrium concentration of Adsorbed metal ions per unit mass of adsorbent (qe) Absorption efficiency (R)
adsorbed metal ions (Ce)
Standard value: Effect of Temperature 0 200 100%
Standard value: Effect of initial metal 0 40, 100, 200, 300 100%
ion concentration

2. Experimental work The structure and properties of synthesized nanomaterials are

affected by the nature of precursor, solvent used, the modifying agents as
2.1. Materials well as the process conditions, such as pH and temperature (Kegl et al.,
2020). However, the high purity and uniform nanostructure achievable
We obtained all the raw materials and samples for our experimental at low temperatures made the sol-gel method attractive for synthesis of
programme from Harare, Zimbabwe. In order for us to synthesize NSHS NHSH in this study.
we used anhydrous calcium chloride (AR, CaCl2⋅2H2O, 99%), anhydrous
potassium carbonate (AR, K2CO3, 99.9%), anhydrous sodium hydroxide
2.4. Adsorption studies
(AR, NaOH, 99.9%), anhydrous hydrochloric acid (AR, HCl, 36%), and
deionised water (millipore).
We carried out experiments to determine the effect of initial sorbate
concentration and temperature, on adsorption rates. We adopted the
2.2. Methods experimental procedure employed in this section from El-Aila et al.
(2016); Kegl et al. (2019).
We carried out the synthesis for NSHS in three stages, apart from the
preparation of sodium silicate step. The details of this synthesis process 2.4.1. Effect of temperature
are covered in Manyangadze et al. (2017). We then further employed We investigated the change in adsorption rates of Pb2þ ions onto
three characterization methods for the analysis of NSHS, namely, X-Ray NHSH as a function of temperature. The experiments we carried out
diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermog- employed a predetermined amount of the adsorbent of 50 mg, optimum
ravimetric Analysis (TGA). Some adsorption studies focusing on pH of 5.0, a contact time of 40 min and stirring speed of 450 rpm, as
adsorption kinetics of Pb2þ ions were discussed in Manyangadze et al. determined in Manyangadze et al. (2017). An initial sorbate concentra-
(2017). The current work focusses primarily on the effect of temperature tion of 200 mg/L was used. We then suspended the adsorbent in 50 ml of
and initial metal ion concentration on adsorption of Pb2þ ions to deter- sorbate solution at a pH of 5.0. We proceeded to vary the temperature
mine equilibria data and adsorption thermodynamics. from 27  1
C, 40  1
C, 50  1
C to 60  1
C. After 40 min of contact
time, we filtered the samples to separate the cake adsorbent from the
2.3. Preparation of NSHS filtrate. The residual sorbate concentration was then analysed for lead
concentration using Atomic Absorption Spectroscopy (AAS).
We employed the sol-gel method which consists of hydrolysis,
condensation, aging, and drying as highlighted in Kegl et al. (2020). Our 2.4.2. Effect of initial sorbate concentration
work on adsorption of Pb2þ ions from aqueous solutions has not been To enable us to investigate the effect of initial metal ion concentration
reported as far as we can tell but Chen et al. (2004) prepared and char- on the rate of adsorption, we suspended 50 mg of the adsorbent in 50 ml
acterized porous hollow silica nanoparticles for drug delivery application of varied sorbate concentration ranging from 40, 100, 200–300 mg/L.
while Mourhly et al. (2015) synthesised and characterized low-cost We then fixed the stirring speed at 450 rpm, pH at 5.0, temperature at 27
mesoporous silica SiO2 from local pumice rock. As such the method for  1
C and a residence time of 40 min. After which, we filtered the
synthesis of NSHS was adapted and modified from their studies. The samples to separate the cake adsorbent. We proceeded to determine the
procedure involves initially disintegrating the CaCO3 template in hy- residual sorbate or equilibrium concentration using AAS. This enables us
drochloric acid to produce NSHS nanoparticles. We then weighed 4 g of to evaluate the optimum initial sorbate concentration.
the prepared CaCO3 nanoparticles into a 500 ml beaker and added 200
ml of deionized water. We then stirred the suspension that was formed 2.4.3. Adsorption isotherms
using a stirring speed of 700 rpm. While still stirring, we dropwise added There are several adsorption isotherms available in literature,
150 ml of a 0.4 M sodium silicate solution and heated the mixture to a namely: Langmuir, Freundlich, BET, Temkin, Dubinin-Radushkevitch,
temperature of 80  1
C for 30 min. After which, we further dropwise Hill, Redlich-Peterson, and Sips (Kegl et al., 2020) but in this study we
added a volume of 75 ml of a 2.0 M HCl acid while still stirring contin- employed only two, Langmuir (equation 1) and Freundlich (equation 3)
uously at an increased speed between 800 and 900 rpm for an additional isotherms as they are the most commonly used theoretical adsorption
40 min. We then left the mixture to cool at room temperature overnight isotherm models. These isotherms show the effect of initial concentration
in order to form a gel. We separated the formed gel by filtration and of metal ions and temperature on the adsorption process. We computed
washed it three times using deionized water. We then dried it in an air the adsorption capacities at equilibrium (qe) from Eqs. (2) and (4) for
oven set at 80  1
C for 5 h. Afterwards we took the dried solid and Langmuir and Freundlich isotherms, respectively. To achieve this, we
pulverized it in an agate mortar before the calcination process. We went used 100 mL beakers to prepare 50 mL volume of Pb2þ ion solutions of
on to carry out calcination at a temperature of 450  1
C for a time varying concentrations, up to the optimum initial concentration of 200
period of 3 h in a muffle furnace in order to produce NHSH. We pro- mg/L. The solution pH was adjusted to the optimum value of pH 5.0
ceeded to characterise the synthesized NSHS using XRD, SEM and TGA using a 0.1 M nitric acid and sodium hydroxide solutions. We proceeded
analyses. XRD was used to determine the composition of NSHS by to add 50 mg of the adsorbent and dispersed it by means of magnetic
identifying distinct peaks linked to functional groups, we used SEM to stirring at 450 rpm for a time period of 2 h. After equilibrium was
determine the morphology of the NSHS including their crystallinity and attained, the samples were then filtered in order to separate the cake
particle sizes and TGA was employed to determine any mass loss in NSHS adsorbent from the filtrate. We went on to determine the residual Pb2þ
as temperature was increased, i.e. this investigates any volatile com- ion concentrations by AAS in the filtrate. We then used the data gener-
pounds within the NSHS structure. ated to best fit both our models as given by Eqs. (2) and (4) as well as the

