Ligand based sustainable composite material for sensitive nickel(II) capturing in aqueous media

Journal Pre-proof Ligand based sustainable composite material for sensitive nickel(II) capturing in aqueous media Rabiul Awual, Munjur Hasan, Jibran Iqbal, Aminul Islam, Aminul Islam, Shahjalal Khandaker, Abdullah M. Asiri, Mohammed M. Rahman

PII:

S2213-3437(19)30714-6

DOI:

https://doi.org/10.1016/j.jece.2019.103591

Reference:

JECE 103591

To appear in:

Journal of Environmental Chemical Engineering

Received Date:

23 July 2019

Revised Date:

29 November 2019

Accepted Date:

3 December 2019

Please cite this article as: Awual R, Hasan M, Iqbal J, Islam A, Islam A, Khandaker S, Asiri AM, Rahman MM, Ligand based sustainable composite material for sensitive nickel(II) capturing in aqueous media, Journal of Environmental Chemical Engineering (2019), doi: https://doi.org/10.1016/j.jece.2019.103591

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier.

Md. Rabiul Awual

a, b, c

oo

f

Ligand based sustainable composite material for sensitive nickel(II) capturing in aqueous media * [email protected], Md. Munjur Hasan d, Jibran Iqbal

, Aminul Islam e, Md. Aminul Islam f , Shahjalal

pr

Khandaker g, Abdullah M. Asiri c, Mohammed M. Rahman c

b

Materials Science and Research Center, Japan Atomic Energy Agency (SPring–8), Hyogo 679–5148, Japan

b

College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates

c

Center of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia

d

Department of Applied Chemistry & Chemical Engineering, University of Dhaka, Dhaka-1000, Bangladesh

e

Department of Petroleum and Mining Engineering, Faculty of Engineering and Technology, Jessore University of Science and Technology,

Bangladesh

Pr

e-

a

Department of Arts and Sciences, Faculty of Engineering, Ahsanullah University of Science and Technology (AUST), Dhaka-1208, Bangladesh

g

Department of Textile Engineering, Dhaka University of Engineering and Technology, Gazipur-1707, Bangladesh.

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f

* Corresponding author.

E–mail address: (M.R. Awual).

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Graphical Abstract

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Research highlights:

Sustainable composite material was fabricated for sensitive Ni(II) ion remediation.



The materials were exhibited immense sensitivity toward Ni(II) ion at optimum state.



The diverse competing ion was not interfered due to the strong affinity at selected pH.

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

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ABSTRACT Organic ligand based sustainable composite material was prepared for the detection and removal of nickel (Ni(II)) ion from contaminated water. The ligand was anchored based on the building-block approach. The carrier silica and ligand embedded composite material were characterized systematically. The detection and removal of Ni(II) ion operation was evaluated according to the solution pH, reaction time, detection limit, initial Ni(II) concentration and diverse co-existing metal ions. The detection limit of Ni(II) ion by the proposed composite

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material was 0.41 µg/L. The detection and removal of Ni(II) ion was significantly influenced

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by the solution pH. However, the neutral pH 7.0 was chosen for sensitive and selective detection and removal of Ni(II) ion. The co-existing diverse metal ions were not interfered

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during the detection and removal of Ni(II) ion because of the high affinity of Ni(II) ion to composite material at the optimum experimental conditions. The Langmuir adsorption

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isotherm model was selected based on the materials morphology and applied to validate the

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adsorption isotherms according to the homogeneous ordered frameworks. The adsorption capacity was 199.19 mg/g as expected due to the high surface area of material. The adsorbed

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Ni(II) ion was completely eluted from the composite material with the eluent of 0.50 M HCl and the regenerated material was used in several cycles without deterioration in its initial

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performances. Therefore, it is expected to that the facile composite material may hold huge potentials in applications and may be scaled up for commercial applications, including environmental detection and removal of Ni(II) ion.

Keywords: Sustainable composite material; Nickel(II) ion; Immense sensitivity and selectivity; High adsorption; Water treatment.

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1. Introduction Heavy metal contamination of water bodies is a serious health matter as metal in drinking water can cause chronic or acute diseases to humans. Bioaccumulation of heavy metals can occur in fish or agriculture, and humans at the highest food chain level, which will receive all of the heavy metals across the food chain creating the highest health risk [1,2]. Among the various heavy-metal ions, nickel (Ni(II)) is an essential nutrient for living organisms and have been involved in the biological processes such as respiration, metabolism

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and biosynthesis [3-5]. While the deficiency of Ni(II) ion, affects the prokaryotic and

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eukaryotic organisms, excess of it creates adverse effects on blood and kidneys and leads to asthma, lung and bone cancer, sinus and other disorders in central nervous systems [1,6].

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Therefore, the Ni(II) ions at low levels offer essential trace nutrients, but it would harmful effects when the amount is excessive. Toxic metals, like copper, nickel and zinc, are most

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commonly found in waste effluents with the result that each country governing body may need

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to strictly maintain to discharge and exposure regulations [7]. Extensive usage of Ni(II) in industrial uses like rechargeable batteries, electrochromic devices, supercapacitors, electroless

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nickel plating technology and precursor for catalysts in chemical reaction [1,7], which comply to wide exposure of Ni(II) for the adverse effect of the respiratory system [2,4]. Thus,

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developing a novel material is always welcome for selective detection and removal of Ni(II) ion in environmental, industrial, food and biological samples. A number of analytical methods for metal ion quantification such as atomic

absorption spectroscopy (AAS), inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry methods have been reported [8-11]. In spite of the fact that these methods are highly sensitive, they are not convenient for “in-the-field” detection as they require expensive instruments which are very difficult to carry [12-14]. Optical recognition and sensing of metal ions has become an active field of research owing to its potential application in several fields

