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Novel optical composite material for efficient vanadium(III) capturing from wastewater
Accepted Manuscript Novel optical composite material for efficient vanadium(III) capturing from wastewater
Md. Rabiul Awual, Md. Munjur Hasan, Abdullah M. Asiri, Mohammed M. Rahman PII: DOI: Reference:
S0167-7322(19)30747-0 https://doi.org/10.1016/j.molliq.2019.03.119 MOLLIQ 10660
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
7 February 2019 19 March 2019 20 March 2019
Please cite this article as: M.R. Awual, M.M. Hasan, A.M. Asiri, et al., Novel optical composite material for efficient vanadium(III) capturing from wastewater, Journal of Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.03.119
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ACCEPTED MANUSCRIPT Novel optical composite material for efficient vanadium(III) capturing from wastewater Md. Rabiul Awual
a,b, c *,
Md. Munjur Hasan d, Abdullah M. Asiri b, Mohammed M.
Rahman b, a
Material Science and Research Center, Japan Atomic Energy Agency (SPring–8), Hyogo
b
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679–5148, Japan
Center of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz
Department of Chemical Engineering, Curtin University, GPO BoxU1987, Perth, WA 6845,
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c
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University, Jeddah 21589, Saudi Arabia
Australia
Department of Petroleum and Mining Engineering, Faculty of Engineering and
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d
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Technology, Jessore University of Science and Technology, Bangladesh
* Corresponding author.
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E–mail address: [email protected] and [email protected] (M.R. Awual).
Research highlights:
Organic-inorganic based composite material was fabricated for V(III) capturing. The material was exhibited cavities and high functionality toward the V(III). The V(III) was captured by naked-eye observation with sensitivity & selectivity.
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ACCEPTED MANUSCRIPT Graphical Abstract
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ACCEPTED MANUSCRIPT ABSTRACT The high-efficient detection and recovery of vanadium (V(III)) using organic ligand embedded inorganic-organic mesoporous composite material (MeCM) was studied in this work. After 2-methyl-8-quinolinol immobilization onto the porous silica, the MeCM was confirmed the high surface area, large pore diameters and ordered morphological
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homogeneity. The MeCM was exhibited fast and specific signal response to V(III) ion, and
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the color was observed by naked-eye based on the charge-transfer stable complexation
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mechanism. The MeCM was influenced by the solution pH and pH 3.50 was selected for the highest detection and adsorption ability. The limit of detection was 0.27 µg/L, which was
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remarkably low as defined. The MeCM was also exhibited comparatively high kinetic performances as the equilibrium adsorption was observer within short contact time. The
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adsorption data were fitted with the Langmuir isotherm model as expected from the MeCM morphology. The maximum capacity was found to be 192.16 mg/g with the monolayer
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adsorption coverage. The presence of diverse metal ion was not affected significantly during
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the detection and adsorption operations. The V(III) ion desorbed from the MeCM using 0.15
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M HCl and then simultaneously regenerated into the initial functionality for next operation as revealed from the several cycles reuses study. Therefore, the proposed MeCM is allowed to the sensitive, selective, easy to use, cost-effective, high efficiency, fast kinetics and stable capturing of V(III) ion even in the presence of diverse competing ion. In addition, there was no more secondary sludge production due to the reusability and makes it a potential candidate in better replacement technology for capturing V(III) ion in a wide range of practical purposes.
Keywords: Composite material; Vanadium(III) ion; Detection and recovery; High adsorption; Immense selectivity.