3
M. Manyangadze et al. Heliyon 6 (2020) e05309

Figure 1. TG/DTA curves for NSHS particles.

equilibrium relationship, Eq. (5) (El-Aila et al., 2016; Gao et al., 2020; of adsorbent (mg/g); qm represents the maximum adsorbed metal ions
Kumar, 2014; Sayago et al., 2020). per unit mass of adsorbent (mg/g), and this is a characteristic Langmuir
Langmuir Isotherm equations parameter; b represents the Langmuir adsorption equilibrium constant
and is sometimes known as KL the equilibrium constant (L/mg); Co rep-
qm bCe resents the initial concentration of metal ions before adsorption (mg/L);
qe ¼ (1)
1 þ bCe Ce represents the equilibrium concentration of adsorbed metal ions (mg/
L); Kf represents the adsorption capacity (L/mg); 1/n represents the
Ce 1 Ce adsorption intensity (g/L) which is the relative distribution of the energy
¼ þ (2)
qe qm b qm and the non-homogeneity of the adsorbate sites (n is adsorption ener-
Freundlich Isotherm equations getics), V represents the total volume of the solution that contains the
Pb2þ ions in litres and W represents the mass of the adsorbent (g) used.
1
q e ¼ Kf Ce n (3) The adsorption studies can be quantified by many parameters and one
of them is the adsorption efficiency, which we used in this study (Kumar,
1 2014; Sayago et al., 2020):
ln qe ¼ ln Kf þ ln Ce (4)
n
Co  Ce
Equilibrium relationship equation %R ¼  100 (6)
Co

ðCo  Ce ÞV
qe ¼ (5) 2.4.4. Adsorption thermodynamics
W
Adsorption thermodynamics shows the impact of temperature on the
In the equations, qe represents the adsorbed metal ions per unit mass adsorption process. The experiments we performed to investigate the

Figure 2. XRD pattern for NSHS particles.

4
M. Manyangadze et al. Heliyon 6 (2020) e05309

Figure 3. SEM images for NSHS particles. (a) SEM micrograph at 5μm showing spherical particles of diameter within range 100–200 nm, (b) SEM micrograph at 5μm
showing particle aggregation, (c) SEM micrograph at 5μm showing particle aggregation.

effect of temperature on the adsorption rates, gave us the basis on which ΔH o ΔSo ΔGo
ln Kp ¼  þ ¼ (11)
to evaluate the associated adsorption thermodynamics. We employed RT R RT
AAS to measure the concentration of the metal ions at equilibrium (Ce) in
where Ca is the concentration of the adsorbed metal ion in mg/L; R is the
mg/L. We went on to evaluate concentration of the adsorbed metal ions
universal gas constant; Kp is adsorption equilibrium constant which is
(Ca) in mg/L, using Eq. (7). We calculated values for the dimensionless
calculated from KL for Langmuir isotherm or Kf for Freundlich isotherm, γ
thermodynamic equilibrium constant (Kp) using Eq. (8). The dimen-
is a dimensionless coefficient of activity (it is assumed as 1 as the
sionless thermodynamic equilibrium constant was computed using the
adsorbate solution is very diluted), G is Gibbs free energy of the process
adsorption equilibrium constant as in Kegl et al. (2019) and Kegl et al.
(J/mol); T is the absolute temperature (K); H is enthalpy of the process
(2020) but modified to our study as Eq. (8) before computing the asso-
(J/mol) and S is entropy of the process (J/mol⋅K).
ciated thermodynamic parameters using equations from (9, 10, 11)
The purpose of adsorption thermodynamics is to determine the if the
(El-Aila et al., 2016; El-Naggar et al., 2019; Gao et al., 2020; Kumar,
adsorption is exothermic (ΔH < 0) or endothermic (ΔH > 0), sponta-
2014; Sayago et al., 2020).
neous (ΔG < 0) or non-spontaneous (ΔG > 0) as well as to see if the metal
Ca ¼ Co  Ce (7) ions like to be in random disorder (ΔS > 0) or ordered on the adsorbent
solid surface (ΔS < 0).
Kf Co
Kp ¼ (8)
γ
2.5. Statistical analysis
ΔGo
ln Kp ¼  (9) We performed two forms of statistical analysis in this study. The first
RT
one was done with analysis of variance (ANOVA). During the experi-
ΔGo ¼ ΔH o  TΔSo (10) ments to determine the effect of temperature and initial metal ion con-
centration on the adsorption process, the experiments were performed
three times and an average value was determined afterwards. Statistical

Table 2. Equilibrium adsorption capacity at T ¼ 27, 40, 50 and 60
C.

Parameter Co (mg/L) W (g) V (ml) pH t (mins) Speed (rpm) Ce (mg/L) qe (mg/g)

27
C Exp 1 200 0.05 50 5.0 40 450 49.50 150.50
Exp 2 200 0.05 50 5.0 40 450 30.35 169.65
Exp 3 200 0.05 50 5.0 40 450 40.90 159.10
40
C Exp 1 200 0.05 50 5.0 40 450 15.10 184.90
Exp 2 200 0.05 50 5.0 40 450 25.35 174.65
Exp 3 200 0.05 50 5.0 40 450 20.36 179.64
50
C Exp 1 200 0.05 50 5.0 40 450 10.46 189.54
Exp 2 200 0.05 50 5.0 40 450 7.50 192.50
Exp 3 200 0.05 50 5.0 40 450 7.85 192.15
60
C Exp 1 200 0.05 50 5.0 40 450 0.00 200.00
Exp 2 200 0.05 50 5.0 40 450 0.00 200.00
Exp 3 200 0.05 50 5.0 40 450 2.56 197.44

Table 3. Summary of results showing effect of temperature on adsorption capacity.