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which includes chemistry, bio-medicine, and environmental studies [15,16]. Detection of Ni(II) is highly important due to its toxic nature and widespread use in various industrial and catalytic processes. Most of the industrial methods for detection of Ni(II) are time consuming and depends on the involvement of sophisticated analytical techniques. Hence detection of Ni(II) using a very simple-to-use method which is rapid and also of low cost, is of utmost demand. The color formation upon addition of specific metal ion is promising based on the optical vision with easy to use facilities. Then there is a growing demand in the development of highly

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sensitive, low cost, specific selectivity and easily prepared colorimetric material for the

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detection of Ni(II) ion by naked-eye observation [17]. Several reports are indicated the detection of Ni(II) ion in colorimetric approach, however; many of them are not sensitive to

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detect in the trace level concentration in the waste samples [12]. Colorimetric sensor ensemble material comprise a class of reagent which shows a optimum color formation visible under

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‘naked eye’, on selectively binding with certain specific metal ions without the using of

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sophisticated and expensive instruments [14]. Thus the development of colorimetric material for the easy and rapid detection of Ni(II) is a demanding field of research as only a few have been reported until today. In earlier, we have prepared diverse functional material for specific

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metal ion detection based on the rapid response and sensitivity [15]. Herein, we have fabricated a novel optical materials for detection of Ni(II) ions based on the sufficient color formation at

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suitable pH condition. This can be simple, efficient, convenient, and versatile for sensitive detection of Ni(II) ions in contaminated water samples. Therefore, the efficient detection of Ni(II) ions in waste samples with other trace heavy metals is always difficult due to the bonding affinity between the metal ion and the functional surface of the fabricated materials [18,19]. Therefore, the preparation of a simple colorimetric detection of Ni(II) ions is our primary objective in this study.

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In order to supply the pure water by removing toxic ions, a number of methods has been reported over the last decades. The chemical precipitation, coagulation, ion-exchange, liquidliquid extraction, adsorption and coordination complexation by solid-liquid separation have been used to separate heavy-metal from wastewater according to each method advantages and limitations in application [20-24]. However, the adsorption is the most attractive and suitable method considering the easy operation, low operating cost and specific selectivity to the metal ion due to the materials functionality [25-27]. The complexation and ion exchange can separate

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dissolved ions from the water and has been used for the supplying of high purity water.

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Moreover, the complexation and ion-exchange functional material have a very strong affinity for dissolved ions, including heavy-metals; the ligand based functional material is highly

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suitable in purifying waste effluent to comply with the most stringent environmental discharge standards [28,29]. The composite materials are prepared with specific organic functional group

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embedded onto the carrier highly porous material, and these are exhibited high adsorption

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capacity and high selectivity to the specific metal ion compared to the non-modified ionexchange materials. From this connection, several ligand functionalized composite materials are indicated for diverse metal ion removal based on the ligand-field effect and pH dependency

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according to the nature of the composite materials [26-28]. The functional groups are highly dependent on selectivity and high adsorption capacity based on the nature of the composite

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material. However, adsorption by metal-oxyhydroxides has been extensively investigated because Ni(II) species adsorption onto the mineral surfaces plays an important role in determining the mobility and bioavailability [30-34]. Moreover, adsorption of solid material is more effective at low concentrations of harmful pollutants removal. However, the high price of material increases the cost of treatment methods [35-37]. Then several research efforts have been performed in order to develop new sensitive, selective and cost-effective materials [27,29].

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Therefore, this study will focus on the ligand based sustainable material fabrication for the use of selective detection and removal of Ni(II) ion from aqueous solutions. In this study, we developed composite material by successful ligand embedded onto the large cage mesostructures silica for the detection and removal of Ni(II) ions. The ligand onto mesoporous silica was associated based on non-covalent interactions, Van der Waals forces and reversible covalent bonds. The porous silica and composite material were characterized by specifically the TEM and N2 adsorption-desorption studies. The detection and adsorption

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operations were carried out in batch approach. Several parameters such as solution pH, limit of

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detection, contact time, and adsorption capacity were systematically investigated and discussed. This study is concerned with operational parameters for optimum detection and removal of

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Ni(II) from wastewater by sustainable composite material. A complete laboratory investigation of this process would generally consist of three parts such as (i) fabrication of composite

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material, (ii) demonstration the detection operation and feasibility low detection limit and (iii)

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optimum adsorption operation to achieve the data to be used in designing the full-scale plant. Moreover, this study highlights a new concept in the designing of composite material for the

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simple use with facile combination method to avoid the need for complicated procedures.

2. Materials and methods

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2.1. Materials All

chemicals

were

used

as

purchased

without

further

purification.

Tetramethylorthosilicate (TMOS), Pluronic F108 and 2-nitroso-1-naphthol (NN) were purchased from Sigma–Aldrich. The other chemicals were also obtained from in analytical grade. The pH adjustments in detection system, buffer solutions of 3–morpholinopropane sulfonic acid (MOPS), 2–(cyclohexylamino) ethane sulfonic acid (CHES), and N-cyclohexyl3-aminopropane sulfonic acids (CAPS), potassium chloride (KCl), concentrated hydrochloric

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acid (HCl) and sodium hydroxide (NaOH) was purchased in analytical grade. The standard nickel solution (1000 mg/L) and other metal salt reagents were purchased in analytical grade.