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ACCEPTED MANUSCRIPT 1. Introduction Vanadium is existed naturally around 65 different minerals and also deposited in fossil-fuel [1,2]. Moreover, there is widely used in many industries due to the good performance [3,4]. Several uses are indicated and specially used to produce special steel alloys such as high-speed tool steel [5]. The oxides such as vanadium pentoxide have
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exhibited important industrial application as a suitable catalyst for the production of sulfuric
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acid and selective catalytic reaction as required [6]. In addition, the application of vanadium
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redox flow battery is enhancing a hot topic in hydrometallurgy, which broadens the application scope of vanadium. Therefore, the recovery of vanadium has a bright future
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nowadays. On the other hand, the vanadium is clearly a threat to the environmental impact, especially in natural waters, with the possibility to be included as a regulated contaminant in
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the near future by the US Environmental Protection Agency (USEPA), and it is presently registered in the Contaminant Candidate List (CCL) [7,8]. The Occupational Safety and
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Health Administration (OSHA) have given the permissible limit [9,10]. The most common
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oxidation states of vanadium are III, IV and V in aqueous solution, where vanadium(V) is the
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most toxic [11]. Vanadium can be frequently found in fuel oil, coal combustion, mineral ores, volcanic emissions, phosphorous ores and foods [12-14]. The chronic exposure to vanadium damages the integumentary, respiratory, central nervous and digestive system, as well as increases the risk of lung cancer [15]. Therefore, the detections and recovery of V(III) have great practical significance in research and establishment for many industries. Many techniques, including inductively coupled plasma mass spectrometry, inductively coupled plasma atomic emission spectrometry, and graphite furnace atomic absorption spectrometry have been reported for the determination of metal ion in water, food and environmental samples [16-23]. The determination of trace levels of vanadium desires the use of sensitive and selective techniques with cost-effective and easy to use methods. The
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ACCEPTED MANUSCRIPT level of vanadium in natural water samples is very low and then the accurate, reliable and sensitive materials are important to the analysis of vanadium. Recently, different organic and inorganic based composite materials are prepared for optical detection and monitoring of diverse metal ion based on the charge-transfer stable mechanism and naked-eye observation without using high-tech instrumentation [24,25]. This has led to design the ligand based
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material for efficient detection of vanadium. Then the optical composite material was
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designed for sensitive detection of V(III) in aqueous media. However, the problem with the
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solid material and stability remains unresolved. Then the designing of robust detection method that can detect the specific pollutants from wastewater with fast environmental
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analysis, easy to handle and cost-effective is always needed. In addition, this is the first approach for the capturing of V(III) in optical approach with naked-eye observation.
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Several materials have been reported for the adsorption of vanadium from aqueous solutions, including ion-exchange, activated carbon, waste metal sludge, sodium carbonate
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softening, calcium hydroxyapatite adsorption, modified chitosan, aluminum-pillared
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bentonite, and Fe(III)/Cr(III) hydroxide waste [26-30]. Various separation methods such as
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co-precipitation, cloud point extraction, flotation, solvent extraction; solid phase extraction has been developed [31-37]. However, the solid-liquid separation method is the suitable candidate as the promising in the second generation techniques. Several methods have many drawbacks such as high toxicity, requiring a high amount, operating complexity and costly. Adsorption has drawn attention based on the operational simplicity, high adsorption capacity and reusability. Then it is necessary to develop an efficient material to capture the ultra-trace vanadium from aqueous solutions that is not only cost effective, but also non-toxic to the environment and environment friendly. In this connection, we have used different ligand immobilized silica based material for various metal ion adsorptions from aqueous solution [38-40]. The materials have high surface area and an absence of internal diffusion resistance,
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ACCEPTED MANUSCRIPT and they have excellent performance to capture the metal ion at the optimum experimental protocol. Therefore, the present study was planned to develop ligand based functionalized mesoporous composite material (MeCM) for efficient V(III) detection and recovery from aqueous solution. In view of the environmental mitigation, we have designed the 2-methyl-8-quinolinol
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functionalized mesoporous composite material for V(III) ion detection and recovery from
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aqueous solutions. The MeCM was fabricated by direct anchoring of the organic ligand onto
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the porous silica. The material morphology of the porous silica and MeCM was characterized systematically to know the detail frameworks for V(III) capturing ability. After ligand
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immobilization, the MeCM was exhibited the high surface area and keep open the functionality for binding with the V(III) by the functional group of MeCM active sites. Here,
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the ligand molecule was played a molecular receptor, which transformed their chemical information into analytical signals upon binding to the V(III) ion. The usage of widely
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studied ligand in adsorbent gave an opportunity to save a lot of experimental efforts when
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studying the sensitivity, selectivity, cost, operational simplicity, and environment eco-
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friendly. The organic ligand was coated onto the porous silica by non-specific interaction via hydrogen bonding, Van der Waals forces and reversible covalent bonds. The performance of V(III) detection and recovery by the MeCM was carried out in batch-mode. Several experimental parameters such as solution pH, initial concentration, reaction time, counter-ion effects, and extraction or desorption were performed systematically. The material was displayed high selectivity toward the V(III) ion over foreign ion and is able V(III) capturing directly by naked-eye visualization.
2. Materials and methods 2.1. Materials
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ACCEPTED MANUSCRIPT All
chemicals
were
used
as
purchased
for
the
experimental
works.