T (oC) Ce (mg/L) qe (mg/g) R Kf (L/mg) Kp 1/T (K1) ln Kp

27 40.25 159.75 79.88% 3.97 793.79 0.0033 6.68
40 20.27 179.73 89.87% 8.87 1773.36 0.0032 7.48
50 8.60 191.40 95.70% 22.25 4449.36 0.0031 8.40
60 0.85 199.15 99.57% 233.38 46675.00 0.0030 10.75

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M. Manyangadze et al. Heliyon 6 (2020) e05309

and 40, 100, 200 and 300 mg/g for effect of initial metal ion
250 100%
concentration?
Adsorp on capacity (qe (mg/g)

200 95% (c) Do the R values obtained in the experiments differ very much from

Adsorp on efficiency
the standard R value of 100%?
150 90%
The standard t-test uses the following hypotheses (Quirk, 2014):
100 85%

50 80%
 Null hypothesis: The calculated value is equal to the standard value
 Alternative hypothesis: The calculated value is not equal to the
0 75% standard value
0 10 20 30 40 50 60
Temperature (oC) If the p-value for two tailed test (P (T<¼t) two-tail from MS Excel) is
less than our significance level which we set at 0.05, then we can reject
qe Adsorp on efficiency
the null hypothesis and conclude that the calculated values are signifi-
cantly not equal to the standard values (Bonamente, 2017; Quirk, 2014).
Figure 4. Effect of temperature on adsorption capacity and sorption efficiency
of NSHS.
3. Experimental results and analysis

analysis using ANOVA's single factor in Microsoft Office Excel was used 3.1. Characterization techniques
to determine if there was any difference between the three experimen-
tally determined values so that we can gain confidence in the average Morphology, thermal stability and particle size are the three charac-
value calculated from the three values (Dekking et al., 2005; Quirk, terization techniques we employed to assess inherent surface character-
2014). istics of the prepared nanomaterials. These characteristics are typically
The standard hypotheses for ANOVA: Single Factor for our study are relevant in understanding the ejection of heavy metals from aqueous
(Quirk, 2014): systems. Outlined below are the results we obtained from the various
analytical techniques of the NSHS.
 Null hypothesis: All the three values from the experiments can be
considered equal 3.1.1. Thermogravimetric analyses (TG/DTA)
 Alternative hypothesis: All the three values from the experiments can Figure 1 shows a significantly low material loss for NSHS. The overall
be considered significantly different material loss is here pegged at approximately 15%. Apparently, a very
low material loss is observed around 100
C, amounting to approximately
If the p-value (P-value from MS Excel) is less than our significance 1% and this endothermic effect is attributed to loss of physically adsor-
level which we set at 0.05, we reject the null hypothesis and conclude bed moisture (Mourhly et al., 2015) but it seems to stretch up to 200
C.
that the values are significantly different, meaning that their average Other endothermic effects are observed at 650
C with a loss of
cannot be considered reliable (Bonamente, 2017; Dekking et al., 2005; approximately 2% and at around 805
C as shown on both the TG and
Quirk, 2014). DTA curves.
The second analysis was performed using Microsoft Office Excel's t-
test: Paired Two Sample for Means to test if the calculated values per- 3.1.2. XRD analysis
forms well against standard values we were supposed to get. T-test was Figure 2 shows XRD analysis of the NSHS particles with distinct peaks
used because the sample for our experiments was small (Bonamente, at 22o, 29.5o, 31.5o, 45o, 56.5o and 75.5o with a characteristic peak of
2017; Dekking et al., 2005). T-test was performed on the parameters importance appearing at 2θ ¼ 22o. In their work, in which SiO2 was
summarised in Table 1. synthesized via neutralization reaction of sodium silicate with sulphuric
The equilibrium concentration (Ce) ideally was supposed to be 0 mg/ acid, Music et al. (2011)located the characteristic peak at 21.8o. Misran
L for both cases but in reality, it was more than that. The equilibrium et al. (2013); Mourhly et al. (2015) and Zulfiqar et al. (2016) indicated
adsorbed metal ions (qe) should ideally be 200 mg/g for the effect of that the 2θ ¼ 22o peak shows the presence of SiO2 which is amorphous
temperature while it changes to the maximum value for the effect of and that there was no crystalline structure. From the XRD pattern, the
initial metal ion concentration. This could only be achieved if Ce values amorphous nature of silica is quite evident and using the Scherrer Eq.
were at their lowest expected values. In addition, adsorption efficiency (12), the average crystal size was also determined and found to be 39.5
ideally should be 100% to show that all metal ions have been adsorbed nm. The presence of CaCO3 was confirmed by the characteristic peak at
but in reality, it was not possible, and the t-test was meant to see if there 29.5o as highlighted in Mohammadifard and Amiri (2017) and Zulfiqar
is any significant effect from the values that we determined. et al. (2016).
The statistical t-tests were based on the following: Kλ
dXRD ¼ (12)
βCosθ
(a) Do the Ce values obtained in the experiments differ very much
from the standard Ce value of 0 mg/L?
3.1.3. SEM analysis
(b) Do the qe values obtained in the experiments differ very much
We employed SEM analysis to gather important information about the
from the standard qe values of 200 mg/g for effect of temperature
morphology, texture, size as well as shape of the nanoparticles. Micro-
graph images of NSHS nanoparticles are shown in Figure 3. The figure

Table 4. Summary of statistical analysis from studies on effect of temperature on adsorption efficiency.

Statistical test ANOVA t-test

Ce data in triplet Ce vs minimum Ce of 0 mg/L qe vs maximum Ce of 200 mg/g %R vs maximum R of 100%

p-value 0.9713 0.2212 0.2212 0.2212

6
M. Manyangadze et al. Heliyon 6 (2020) e05309

Table 5. Equilibrium adsorption capacity at Co ¼ 27, 40, 50 and 60
C.

Parameter T (oC) W (g) V (ml) pH t (mins) Speed (rpm) Ce (mg/L) qe (mg/g)

40 mg/L Exp 1 27 0.05 50 5.0 120 450 0.00 40.00
Exp 2 27 0.05 50 5.0 120 450 0.00 40.00
Exp 3 27 0.05 50 5.0 120 450 0.00 40.00
100 mg/L Exp 1 27 0.05 50 5.0 120 450 0.00 100.00
Exp 2 27 0.05 50 5.0 120 450 0.30 99.70
Exp 3 27 0.05 50 5.0 120 450 0.80 99.20
200 mg/L Exp 1 27 0.05 50 5.0 120 450 0.00 200.00
Exp 2 27 0.05 50 5.0 120 450 15.10 184.90
Exp 3 27 0.05 50 5.0 120 450 9.50 190.50
300 mg/L Exp 1 27 0.05 50 5.0 120 450 15.12 284.88
Exp 2 27 0.05 50 5.0 120 450 53.10 246.90
Exp 3 27 0.05 50 5.0 120 450 45.25 254.75

Table 6. Summary of results showing effect of initial sorbate concentration on adsorption capacity.