2.2. Fabrication of porous silica and composite material The preparation of mesoporous silica monolith method was involved by adding of TMOS and triblock copolymers F108 to obtain a homogenized Sol–gel mixture based on the F108/TMOS mass ratio. The liquid-crystal phase was achieved after quick addition of acidified

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aqueous solution and to promote hydrolysis of the TMOS around the liquid-crystal phase

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assembly of the triblock copolymer surfactants. However, the mesoporous silica monoliths were synthesized according to the reported methods with slight modification [38,39]. In typical

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conditions, the composition mass ratio of F108:TMOS:HCl/H2O was 1.4:2:1 respectively. The homogeneous Sol-gel synthesis was achieved by mixing F108/TMOS in a 200 mL beaker and

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then shaking at 60 °C until homogeneous. The exothermic hydrolysis and condensation of

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TMOS occurred rapidly by addition of acidified aqueous solution of HCl (at pH = 1.3) to this homogeneous solution. The methanol produced from the TMOS hydrolysis was removed by rotary evaporator at 45 °C. Then the material was dried at 45 °C for 24 h to complete the drying

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process. The organic moieties were removed by calcination at 530 °C for 6 h under the normal atmosphere. After calcinations, the material was grounded properly and ready to use as carrier

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material for the preparation of composite material. The composite material was fabricated via direct ligand immobilization of NN onto

mesoporous silica monoliths [40]. Then NN (70 mg) in ethanol solution was contacted with 1.0 g mesoporous silica materials. Immobilization was performed under vacuum at 30 °C until NN saturation was achieved. Then the ethanol was removed by a vacuum connected to a rotary evaporator at 45 °C and the resulting composite material was rinsed with warm water to check the stability and elution of NN from mesoporous silica. Then the material was dried at 45 °C

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for 6 h and ground to fine powder for detection and removal of Ni(II) ions experiments. In NN anchoring onto mesoporous silica, the final concentration/supernatant concentration of NN was counted the total washing amount of solution after NN immobilization operation. The MBHB immobilization amount (0.13 mmol/g) was determined by the following equation: Q = (Ci – Cf) V/m

(1)

where, Q is the adsorbed amount (mmol/g), V is the solution volume (L), m is the mass of

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mesoporous silica (g), Ci and Cf are the initial and final concentration of the NN, respectively.

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2.3. Detection and removal of Ni(II) ions

In the detection of Ni(II) ion, the composite material was immersed in a mixture of

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specific Ni(II) ion concentrations (2.0 mg/L) and adjusted at appropriate pH of 2.0, 3.50 (0.2 M of KCl with HCl), 5.20 (0.20 M CH3COOHCH3COONa with HCl), 7.0 (3-

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morpholinopropane sulfonic acid (MOPS) with NaOH), 9.50 (0.20 M 2-(cyclohexylamino)

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ethane sulfonic acid (CHES) with NaOH) and 11.02 (0.20 M N-cyclohexyl-3-aminopropane sulfonic acid (CAPS) with NaOH) at constant volume (10 mL) with shaking in a temperaturecontrolled water bath with a mechanical shaker at 25 °C for 10 min at a constant agitation speed

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of 110 rpm to achieve good color separation. A blank solution was also prepared, following the same procedure for comparison with color formation. After color optimization, the solid

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materials were separated with filtration methods and used for color assessment and absorbance spectra for the qualitative and quantitative Ni(II) ion estimation. The composite material was grounded properly into fine powder to achieve homogeneity in the absorbance spectra. The detection limit (LD) of Ni(II) ion using the newly prepared composite material was measured from the linear part of the calibration plot according to the following equation [41]: LD = KSb/m

(2)

where, K value is 3, Sb is the standard deviation for the blank and m the slope of the calibration

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graph in the linear range, respectively. In the removal process, the composite material was added in Ni(II) ion containing solution and adjusted at specific pH values by adding of HCl or NaOH (0.05 M) in 20 mL solutions, and the amount of composite material was 10 mg. After stirring for 1 h at room temperature, the solid material was separated by filtration system and Ni(II) concentrations in before and after adsorption operations were analyzed by ICP–AES. During the removal operation, the amount of adsorbed Ni(II) was calculated according to the following equations: Mass balance qe = (C0 – Cf) V/M (mg/g) (C0 – Cf) x 100 (%)

(4)

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and metal ion removal efficiency Re =

of

(3)

C0

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where, V is the volume of the aqueous solution (L), and M is the weight of the composite

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material (g), C0 and Cf are the initial and final concentrations of Ni(II) ion in solutions, respectively.

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To determine the equilibrium adsorption versus contact time, 10 mg of composite material was added to 20 mL solution containing 5.0 mg/L concentrations of Ni(II) ion. The

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mixture was then stirred, and composite material was filtered at different time intervals, and the filtrate solution was analyzed by ICP–AES. In the case of maximum removal capacity, 10

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mg of composite material was also added in various initial Ni(II) concentration and stirred for 3 h and filtrate solutions were analyzed by ICP–AES. The Ni(II) and the foreign ions were carried out to understand the selective adsorption

ability where diverse counter-ions were used. The solution was contained 20 mg/L of each Na(I), K(I), Li(I), Ca(II), Ba(II), Mg(II), Mn(II), Zn(II), Bi(III), Fe(III), Al(III) ion and the Ni(II) amount was 1.0 mg/L. The sample volume was to be 30 mL and composite material amount was 20 mg. Then the mixture was stirred for 2 h and separated by filtration. The solution was analysed by the ICP-AES. 11

In order to investigate the most efficient eluting agent, first 30 mL of 3.0 mM Ni(II) ion solution was adsorbed by the 50 mg composite material and then desorption experiments were carried out using 0.50 M HCl acid. The adsorbed Ni(II) ion onto the composite material was washed with deionized water several times and transferred into 50 mL beaker. To this 5.0 mL of the eluting agent was added, and then the mixture was stirred for 10 min. The concentration of Ni(II) ion released from the composite material into aqueous phase was analyzed by ICP– AES. Then the composite material was reused several cycles after washing with water to

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perform the reusability in several cycles.