Tetramethylorthosilicate (TMOS), Pluronic F108, and 2-methyl-8-quinolinol (MQNL) were purchased from Sigma–Aldrich. The other chemicals were also obtained from in analytical grade. The pH adjustments in monitoring system, buffer solutions of 3–morpholinopropane sulfonic acid (MOPS), and N-cyclohexyl-3-aminopropane sulfonic acids (CAPS), potassium
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chloride (KCl), concentrated hydrochloric acid (HCl) and sodium hydroxide (NaOH) was
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purchased in analytical grade. The standard vanadium solution (1000 mg/L) and other metal
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salt reagents were purchased in analytical grade.
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2.2. Preparation mesoporous silica and composite material (MeCM) The preparation of mesoporous silica monolith procedure was involved by adding of
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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
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acidified aqueous solution and to promote hydrolysis of the TMOS around the liquid-crystal
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phase assembly of the triblock copolymer surfactants. However, the mesoporous silica
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monoliths were synthesized according to the reported methods with slight modification [41,42]. In typical conditions, the composition mass ratio of F108:TMOS:HCl/H2O was 1.3:2:1 respectively. The homogeneous Sol-gel synthesis was achieved by mixing F108/TMOS in a 200 mL beaker and then shaking at 60°C until homogeneous. The exothermic hydrolysis and condensation of 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 materials were dried at 45°C for 24 h to complete the drying process. The organic moieties were removed by calcination at 510°C for 6 h under the normal atmosphere. After calcinations, the material was grounded properly and ready to use as carrier material for the preparation of
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ACCEPTED MANUSCRIPT MeCM. The mesoporous composite material (MeCM) was fabricated by direct immobilization of MQNL (60 mg) in methanol solution into 1.0 g mesoporous silica. The anchoring procedure was performed under vacuum at 30°C until MQNL saturation was achieved. The methanol was removed by a rotary evaporator at 45°C and the resulting MeCM was rinsed
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with warm water to check the stability and leaching of MQNL from silica material. Finally,
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the MeCM was dried at 45°C for 8 h and ground to fine powder for V(III) ion detection and
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removal experiments under optimum conditions. The MQNL immobilization amount was calculated from the following equation:
(1)
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Q = (Ci – Cf) V/m
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 MQNL,
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respectively.
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2.3. V(III) ion detection, adsorption and recovery studies
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In order to detect V(III), the MeCM was immersed in a mixture of specific V(III) ion concentrations (2.0 mg/L) and adjusted at appropriate pH of 1.0, 2.50, 3.50 (0.2 M of KCl with 2.0 M HCl), 5.20 (0.2 M CH3COOHCH3COONa with 1.0 M HCl) and 7.01 (0.2 M MOPS with NaOH) at constant volume (10 mL) with shaking in a temperature-controlled water bath with a mechanical shaker at 25°C for 10 min at a constant agitation speed 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 materials were separated with filtration methods and used for color assessment and absorbance spectra for the qualitative and quantitative V(III) ion estimation. The MeCM was grounded properly into fine powder to achieve homogeneity in the absorbance spectra. The detection limit (LD)
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ACCEPTED MANUSCRIPT of V(III) ion using the MeCM was measured from the linear part of the calibration plot according to the following equation [43]: LD = KSb/m
(2)
where, K value is 3, Sb is the standard deviation for the blank and m the slope of the calibration graph in the linear range, respectively.
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In the removal process, the MeCM was added in V(III) ion containing solution and
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adjusted at specific pH values by adding of HCl or NaOH in 20 mL solution, and the amount
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of MeCM was 10 mg. After stirring for 1 h at room temperature, the solid materials were separated by filtration system and V(III) concentrations in before and after sorption
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operations were analyzed by the ICP–AES. During the removal operation, the amount of adsorbed V(III) was calculated according to the following equations:
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Mass balance qe = (C0 – Cf) V/M (mg/g)
(3)
(C0 – Cf)
and metal ion removal efficiency Re =
x 100 (%)
(4)
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C0
where, V is the volume of the aqueous solution (L), and M is the weight of the MeCM (g), C0
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and Cf are the initial and final concentrations of V(III) ion in solutions, respectively. To determine the equilibrium adsorption versus contact time, 10 mg of MeCM was added to 20 mL solution containing 5.0 mg/L concentrations of V(III) ion. The mixture was then stirred, and MeCM was filtered at different time intervals, and the filtrate solution was analyzed by ICP–AES. In the case of maximum removal capacity, 10 mg of MeCM was also added in various initial V(III) concentration and stirred for 3 h and filtrate solutions were analyzed by ICP–AES. In order to investigate the most efficient eluting agent, first 30 mL of 3.0 mM V(III) ion solution was adsorbed by the 40 mg MeCM and then desorption experiments were carried out using 0.15 M HCl acid. The adsorbed V(III) ion onto MeCM was washed with deionized 9
ACCEPTED MANUSCRIPT 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 V(III) ion released from the MeCM into aqueous phase was analyzed by ICP–AES. Then the MeCM was reused several cycles after washing with water to perform the reusability in several
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cycles.