Co Ce qe R Ce/qe lnqe lnCe

40 0.00 40.00 100% 0.00 3.69 -
100 0.37 99.63 99.63% 0.00 4.60 -1.00
200 8.20 191.80 95.90% 0.04 5.26 2.10
300 37.82 262.18 87.39% 0.14 5.57 3.63

3.2.1. Effect of temperature

300
100% Table 2 presents results showing the effect of temperature on the rate
Adsorp on capacity (qe) (mg/g)

98% of adsorption and adsorption capacity, while Table 3 gives a summary of

250
the results which are then plotted in Figure 4. Table 4 shows p-values
Adsorp on efficiency

96%
200 from statistical analysis using ANOVA for Ce values in triplet, and using t-
94% test for Ce, qe and %R values.
150
92% Table 4 indicates that the means for Ce values range from a low of
100
90% 15.800 to a high of 18.765 showing that our means are very close from
50
ANOVA analysis. The p-value is 0.9713 which is greater than our sig-
88%
nificance level of 0.05 and therefore we accept the null hypothesis that
0 86% our sample data provide strong enough evidence to conclude that the
0 50 100 150 200 250 300
three Ce values for each temperature can be considered to be equal. This
Ini al metal ion concentra on (mg/L)
gives us the confidence that the average values we calculated and used in
qe Adsorp on efficiency our calculations are a representative of the actual experimental results
obtained. From t-test analysis, the mean for the actual and standard
Figure 5. Adsorption isotherm for Pb2þ on NSHS.
values for Ce, qe and %R are 9.91 versus 0, 190.10 versus 200 and 0.95
versus 1, respectively. Our p-values for Ce, qe and %R are all greater than
the confidence level of 0.05 and therefore we accept the null hypothesis.
reveals that the particles are mostly spherical in shape and particle ag-
Our sample data support the hypothesis that there is no significant dif-
gregation is also observed. The size of the particles was found to be in the
ference between our calculated values of Ce, qe and %R and their stan-
range of 100–200 nm. Also, from the micrographs, distinct particles are
dard values.
not clearly separated, hence the morphology of the material could not be
Figure 4 shows a near linear relationship between temperature versus
easily ascertained.
adsorption capacity as well as adsorption efficiency. It can be observed
from the plot that as temperature is increased from ambient (27
C) to 60
3.2. Adsorption studies

C there is a corresponding increase in the adsorption capacity. For Pb2þ
ions to be adsorbed, dehydration has to occur, and the process has to
We investigated the removal of Pb2þ ions using NSHS. We system-
absorb heat that is availed by an increase in temperature (Lei et al.,
atically looked at the effect of two of the various adsorption parameters,
2019). As the temperature further increases, the degree of hydration of
temperature and initial sorbate concentration.
hydrated metal ions also increases, justifying improved adsorption rates
associated with higher temperatures (Lei et al., 2019). Mustapha et al.
(2019) argued that the increase in adsorption capacity with an increase
in temperature resulted in an increase in the mobility of the Pb2þ metal

Table 7. Summary of statistical analysis from studies on effect of initial metal ion concentration on adsorption efficiency.

Statistical test ANOVA t-test

Ce data in triplet Ce vs minimum Ce of 0 mg/L qe vs maximum Ce of 40, 100, 200 and 300 mg/g %R vs maximum R of 100%
p-value 0.6163 0.3080 0.3080 0.2567

7
M. Manyangadze et al. Heliyon 6 (2020) e05309

with an increase in temperature. They argued that this was in contra-

300
diction with what should happen with ordinary adsorption process
250 behaviour which normally should be exothermic, thereby decreasing
with an increase in temperature. However, this contradiction which was
200 observed by other researchers mentioned above as well further gives
qe (mg/g)

evidence that the adsorption process is not just a “simple adsorption

150
process”.
100 El-Naggar et al. (2019) studied the removal of Pb2þ ions from
wastewater using a natural composite adsorbent called Kaolini-
50 te/Smectite. They observed that increasing temperature increases
adsorption capacity. They attributed this trend to an increase in reaction
0
0 5 10 15 20 25 30 35 40 rate due to increased average velocity and diffusion of ions as they
Ce (mg/L) adhere onto the surface of the adsorbent. Our experimental results show
that there is a positive correlation between adsorption efficiency and
temperature in the range 27–60
C. We elucidate that the adsorption
Figure 6. Adsorption isotherm for Pb2þ on NSHS.
process was indeed endothermic hence chemisorption as similarly
observed by El-Naggar et al. (2019) and other investigators mentioned
above.
0.16 Li et al. (2020) investigated adsorption of Hg2þ ions from aqueous
0.14 solutions using thiol functionalized cobalt ferrite magnetic mesoporous
0.12 silica composite and found an inverse relationship between temperature
y = 0.0037x + 0.0042 and adsorption efficiency which they attributed to weakening of bonds
0.10 R² = 0.9937
Ce/qe (g/L)