2.4. Instrumentations

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The N2 adsorption-desorption isotherms were measured using the 3Flex analyzer (Micromeritics, USA) at 77 K for determining the material morphology in terms of surface

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characterization. The pore size was measured based on the Barrett–Joyner–Halenda (BJH)

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method. Both silica and composite material were preheated at 110 °C for 3 h. The TEM micrographs were received by using JEOL (JEM-2100F). To detect the color form of Ni(II) ion by UV–vis in the solid state was utilized for color optimization and their corresponding

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signal absorbance spectra measurement. The Ni(II) ion determination was analysed using ICPAES (PerkinElmer, Germany, 8300).

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All experiments in this study were duplicated to assure the consistency and

reproducibility of the results.

3. Results and discussion 3.1. Characterization of carrier silica and composite material The N2 adsorption-desorption isotherms of mesoporous silica showed the IV-type isotherm with a broad hysteresis loop of H2 type for typical mesopores with uniform entrances

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as shown in Fig. 1. In addition, adsorption branches significantly shifted toward lower relative pressure (P/P0). Moreover, the mesoporous silica monoliths exhibited the appreciable textural parameters of specific surface area (SBET), mesopore volume (Vp), and tunable pore diameters [38,41]. Moreover, the framework porosity in the N2 isotherm indicated the porosity contained within the uniform channels with well pore size distribution having pore diameter of 9.1 nm, high surface area (589 m2/g), and high pore volume (0.76 cm3/g). The high surface area and large pore size of this silica monoliths are great advantages in the fabrication of composite

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material that simultaneously detect and remove ultra-trace concentration of Ni(II) ions. After

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NN ligand immobilization (Fig. 1 (inset)), a decrease in the surface area and pore volume of composite material provided further evidence that the organic moieties of NN was embedded

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inside the mesoporous silica.

The TEM images of the porous silica show the uniform arrangement pores and

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continuous arrays along all directions with connecting each other as shown in Fig. 2 (A, B).

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Such porosity is advantageous because the direct interaction between the organic ligand molecules and the porous silica into the rigid condensed pore surfaces for high transportation of Ni(II) ion during the detection as charge-transfer and adsorption by stable complexation

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mechanism [27,39]. Moreover, the TEM micrographs also showed well-organized uniform parallel channels with hexagonal arrays in all directions. However, the surface modification

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method increased the stability of the composite material because of the strong electrostatic interactions between heteroatoms of organic ligand molecule and charged porous silica moieties. After successful NN ligand anchoring onto the porous silica, the significant pore with the ordered homogeneous porous morphology of the composite material was exhibited as the TEM images are shown in Fig. 2 (C, D). The data clarified that the ability to achieve flexibility in the specific activity of the electron acceptor or donor strength of the chemically responsive organic ligand molecule may lead to easy generation and transduction of visual naked-eye

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detection and removal of Ni(II) ion by stable complexation mechanism at optimum conditions.

3.2. Detection of Ni(II) ion in optical vision The pH of the solution is an important factor for selective and optical detection of trace Ni(II) ions. The present composite material was influenced by the solution pH in the detection of Ni(II) ions. The reflectance spectra of the [Ni-ligand]n+ complex at λ = 423 nm was carefully measured over a wide pH ranges as shown in Fig. 3. The data clarified that the amount of

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composite material was sufficient to achieve good color separation for Ni(II) ion according to the “signal” between the composite material “blank” and detection of Ni(II) ion “sample,” even

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at low levels of Ni(II). The composite material was sensitive in terms of its optical “color

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intensity” and signal response for Ni(II) ions at neutral pH region. In the signal responses, the highest absorbance at 423 nm was indicated as 100% in pH evaluation by the composite

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material. The results clarified that the composite material has high functionality and immense

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affinity in terms of selectivity and sensitivity towards the Ni(II) ions at pH 7.0. This pH region also suggested that the Ni(II) ions can bind strongly to functional group of the composite material with high stability during complex formation in the optical detection system.

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The sensitive detection is the great advantageous because the heavy-metal ion is existed in the water bodies in trace levels [9,11]. Then a series of samples containing different Ni(II)

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concentrations was evaluated to measure the sensitivity based on the color formation as well as corresponding signal intensity. The data are shown in Fig. 4(A). Upon addition of Ni(II) ion to the composite material containing solution, the color change was occurred as the signal intensity was indicated. The signal intensity of the composite material was also evaluated in the presence of various concentrations of diverse matrices. Increasing of the concentration of Ni(II) ion, the signal intensity was correspondingly increased. However, the highest concentration of Ni(II) ion was 2.0 mg/L, which gave sufficient color and signal intensity. Then

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the results are emphasized that even low concentration of Ni(II) ion could be detected by optical vision without using highly sophisticated apparatus. The calibration curve during the detection of Ni(II) ion by the composite material was also determined based on linear part of the calibration plot. Fig. 4(B) shows the calibration plot of the composite material during optical detection of Ni(II) ions. Several quantification measurements were evaluated using a wide range of concentrations of standard Ni(II) ion solutions under specific sensing conditions. The standard deviation of the Ni(II) ion analysis

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using composite material was 0.5% as evidenced by the fitting plot of the calibration graphs

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(Fig. 4(B), inset). The linear correlation at low Ni(II) ion concentration ranges indicated that Ni(II) can be detected and removed with the highest sensitivity and selectivity over a wide-

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range of concentrations. The detection limit (LD) of Ni(II) ions using the composite material was 0.41 µg/L according to Eq. (2), which indicates that the composite material simultaneously

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detect the Ni(II) ions at the ultra-trace concentration level [41].

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The ion selectivity is also the key factor for selective detection of metal ion by the material [40]. Moreover, the selectivity is completely dependent of the ligand functionality by the organic ligand based composite material [29]. Then the selectivity of this proposed material

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was measured using other metallic ions of Na(I), K(I), Li(I), Ca(II), Ba(II), Mg(II), Mn(II), Zn(II), Bi(III), Fe(III), Al(III), where the metal ion concentration was 20 times higher than the

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Ni(II) ion. Furthermore, the common anions ware also carried as shown in Fig. 5. These ions were considered to interfere if each metal ion exhibited the ±5% variation in the signal intensity compared with blank sample. In the presence of 1.0 mg/L of Ni(II), the color and the corresponding signal intensity were found, whereas no significant signal intensity was measured by the other metal ion as judged from Fig. 5. This result was confirmed that the Ni(II) has a strong coordination with soft donor atoms of the composite material active sites to form the stable complexation rather than other metal ions at this pH area. Then the possible

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complexation bonding mechanism between the Ni(II) and NN is shown in Scheme 1. The affecting parameters in the detection process clearly clarified the suitability of the composite material in the detection of Ni(II) ion from wastewater samples as well as onsite field application.

3.3. Adsorption of Ni(II) ion The solution pH is very important factor in any water treatment process and more so in

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metal ions removal from (waste) water. This is because the chemistry of water changes with a

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change in pH and often affects the removal of metal ions due to change in oxidation states of metal ions or change in charge density of composite material. In the current study, the Ni(II)

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ion adsorption experiment was carried out from pH 2.0–8.0. In this pH region, no precipitation occurred during adsorption experiment. Similar results were also reported by many researchers

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[42-44]. The data clarified that the Ni(II) adsorption was varied highly with the variation in

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pH, demonstrating that the Ni(II) removal efficiency was highly affected by the solution pH as shown in Fig. 6(A). As pH increased, the Ni(II) ion adsorption also increased due to protonation to deprotonation effect. However, the high Ni(II) ion adsorption was found at neutral pH of

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7.0. This is also noted that the ligand based materials are highly affected by the specific pH solution [45,46]. In other cases, the adsorption efficiency was increased with increasing pH due

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to the lower electrostatic repulsions between adsorbate and adsorbent functional surface. However, the pH 7.0 was chosen to evaluate the other experimental parameters in this study for readers understanding.

The effect of the reaction time between the composite material and Ni(II) ions in

aqueous solution was evaluated to determine the equilibrium adsorption time. A series of batch contact time experiments was performed to define and evaluate the equilibrium Ni(II) adsorption capacity and the filtrate solution was analysed by ICP–AES after each interval

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fraction. In this evaluation, the initial Ni(II) concentration was 5.0 mg/L in 20 mL volume and the composite material was 10 mg. The results are illustrated in Fig. 6(B). The data clarified that the adsorption of Ni(II) ions was rapid even in few minutes contact time. Increasing the contact time, increases the adsorption efficiency and the equilibrium adsorption was attained in 45 min. Therefore, contact time of 1 h was found to be sufficient to reach equilibrium and it was selected in further experimental works. It is reported that a long time is needed to attain equilibrium for precious metals with several ion exchangers and granular chelating resins [47].

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However, in the present study, the Ni(II) was adsorbed in a short time. It can be assumed that

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the adsorption of Ni(II) ions onto composite material follows mainly intraparticle diffusion and adsorption reaction mechanisms. This can be also attributed to the large surface area and the

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high surface reactivity of the composite material. However, the ion-exchange resin, fibrous and ligand exchange adsorbents are exhibited high kinetic performances [48,49].

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The adsorption behavior and capacity by the composite material depend on mainly the

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bonding strategy between the individual atoms or ions of the adsorbate and the donor atoms of the adsorbent material surface. Therefore, the behavior of the adsorption process was carried out by a set of experiments at pH 7.0 as indicated the optimum condition in the preceding

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section. The Langmuir adsorption isotherms are often used to describe adsorption of a solute from a liquid solution and can be used to predict the sorption efficiency at the equilibrium limit.

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Similarly, an isotherm assumes that adsorption occurs at homogeneous adsorption sites by the material and intermolecular forces decrease rapidly with the distance from the adsorption surface. Therefore, the nature of the adsorption process and the relation between the equilibrium concentrations of the adsorbate in the liquid phase and in the solid phase of the composite material were investigated with respect to the following well-known Langmuir adsorption model [16].

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Ce/qe = 1/(KLqm) + (1/qm)Ce (linear form)

(5)

where qe (mg/g) is the adsorption capacity at equilibrium, Ce (mg/L) is the equilibrium Ni(II) ion concentration, and qm (mg/g) and KL (L/mg) are the Langmuir constants related to the maximum adsorption capacity and energy of adsorption, respectively. The values of qm and KL were calculated from the slope and intercept of the linear plot of Ce/qe versus Ce. The data are shown in Fig. 7. The coefficient (R2) for Langmuir model was 0.997. The adsorption data and

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Langmuir model implies the good agreement and Ni(II) ion adsorption on the composite

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material appeared as a single monolayer coverage [50,51]. The maximum Ni(II) adsorption capacity on the composite material was determined from Langmuir adsorption isotherm was

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199.19 mg/g. The composite material has shown excellent capability for Ni(II) capturing from water solutions at this experimental protocol. This adsorption capacity was compared to the

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other forms of diverse adsorbents and the data are summarized in Table 1. The high adsorption

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capacity indicated that composite material is effective to adsorb Ni(II) ion in terms of efficiency and makes the material as a promising candidate for applications to in situ environmental remediation of the water samples [11,15].