between cations and adsorption sites as temperature increased. Fathy

0.08 et al. (2019) observed an inverse relationship between adsorption effi-
0.06 ciency and temperature when they were investigating adsorption of Pb2þ
0.04
and Co2þ ions using CaCO3/HPC core-shell composite from aqueous
solutions. They reasoned that the adsorption process was exothermic for
0.02
both ions. They suggested further that increasing the temperature should
0.00 weaken the physical or chemical attractive forces thereby reducing the
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
sorbent ability.
Ce (mg/L)
Researchers have found the adsorption of Pb2þ ions onto adsorbents
to be either endothermic as in our case or exothermic as in other cases.
Figure 7. Linearized plot for the Langmuir isotherm model. The endothermic nature of our process can be attributed to reduced
desorption and an increase in adsorption sites as temperature is
ions as they acquired more kinetic energy due to increased velocity increased. This can be backed up by a steep increase in adsorption ca-
resulting from higher temperatures in the system. They postulated that pacity and efficiency when temperature was increased from room tem-
this process is endothermic in nature, thereby it could be considered as a perature (27
C) to 40
C. However, the increase was lower above 40
C,
chemical adsorption process. Gusain et al. (2019) investigated adsorption showing the initial impact of adding heat to move above the room
of Pb2þ and Cd2þ ions from industrial mine using hierarchical temperature.
MoS2/SH-MWCNT nanocomposite and observed a similar trend which
they attributed to an endothermic adsorption process and increased 3.2.2. Effect of initial sorbate concentration
mobility of metal ions with an increase in temperature due to an increase The relationship between the equilibrium values of the sorbate con-
in thermal energy of the system. They also added that an increase in centration (Ce) and the adsorption capacity (qe) is given in Table 5 while
temperature reduced the required activation energy by opening the Table 6 gives the summary of the results for different initial metal con-
MWCNT network structure as well as increasing the deprotonation of centration. Figure 5 gives the adsorption isotherm for Pb2þ onto NSHS
functional groups leading to additional binding sites. Mohammadifard and Table 7 shows p-values from statistical analysis using ANOVA for Ce
and Amiri (2017) investigated the removal of Cu2þ ions from aqueous values in triplet, and using t-test for Ce, qe and %R values.
solutions using novel synthesized CaCO3 nanoparticles prepared in a Table 7 indicates that the means for Ce values range from a low of
colloidal gas aphron and observed an increase in adsorption efficiency 3.78 to a high of 17.125 showing that our means are not very close from
ANOVA analysis. The p-value we determined is 0.6163 which is greater
than our significance level of 0.05. We accept the null hypothesis that our
6.00 sample data provide strong evidence to conclude that the three Ce values
for each of the initial metal ion concentration can be considered to be
5.00
equal. This gives us the confidence that the average values we calculated
4.00 y = 0.311x + 4.4109 and used in our calculations are a representative of the actual experi-
R² = 0.6084
mental results obtained. From t-test analysis, the mean for the actual and
ln qe

3.00 standard values for Ce, qe and %R are 15.46 versus 0, 184.54 versus 200
and 0.94 versus 1, respectively. Our p-values for Ce, qe and %R are all
2.00
greater than the confidence level of 0.05 and therefore we accept the null
1.00 hypothesis as our sample data support the hypothesis that there is no
significant difference between our calculated values of Ce, qe and %R and
0.00 their standard values.
-2.00 -1.00 0.00 1.00 2.00 3.00 4.00
Figure 5 shows that there is a positive correlation between concen-
ln Ce
tration of Pb2þ ions and qe. This is because increased amount of Pb2þ ions
will be available at a higher initial ion concentration, increasing the
Figure 8. Linearized plot for the Freundlich isotherm model. possibility of contact between the ions and the adsorbent (Lei et al.,

8
M. Manyangadze et al. Heliyon 6 (2020) e05309

Figure 9. Langmuir isotherm from experimental and simulated data.

2019). In addition, a high initial metal ion concentration enhances Figure 6 shows that as the equilibrium concentration of Pb2þ ions is
diffusion from the solution to the adsorbent's active sites i.e. there is an increased initially but the rate of adsorption at equilibrium plateaus i.e.
increase in the diffusion gradient leading to an increase in the mass the trend is levelling out. This is due to reduction of binding sites
transfer process (Lei et al., 2019). available for adsorption as initial metal ion concentration increases. This
In general, our experimental results elucidate that there is a positive helps to explain our trend which shows that the rate of adsorption de-
correlation between the initial metal ion concentration and adsorption creases with an increase in initial metal ion concentration (Co). Higher Co
capacity. In this study, we also observed that the adsorption efficiency led to a higher Ce, leading to reduced rate of adsorption (qe). In addition,
decreased with an associated increase in initial metal ion concentration. higher Ce led to low qe based on Eq. (5) and this is because of fixed
At low initial concentration, all of the Pb2þ ions were successfully binding sites available but now there is increased Pb2þ ions in solution
adsorbed (40–100 mg/g) of the adsorbent, proving that indeed at low with limited sites to bind to as the adsorbent mass was kept constant at 50
concentrations the adsorbent is very effective and efficient. Fathy et al. mg.
(2019) observed a similar trend when investigating adsorption of Pb2þ
and Co2þ ions using CaCO3/HPC core-shell composite from aqueous 3.2.3. Adsorption isotherms
solutions. They reasoned that at high initial metal concentrations there The two adsorption isotherms we considered during our studies were
was increased competitive dispersion of metal ions at the adsorbent the Langmuir and the Freundlich isotherms. Results for the Langmuir
surface i.e. the pores of the adsorbent were closed and metal ions found it isotherm model are given in Figure 7 and those for the Freundlich
difficult to pass deep into the adsorbent pores, restricting adsorption to isotherm model are given in Figure 8.
occur only on the adsorbent surface. This meant that if the adsorbent sites Figure 7 shows a plot obtained from application of Eq. (2) while
were reduced there was reduced adsorption efficiency. Mustapha et al. Figure 8 results from application of Eq. (4). From the regression analysis,
(2019) observed a similar trend in their adsorption experiments of Pb2þ, the line of best fit for the plots gave correlation coefficients (R2) values of
Cd2þ, Zn2þ and Cu2þ ions using Albizia lebbeck pods from aqueous so- 0.9937 and 0.6084 for Langmuir and Freundlich isotherms, respectively.
lutions for initial metal concentration of 10–30 mg/L. They reasoned that A comparison with the coefficient of correlation for the Freundlich
when the initial concentration is increased, enhanced driving force be- model, with a value of 0.6098 shows that the best model to describe the
tween the solid and liquid phases results in saturation of the adsorption adsorption of Pb2þ on NSHS is the Langmuir isotherm. This suggests that
sites. We attribute this kind of behaviour to depletion of active sites on the adsorption of Pb2þ ions on NSHS occurs on a homogeneous surface by
the surface of NSHS. However, when the initial concentration is lower, a single layer (El-Naggar et al., 2019; Mustapha et al., 2019). A corre-
the trend reverses (Mustapha et al., 2019). Gusain et al. (2019) investi- lation coefficient of 0.6098, in comparison with that of the Langmuir,
gated adsorption of Pb2þ and Cd2þ ions from industrial mine while using shows a poor fit implying that the Freundlich isotherm cannot be used to
hierarchical MoS2/SH-MWCNT nanocomposite synthesized using a facile model the equilibrium relationship between adsorption capacity and
hydrothermal method and observed a slight decrease in adsorption ef- sorbate concentration for the adsorption of Pb2þ ions on NSHS i.e.
ficiency with an increase in initial metal concentration for Pb2þ ions but a adsorption is not on a heterogeneous surface.
bigger decrease for Cd2þ ions. They attributed this observation to a In this study, we used the Langmuir isotherm to best describe the
decrease in binding sites with an increase in initial metal ion concen- adsorption equilibrium and we made use of Figure 7 and Eq. (2), to
tration due to saturation of the binding sites. El-Naggar et al. (2019) determine the parameters for Langmuir (b and qm). We substituted the
observed a similar trend when they employed a Kaolinite/Smectite nat- gradient and intercept values into some Eq. (2) to determine qm and b,
ural composite adsorbent to study the removal of Pb2þ ions from respectively and we determined qm ¼ 266.89 mg/g and b ¼ 0.89 L/mg.
wastewater, using different concentrations of Pb2þ ions ranging from 125 The Langmuir isotherm for Pb2þ ions adsorption from wastewater using
to 500 mg/L Lei et al. (2019) also observed a similar trend when using NSHS is given as:
dopamine-modified magnetic nano-adsorbents to adsorb Cd2þ ions from
an aqueous solution. 236:96Ce
qeðNSHSÞ ¼ (13)
A plot of adsorbed metal ions per adsorbent (qe) versus equilibrium 1 þ 0:89Ce
concentration (Ce) is given in Figure 6 and it helped to explain our trend. A plot of qe versus Ce for calculated qe from Langmuir equation

9
M. Manyangadze et al. Heliyon 6 (2020) e05309

Table 8. Comparison of different adsorption capacities of metal ions from aqueous solutions based on Langmuir adsorption isotherm.

Sample Metal ion adsorbed qm (mg/g) b (L/mg) Contact time (mins) Reference
Novel synthesized CaCO3 nanoparticles Cu2þ 666.67 0.1293 120 Mohammadifard and Amiri (2017)
Magnesium silicate hierarchical nanostructures Pb2þ 436.68 1.3880 1440 Huang et al. (2017)
Hydroxyapatite nanostructures Pb2þ 322.60 0.0830 80 Safatian et al. (2019)
NSHS Pb2þ 266.89 0.8900 40 Present work
Thiol-functionalized cobalt ferrite magnetic Hg2þ 258.80 (No model used) - 180 Li et al. (2020)
mesoporous silica composite (SH-mSiO2@CoFe2O4)
Jujube Pit Biochar Pb2þ 192.00 0.0036 30 Gao et al. (2020)
Hierarchical MoS2/SH-MWCNT nanocomposite Pb2þ 90.00 (Freundlich isotherm) - 60 Gusain et al. (2019)
CaCO3/HPC core-shell composite Pb2þ 82.99 0.5119 150 Fathy et al. (2019)
Hierarchical MoS2/SH-MWCNT nanocomposite Cd2þ 66.67 (Freundlich isotherm) - 60 Gusain et al. (2019)
Dopamine-modified magnetic nano-adsorbent Cd2þ 21.58 0.0397 100 Lei et al. (2019)
Cashew nutshell adsorbent Pb2þ 17.82 0.2197 30 Kumar, 2014
Albizia lebbeck pods Pb2þ 7.17 0.4300 30 Mustapha et al. (2019)
Kaolinite/Smectite-B clay Pb2þ 6.51 0.2700 120 El-Naggar et al. (2019)
Kaolinite/Smectite-A clay Pb2þ 5.84 0.1620 120 El-Naggar et al. (2019)
CaCO3/HPC core-shell composite Co2þ 3.47 (Freundlich isotherm) - 150 Fathy et al. (2019)

against experimental qe shows good estimation using the equation unit mass of adsorbent that forms a complete surface monolayer. The
(Figure 9). high adsorption capacity for NSHS and other nano-based materials can be
Huang et al. (2017) investigated adsorption of Pb2þ, Zn2þ and Cu2þ attributed to their higher surface area to volume ratio as alluded to
ions from aqueous solution using magnesium silicate hierarchical nano- earlier. In addition to this, the high adsorption capacity and efficiency of
structures and determined that adsorption of Pb2þ, Zn2þ and Cu2þ ions NSHS supported on CaCO3 can partly be attributed to the polymorph and
were best modelled by Langmuir isotherm (R2 ¼ 0.999) with maximum size of the applied CaCO3 particles which can assist with adsorption of
adsorption capacity of 436.68, 78.86 and 52.30 mg/g, respectively. Pb2þ ions from aqueous solution. These results show that the NSHS we
Safatian et al. (2019) investigated the adsorption of Pb2þ ions from water synthesized in this investigation is capable of removing lead ions from
and wastewater using hydroxyapatite nanostructures that were synthe- wastewater competitively.
sized from eggshells using microwave irradiation. Their adsorption In addition, the NSHS had very high maximum adsorption rates (qm)
process was better modelled using the Langmuir isotherm (R2 ¼ 0.994). and Langmuir adsorption equilibrium constant (b). The high qm and b
Fathy et al. (2019) investigated the adsorption of Pb2þ and Co2þ ions makes NSHS superior as the equations for determining qe for adsorbents
using CaCO3/HPC core-shell composite from aqueous solutions and on Pb2þ ions higher than NSHS in Table 8 were qeðMSHNÞ ¼ 1þ1:3884C
606:11Ce
e
and
observed that the adsorption process for Pb2þ ions was better modelled qe ðHNÞ ¼ 1þ0:083C
26:75Ce
which were plotted on Figure 9. The plots show that
with Langmuir isotherm (R2 0.930) but the adsorption of Co2þ was e