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A variety of ionic compounds coexists in natural waters and competes with each other for available adsorption sites [15,26,41]. Therefore, the Ni(II) adsorption capacity of the

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composite material was investigated in the presence of diverse competing ions. The presence of interfering metal ion of Na(I), K(I), Li(I), Ca(II), Ba(II), Mg(II), Mn(II), Zn(II), Bi(III), Fe(III) and Al(III) on Ni(II) adsorption by the composite material was evaluated and the results are depicted in Fig. 8(A). Usually, the introductions of competing metal ion into working solutions have brought some negative effects on the target metal ion adsorption as defined by the several reports [12,17,42]. As regards the impact of diverse metal ion, the existence of the indicated metal ion showed no significant effect and had not caused a distinct reduction on

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Ni(II) adsorption capacity of the proposed composite material. The soft donor atoms are always favorable for stable complexation mechanism, and this may be main assumption for high selectivity by the composite material as expected.

3.4. Elution and reuses The elution and regeneration is the key factor to understand the material’s use in real sample treatment in large-scale [11,49]. Then the reusability composite material was performed

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after Ni(II) ion adsorption. In this study, 0.50 M HCl was used eluent for the recovery and

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reusability of the composite material after Ni(II) adsorption. After elution operation, the material was subsequently regenerated into the initial form after washing with water. The

-p

reuses data are shown in Fig. 8(B). As judged from Fig. 8(B), there was a slight decrease in adsorption efficiency from 98.9% to 90.0% for Ni(II) after eight cycles. Moreover, the

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composite material exhibited high structural stability even after multi-cycles use; such novel

lP

material is particularly applicable for metal ion capturing from environmental samples. Also the stable complexation was highly affected for the suitable Ni(II) ion capturing as depicted in Scheme 1. Therefore, the fabricated composite material can be used as potential material for

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the detection and removal of Ni(II) ion from waste solutions as effective material in large-scale

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use.

4. Conclusions

The suitable composite material was fabricated by ligand embedded onto the

mesoporous silica by building-block approach for efficient detection and removal of Ni(II) ion from aqueous solution. The reflectance spectra and specific color was formed when the Ni(II) ions made a stable complexation with the composite material. The color formation gave an extra advantage to detect the Ni(II) ion without using highly sophisticated apparatus. The

19

detection limit to Ni(II) ions by the material was 0.41 μg/L. Compared to traditional methods, this method was rapid, cheap and sensitive toward the Ni(II) ions at optimum experimental protocol. The adsorption properties of the material worsened to Ni(II) ions at lower pH regions. Increasing the solution pH lead to an increase the Ni(II) ions removal and the neutral pH 7.0 was chosen both in the detection and removal operation. The equilibrium data were well described by the Langmuir adsorption isotherm and the maximum adsorption capacity was 199.19 mg/g. The adsorbed Ni(II) ion onto the material was eluted with 0.50 M HCl and then

of

simultaneously regenerated into the initial form for next detection and adsorption operation

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without significant loss in its initial performances. The data suggested that the provided results are encouraging for the real application in large-scale for the environmental Ni(II) containing

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water samples. Therefore, the detection and removal of Ni(II) ions by the sustainable composite

lP

and collaborating with the environment.

re

material is an alternative to better use of wastewater treatment, being economically beneficial

Author Contributions Section

M.R.A. was designed the work by conjugation of organic ligand and inorganic mesoporous

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silica, performed the experiments, analysed the data, wrote and revised the manuscript. M.M.M was collected the all relevant references and added. J.I., A.I., M.A.I., S.K., A.M.A. and M.M.R

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were participated in scientific discussions in the final submission.

Acknowledgments

The research was partially supported by the RIF grant (R19052) from Zayed University, Abu Dhabi, United Arab Emirates. Also the research was partially supported by the Grant-inAid for Research Activity Start-up (24860070) from the Japan Society for the Promotion of 20

Science. The part of the experimental works was carried out at Japan Atomic Energy Agency. The author also wishes to thanks to the anonymous reviewers and editor for their helpful

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suggestions and enlightening comments.

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novel nano-conjugate material for effective cobalt(II) ions capturing from wastewater, Chem. Eng. J. 324 (2017) 130–139; (c) M.R. Awual, An efficient composite material for selective lead(II) monitoring and removal from wastewater, J. Environ. Chem. Eng. 7 (2019) 103087; (d) M.R. Awual, M.M. Hasan, A.M. Asiri, M.M. Rahman, Novel optical composite material for efficient vanadium(III) capturing from wastewater, J. Mol. Liq. 283 (2019) 704–712. [42] (a) M. Naushad, Z.A. ALOthman, T. Ahamad, M.R. Awual, Adsorption of Rose Bengal dye from aqueous solution by amberlite IRA-938 resin: Kinetics, isotherms and thermodynamic studies, Desalination Water Treat. 57 (2016) 13527–13533; (b) M.R. Awual, M.M. Hasan, A ligand based innovative composite material for selective lead(II) capturing from wastewater, J. Mol. Liq. 294 (2019) 111679; (c) M.R. Awual, M.M. Hasan, A. Islam, M.M. Rahman, A.M. Asiri, M.A. Khaleque, M.C. Sheikh, Introducing an amine functionalized novel conjugate material for toxic nitrite detection and adsorption from wastewater, J. Clean. Prod. 228 (2019) 778–785; (d) M.R. Awual, Mesoporous composite material for efficient lead(II) detection and removal from aqueous media, J. Environ. Chem. Eng. 7 (2019) 103124. [43] B. Xiang, D. Ling, H. Lou, H. Gu, 3D hierarchical flower-like nickel ferrite/manganese dioxide toward lead (II) removal from aqueous water, J. Hazard. Mater. 325 (2017) 178-188. [44] (a) S. Khan, T.G. Kazi, M. Soylak, A green and efficient in-syringe ionic liquid-based single step microextraction procedure for preconcentration and determination of cadmium in water samples, J. Ind. Eng. Chem. 27 (2015) 149–152; (b) A. Islam, S.H. Teo, M.R. Awual, Y.H. Taufiq-Yap, Improving the hydrogen production from water over MgO promoted Ni-Si/CNTs photocatalyst, J. Clean. Prod. 238 (2019) 117887; (c) A. Islam, S.H. Teo, M.R. Awual, Y.H. Taufiq-Yap, Assessment of clean H2 energy production from water using novel silicon photocatalyst, J. Clean. Prod. https://doi.org/10.1016/j.jclepro.2019.118805; (d) A. Islam, T. Ahmed, M.R. Awual, A. Rahman, M. Sultana, A.A. Aziz, M.U. Monir, S.H. Teo, M. Hasan, Advances in sustainable approaches to recover metals from e-waste-A review, J. Clean. Prod. https://doi.org/10.1016/j.jclepro.2019.118815. [45] (a) M. Ghaedi, A. Shokrollahi, K. Niknam, E. Niknam, A. Najibi, M. Soylak, Cloud point extraction and flame atomic absorption spectrometric determination of cadmium(II), lead(II), palladium(II) and silver(I) in environmental samples, J. Hazard. Mater. 168 (2009) 1022–1027; (b) M.M. Rahman, K.A. Alamry, M.R. Awual, A.E.M. Mekky, Efficient Hg(II) ionic probe development based on one-step synthesized diethyl thieno[2,3-b]thiophene-2,5-dicarboxylate (DETTDC2) onto glassy carbon electrode, Microchem. J. 152 (2020) 104291. [46] M. Soylak, E. Yilmaz, Ionic liquid dispersive liquid-liquid micro extraction of lead as pyrrolidinedithiocarbamate chelate prior to its flame atomic absorption spectrometric determination, Desalination. 275 (2011) 297–301. [47] (a) A. Shahat, H.M.A. Hassan, H.M.E. Azzazy, M. Hosni, M.R. Awual, Novel nanoconjugate materials for effective arsenic(V) and phosphate capturing in aqueous media, Chem. Eng. J. 331 (2018) 54–63; (b) M.R. Awual, M.A. Hossain, M.A. Shenashen, T. Yaita, S. Suzuki, A. Jyo, Evaluating of arsenic(V) removal from water by weak-base 28

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anion exchange adsorbents, Environ. Sci. Pollut. Res. 20 (2013) 421–430; (c) M.R. Awual, M.A. Shenashen, T. Yaita, H. Shiwaku, A. Jyo, Efficient arsenic(V) removal from water by ligand exchange fibrous adsorbent, Water Res. 46 (2012) 5541–5550; (d) M.R. Awual, A. Jyo, Assessing of phosphorus removal by polymeric anion exchangers, Desalination 281 (2011) 111–117. [48] (a) M.R. Awual, A. Jyo, T. Ihara, N. Seko, M. Tamada, K.T. Lim, Enhanced trace phosphate removal from water by zirconium(IV) loaded fibrous adsorbent, Water Res. 45 (2011) 4592–4600; (b) M.R. Awual, A. Jyo, S.A. El-Safty, M. Tamada, N. Seko, A weak-base fibrous anion exchanger effective for rapid phosphate removal from water, J. Hazard. Mater. 188 (2011) 164–171; (c) M.R. Awual, S.A. El-Safty, A. Jyo, Removal of trace arsenic(V) and phosphate from water by a highly selective ligand exchange adsorbent, J. Environ. Sci. 23 (2011) 1947–1954; (d) M.R. Awual, A. Jyo, Rapid column-mode removal of arsenate from water by crosslinked poly(allylamine) resin, Water Res. 43 (2009) 1229–1236. [49] (a) M.R. Awual, S. Urata, A. Jyo, M. Tamada, A. Katakai, Arsenate removal from water by a weak-base anion exchange fibrous adsorbent, Water Res. 42 (2008) 689–696; (b) M.R. Awual, M.A. Shenashen, A. Jyo, H. Shiwaku, T. Yaita, Preparing of novel fibrous ligand exchange adsorbent for rapid column–mode trace phosphate removal from water, J. Ind. Eng. Chem. 20 (2014) 2840–2847; (c) M.R. Awual, Efficient phosphate removal from water for controlling eutrophication using novel composite adsorbent, J. Clean. Prod. 228 (2019) 1311–1319; (d) M.R. Awual, M.M. Hasan, A.M. Asiri, M.M. Rahman, Cleaning the arsenic(V) contaminated water for safe-guarding the public health using novel composite material, Compos. Part B-Eng. 171 (2019) 294–301. [50] (a) M.A. Islam, D.W. Morton, M.J. Angove, Recent innovative research on chromium(VI) adsorption mechanism, Environ. Nanotechnol, Mont. Manage. 12 (2019) 100267; (b) M.A. Islam, M.J. Angove. D.W. Morton, B.K. Pramanik, M.R. Awual, A mechanistic approach of chromium(VI) adsorption onto manganese oxides and boehmite, J. Environ. Chem. Eng. https://doi.org/10.1016/j.jece.2019.103515; (c) M.R. Awual, M.M. Hasan, J. Iqbal, A. Islam, M.A. Islam, S. Khandaker, A.M. Asiri, M.M. Rahman, Naked-eye lead(II) capturing from contaminated water using innovative large-pore facial composite materials, Microchem. J. (2020); (d) M.R. Awual, M.M. Hasan, A. Islam, A.M. Asiri, M.M. Rahman, Optimization of an innovative composited material for effective monitoring and removal of cobalt(II) from wastewater, J. Mol. Liq. https://doi.org/10.1016/j.molliq.2019.112035. [51] (a) M.A. Islam, D.W. Morton, M.J. Angove, Macroscopic and modeling evidence for nickel(II) adsorption onto selected manganese oxides and boehmite, J. Water Proc. Eng. 32 (2019) 100964; (b) M.R. Karim, M.O. Aijaz, N.H. Alharth, H.F. Alharbi, F.S. AlMubaddel, M.R. Awual, Composite nanofibers membranes of poly(vinyl alcohol)/chitosan for selective lead(II) and cadmium(II) ions removal from wastewater, Ecotox. Environ. Saf. 169 (2019) 479–486; (c) S.H. Teo, A. Islam, E.S. Chan, S.Y.T. Choong, N.H. Alharthi, Y.H. Taufiq-Yap, M.R. Awual, Efficient biodiesel production from Jatropha curcus using CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles, J. Clean. Prod. 208 (2019) 816–826; (d) R.M. Kamel, A. Shahat, W.H. Hegazy, E.M.