only adsorption using magnesium silicate hierarchical nanostructures

better modelled by Freundlich isotherm (R2 0.900). Mustapha et al.
(MSHN) gave better results than NSHS while adsorption using hy-
(2019) observed that the Langmuir isotherm better fitted adsorption of
droxyapatite nanostructures (HN) had lower qe values for the same
Pb2þ ions from aqueous solutions when using Albizia lebbeck pods,
equilibrium concentration range from our study. This shows that NSHS
however, Cd2þ, Zn2þ and Cu2þ ions could be modelled by either the
nanoparticles are able to compete successfully with other adsorbents
Langmuir or the Freundlich isotherm from the same experimental
being synthesized to remove Pb2þ ions from aqueous solutions.
studies.
We then used Eq. (14) and the Langmuir isotherm parameters to
Gusain et al. (2019) investigated adsorption of Pb2þ and Cd2þ ions
evaluate the affinity between the adsorbent and adsorbate through a
using hierarchical MoS2/SH-MWCNT nanocomposite and the adsorption
dimensionless separation factor, RL.
was better modelled using the Freundlich isotherm for both metal ions
indicating chemisorption i.e. multilayer adsorption of metal ions on 1
heterogeneous surfaces. El-Naggar et al. (2019) noticed that the RL ¼ (14)
1 þ bCo
adsorption of Pb2þ ions from wastewater using Kaolinite/Smectite nat-
ural composite adsorbents followed Freundlich isotherm based on cor- The RL values makes it easy to determine whether the adsorption is
relation coefficient values, unlike Langmuir isotherm for this study. Gao irreversible (RL ¼ 0), favorable (0 < RL < 1), linear (RL ¼ 1) or unfav-
et al. (2020) observed that the adsorption of Pb2þ ions from wastewater ourable (RL >1) (Mustapha et al., 2019). In Table 9 we show the calcu-
using biochar adsorbent obtained from jujube pit followed Freundlich lated values of RL for all the different initial metal ion concentrations.
isotherm based on correlation coefficient values. The RL values showed that the adsorption is favourable for all initial
The majority of the studies using different adsorbents for adsorption metal ion concentrations. Table 9 reveals that there is a negative corre-
of Pb2þ ions from aqueous solutions modelled the adsorption process lation between RL and metal ion concentration, which implies enhanced
using the Langmuir adsorption isotherm. This gives further evidence that adsorption of ions at lower initial metal ion concentrations. This gave
the adsorption process was homogeneous by a single layer and it was not further evidence to support observation of a reduction in adsorption ef-
chemisorption controlled. In Table 8, we illustrate the differences in ficiency/rate with an increase in initial metal ion concentration.
performance of various adsorbents in terms of their adsorption capacities
for lead ions. 3.2.4. Adsorption thermodynamics
From Table 8, the performance of NSHS was found to be very To determine the thermodynamic parameters, we plotted ln Kp versus
competitive and favourable in comparison to other adsorbents. The other 1/T (K1) from Table 3 and the results are shown in Figure 10.
adsorbents that outshone ours were nano based showing the impact of We then performed a regression analysis and determined the corre-
nanomaterials in adsorption process. The NSHS adsorbent has one of the lation coefficient to be 0.8787. The corresponding equation of the line of
best fit gave a gradient of -11698, corresponding to ΔH
o
largest intensity of adsorption and the highest amount of metal ions per R and an intercept

10
M. Manyangadze et al. Heliyon 6 (2020) e05309

Table 9. Separation factors for the adsorption of Pb2þ ions from wastewater using NSHS.

Initial concentration (mg/L) 40 100 200 300

RL 0.0274 0.0111 0.0056 0.0037

Figure 10. Relationship between the inverse of temperature and the adsorption equilibrium constant.

of 45.237 corresponding to ΔSR . Therefore, using Eqs. (10) and (11), the
o
Again, NSHS adsorbents are showing good performance against other
thermodynamic parameters were determined as follows: ΔH ¼ 97.255 adsorbents by giving higher thermodynamic values. This is proving their
kJ/mol, ΔS ¼ 0.376 kJ/mol⋅K and ΔG ¼ -22.120 kJ/mol. These three worth in removing Pb2þ ions from aqueous solutions. The activation
values show that the adsorption process for Pb2þ ions on NSHS is energy and activity constant were determined using Arrhenius law, Eq.
endothermic as evidenced by a positive ΔH value; and spontaneous as (16) and Figure 10 (El-Aila et al., 2016).
evidenced by a negative ΔG value. ΔH
values for adsorption can be used Ea
to determine whether the process is physical (2 < ΔHo < 21 kJ/mol), Kp ¼ AeRT (15)
physico-chemical (21 < ΔHo < 80 kJ/mol) or chemical (80 < ΔHo < 200 Taking natural logarithms:
kJ/mol) adsorption (Lei et al., 2019). This means that adsorption was of
the chemisorption type due to a ΔHo value that lies in the range 80–200 Ea
ln Kp ¼ ln A  (16)
kJ/mol. The positive ΔS value indicates that Pb2þ ions in the bulk RT
aqueous phase/solution are in a state of disorder as compared to the
relatively orderly state on the adsorbent's surface. However, the lower where Kp is adsorption equilibrium constant, A is pre-exponential con-
value of ΔS indicate that the ions are moving towards the ordered nature stant, Ea is activation energy for the reaction (kJ/mol), R is ideal gas
on the adsorbent surface. constant (kJ/mol⋅K) and T is absolute temperature (K).
The values of ΔG at the various temperatures were negative. We also Using the same gradient and intercept, the activation energy (Ea) was
observe that there is a negative correlation between ΔG and the solution found to be 97.255 kJ/mol and pre-exponential constant was found to be
temperature, which show that the adsorption process of Pb2þ ions on 4.43  1019. Therefore the Arrhenius law for adsorption of Pb2þ ions
NSHS was enhanced at higher temperatures i.e. the degree of sponta- from wastewater using NSHS is given by:
neous reaction increases with an increase in temperature (Mustapha  
11697:75
et al., 2019). The comparison between the thermodynamic data of NSHS TðKÞ

and other adsorbents is summarised in Table 10. Kp ¼ 4:43x1019  e (17)

Table 10. Differences in thermodynamic data for adsorption capacities of Pb2þ from wastewater between NSHS and other adsorbents.

Sample Metal ion adsorbed ΔHo (kJ/mol) ΔSo (J/mol⋅K) ΔGo (kJ/mol) Average T (oC) Reference
2þ 7
Kaolinite/Smectite-B clay Pb 2.18  10 79.00 -6700 53 El-Naggar et al. (2019)
NSHS Pb2þ 97.255 376.10 -22.120 44 Present work
CaCO3/HPC core-shell composite Pb2þ 41.912 90.68 -15.034 42.5 Fathy et al. (2019)
Albizia lebbeck pods Pb2þ 33.161 94.49 2.641 55 Mustapha et al. (2019)
Dopamine-modified magnetic nano-Adsorbent Cd2þ 25.714 0.13 -14.847 33 Lei et al. (2019)
Jujube Pit Biochar Pb2þ 22.520 170.00 -29.85 30 Gao et al. (2020)
Hierarchical MoS2/SH-MWCNT nanocomposite Pb2þ 8.06 54.30 -8.66 40 Gusain et al. (2019)
Kaolinite/Smectite-A clay Pb2þ 0.015 28.30 -584 53 El-Naggar et al. (2019)
Cashew nutshell adsorbent Pb2þ -5.607 -7.96 -3.112 45 Kumar, 2014

11
M. Manyangadze et al. Heliyon 6 (2020) e05309

This is the Arrhenius law for Pb2þ ions adsorption using NHSH from Hyderabad, India and Department of Chemical, Materials and Metallur-
wastewater. Mustapha et al. (2019) determined the activation energy of gical Engineering, College of Engineering and Technology, Botswana
33.161 kJ/mol when using Albizia lebbeck pods to remove metal ions International University of Science and Technology, Botswana.
include lead from aqueous solutions. The performance of NSHS on
adsorption of Pb2þ ions can be seen plotted on Figure 10 for the Competing interest statement
simulated equation. The estimate is very good within the temperature
range. The authors declare no conflict of interest.