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Khodier, M.R. Awual, Efficient toxic nitrite monitoring and removal from aqueous media with ligand based conjugate materials, J. Mol. Liq. 285 (2019) 20–26.

30

Table 1 Comparison of adsorption capacities with other forms of adsorbent material reported in the literature for Ni(II) ion

Adsorption capacity (mg/g)

Ref.

Date seed biochar

40.61

[3]

Hydrocalumite

369.74

[4]

of

Used adsorbents

91.70

[5]

Clarified sludge

14.30

[6]

956.60

[7]

-p

Cellulose nanocrystal

ro

Green alga

17.10

Diatomaceous earth composite

149.64

Activated carbon

57.14

[35]

Composite material

199.19

This study

Jo ur

na

lP

re

Lignocellulosic materials

31

[22] [24]

of ro -p re lP na

Fig. 1. N2 adsorption-desorption of (a) mesoporous silica, (b) ligand functionalized composite

Jo ur

material with different surface areas, pore sizes and pore volumes.

32

of ro -p re lP na

Jo ur

Fig. 2. The TEM images of the porous silica (A, B) and ligand embedded composite material (C, D) with uniformly arranged pores and ordered structures.

33

of ro -p re lP na

Jo ur

Fig. 3. Effect of solution pH for the detection of Ni(II) ions by the ligand functionalized composite material when equilibrated individually at different pH conditions with 2.0 mg/L of Ni(II). The standard deviation was >3.0% for the analytical data of duplicate analyses.

34

f oo pr ePr Jo ur na l

Fig. 4. Increasing the signal intensity in color optimization with increasing Ni(II) concentrations (A) and calibration profiles with signal intensity in different Ni(II) concentration (B). The inlets in graph (B) optical responses for Ni(II) ions with a linear fit in the linear concentration ranges. The R and R0 is the absorption signal responses of the adsorbent after and before addition of Ni(II). 32

of ro -p re lP na Jo ur

Fig. 5. Ion selectivity measurement of (1.0 mg/L) Ni(II) ion by the composite material after adding various competing ion in higher concentrations. The interfering cations (20.0 mg/L) listed in order (1 to 13): (1) Na(I), (2) K(I), (3) Li(I), (4) Ca(II), (5) Ba(II), (6) Mg(II), (7) Mn(II), (8) Zn(II), (9) Bi(III), (10) Fe(III), (11) Al(III), (12) Blank and (13) 1.0 mg/L Ni(II) ion. The interfering (200 mg/L) anions listed in order (7 to 13): (7) chloride, (8) nitrate, (9) bicarbonate, (10) carbonate (11) sulfate, (12) phosphate and (13) citrate.

33

f oo pr ePr Jo ur na l

Fig. 6. The Ni(II) adsorption indifferent solution pH (A) and effect of contact time for the evaluation of equilibrium adsorption when Ni(II) concentration was 5.0 mg/ in 20 mL.

34

of ro -p re lP na Jo ur

Fig. 7. Langmuir adsorption isotherms for Ni(II) ion and the linear form (inlet) of the Langmuir plot (initial Ni(II) concentration from 2.0 to 82.0 mg/L; solution pH 7.0; composite material amount 10 mg; solution volume 30 mL; contact time for 3 h).

35

f oo pr ePr Jo ur na l

Fig. 8. The Ni(II) adsorption in the presence of diverse competing ion while Ni(II) concentration was 1.0 mg/L and competing ion concentration was 20.0 mg/L in each; (B) Reversibility and reusability of the composite material in adsorption-elution/recovery operations.

36

f oo pr ePr Jo ur na l Scheme 1. Possible complexation mechanism between the Ni(II) ion and the composite material active site at the optimum conditions.

37