4. Conclusion Additional information

In this equilibrium and thermodynamic investigation, we successfully No additional information is available for this paper.
synthesized nano silica hollow spheres (NSHS) that were verified by the
three characterization techniques employed. We then used the synthe- References
sized NSHS particles to remove Pb2þ ions from wastewater. From our
experimental results, we can conclude that temperature and initial metal Badruddoza, A.Z.Md., Shawon, Z.B.Z., Rahman, Md.T., Hao, K.W., Hidajat, K.,
ion concentration affect the adsorption of Pb2þ ions onto NSHS. We Uddin, M.S., 2013. Ionically modified magnetic nanomaterials for Arsenic and
Chromium removal from water. Chem. Eng. J. 225, 607–615.
elucidated that the Langmuir model best describes the relationship be- Bonamente, M., 2017. Statistics and Analysis of Scientific Data. Springer-Verlag, New
tween adsorption capacity at equilibrium and the corresponding sorbate York, USA.
concentration which means that it was monolayer and physical adsorp- Chen, J.F., Ding, H.M., Wang, J.X., Shao, L., 2004. Preparation and characterization of
porous hollow silica nanoparticles for drug delivery application. Biomaterials 25,
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for Pb2þ ions was 266.89 mg/g. We discovered from our experimental Dekking, F.M., Kraaikamp, C., Lopuha€a, H.P., Meester, L.E., 2005. A Modern Introduction
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so an in-depth study using continuous systems is highly recommended. large-pore-size porous magnesium silicate hierarchical nanostructures for high-
This is because continuous systems give a more realistic resemblance to efficiency removal of heavy metal ions. ACS Sustain. Chem. Eng. 5 (3), 2774–2780.
the industrial setup. In addition, desorption and reusability test experi- Kegl, T., Ban, I., Lobnik, A., Kosak, A., 2019. Synthesis and characterization of novel
γ-Fe2O3-NH4OH@SiO2(APTMS) nanoparticles for dysprosium adsorption. J. Hazard
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Declarations Kumar, P.S., 2014. Adsorption of lead(II) ions from simulated wastewater using natural
waste: a kinetic, thermodynamic and equilibrium study. Environ. Prog. Sustain.
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Author contribution statement Lei, T., Li, S.-J., Jiang, F., Ren, Z.-X., Wang, L.-L., Yang, X.-J., Tang, L.-H., Wang, S.-X.,
2019. Adsorption of cadmium ions from an aqueous solution on a highly stable
dopamine-modified magnetic nano-adsorbent. Nanoscale Res. Lett. 14, 352.
Milton Manyangadze: Conceived and designed the experiments; Li, K., Xie, L., Hao, Z., Xiao, M., 2020. Effective removal of Hg(II) ion from aqueous
Performed the experiments; Analyzed and interpreted the data; solutions by thiol functionalized cobalt ferrite magnetic mesoporous silica composite.
Contributed reagents, materials, analysis tools or data; Wrote the paper. J. Dispersion Sci. Technol. 41 (4), 503–509.
Manyangadze, M., Govha, J., Narsaiah, B.T., Kumar, P., Chakra, Ch.P.S., 2017. Removal
Nyaradzai M.H. Chikuruwo, Gratitude Charis, Gwiranai Danha & of Pb2þ from Water Using Silica Nano Spheres Synthesized on CaCO3 as a Template –
Tirivaviri A. Mamvura: Analyzed and interpreted the data; Contributed Adsorption Kinetics, Innovative Technologies for the Treatment of Industrial
reagents, materials, analysis tools or data; Wrote the paper. Wastewater: A Sustainable Approach. Apple Academic Press Publications, New
Jersey, USA.
T. Bala Narsaiah & Ch. Shilpa Chakra: Conceived and designed the Misran, H., Yarmo, M.A., Ramesh, S., 2013. Synthesis and characterization of silica
experiments; Analyzed and interpreted the data; Contributed reagents, nanospheres using nonsurfactant template. Ceram. Int. 39, 931–940.
materials, analysis tools or data; Wrote the paper. Mohammadifard, H., Amiri, M.C., 2017. Evaluating Cu(II) removal from aqueous
solutions with response surface methodology by using novel synthesized CaCO3
nanoparticles prepared in a colloidal gas aphron system. Chem. Eng. Commun. 204
Funding statement (4), 476–484.
Mourhly, A., Khachani, M., El Hamidi, A., Kacimi, M., Halim, M., Arsalane, S., 2015. The
synthesis and characterization of low-cost mesoporous silica SiO2 from local pumice
The authors would like to acknowledge their individual institutions
rock. Nanomater. Nanotechnol. 5, 35.
for assisting with the study. The institutions are Chemical and Process Mustapha, S., Shuaib, D.T., Ndamitso, M.M., Etsuyankpa, M.B., Sumaila, A.,
Systems Engineering Department, Harare Institute of Technology, Har- Mohammed, U.M., Nasirudeen, M.B., 2019. Adsorption isotherm, kinetic and
are, Zimbabwe; Industial and Manufacturing Engineering Department, thermodynamic studies for the removal of Pb(II), Cd(II), Zn(II) and Cu(II) ions from
aqueous solutions using Albizia lebbeck pods. Appl. Water Sci. 9, 142.
Harare Institute of Technology, Harare, Zimbabwe; Institute of Chemical Music, S., Filipovic-Vincekovic, N., Sekovanic, L., 2011. Precipitation of amorphous SiO2
Sciences and Technology, Jawaharlal Nehru Technological University, particles and their properties. Braz. J. Chem. Eng. 28 (1), 89–94.

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