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2.4. Analyses
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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) method. Both silica and MeCM were preheated at 110 0C for 3 h. The TEM micrographs
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were received by using JEOL (JEM-2100F). To detect the color form of V(III) ion by UV–vis in the solid state was utilized for color optimization and their corresponding signal
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absorbance spectra measurement. The V(III) ion determination was analysed using the ICP-
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AES (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. Mesoporous silica and composite material The porosity of the porous silica and MeCM was measured by the N2 adsorptiondesorption isotherms. The N2 adsorption-desorption isotherms of the porous silica and the MeCM are shown in Fig. 1. The data clarified that both materials are exhibited high surface areas, large pore size and high pore volumes. These are advantages that after ligand immobilization, the MeCM was shown high surface but lower than the porous silica. A
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ACCEPTED MANUSCRIPT typical IV-type with broad H2 hysteresis loop was observed in both material [42,43]. The pore distribution was a regular framework with inter-particle as depicted from the textural porosity of the porous silica and MeCM. The surface areas were found to be 573 m2/g for porous silica and 417 m2/g for MeCM, respectively. The material also exhibited large pore volumes, and adsorption branch was shifted towards the lower relative pressure. The surface
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area, pore size and pore volume of the MeCM was lower than porous silica as expected
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because of the presence of ligand molecules onto the silica surface and a significant amount
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MQNL was embedded on the inner and outer surfaces of the silica monolith. The mesoporous structure was also measured by the TEM images. The TEM
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micrographs show (Fig. 2(A, B) the high ordered mesoporous structure in their frameworks, where the pores were well arranged as mesocage structures, which clarified that the direct
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interaction between MQNL and silica into the rigid condensed pore surfaces with retention of the ordered structures. The framework using TEM confirmed the hexagonal arrangement of
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mesopores in all directions [44]. These images show uniformly sized pores arranged and
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clarified the high accessibility of specific ion accumulation after modification by successful
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ligand anchoring. In the fabrication of MeCM, the hydrogen bonding or hetero atoms bonding might be happened between the abundant hydroxyl groups of pore surface silicates and the heteroatoms of the MQNL functional molecule. After successful MQNL anchoring, the appreciable mesopores were measured as shown in Fig. 1 (C, D).
3.2. V(III) detection The solution pH is the most affection parameters for metal ion detection by the ligand based material [45]. This is possible due to the functional group affinity to the specific metal in the pH regions [41,43]. Then the performance of the significant color change and corresponding signal intensity was measured at different pH regions for V(III) ion detection
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ACCEPTED MANUSCRIPT by the MeCM. The data are shown in Fig. 3. The color change and significant signal intensity compared to the blank sample were evaluated where the V(III) concentration was fixed to 2.0 mg/L and the pH ranges from 1.0–7.0. Fig. 3 shows that the maximum signal intensity was observed at pH 3.5. The data also clarified that the amount of MeCM was sufficient to observe the good color separation between the MeCM ‘‘blank’’ and V(III)–MeCM “sample”
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even in the trace V(III) levels. In the highly acidic region, the hydronium ion was high and
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hindered the V(III) ion accumulation. On the other hand, pH 3.50 was suitable for making the
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significant color for maximum charge-transfer mechanism. Then the pH 3.50 was chosen as the optimum experimental condition for V(III) detection, and all other affecting parameters
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on the detection process were carried at this pH area.
The sensitive detection is the advantages of the ligand functional material [46-50].
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Then the V(III) detection was carried from low to high concentration levels and the data shown in Fig. 4(A). The data revealed that the signal intensity was increased with increasing
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the V(III) concentration, and the color optimization was observed. At higher V(III)
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concentrations, the functional group of the MeCM was connected tightly with V(III) ion as
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stated by the color optimization and signal intensity enhancement. The color change during different concentration of V(III) ion was measured, and color formation was developed up to the concentration at 2.0 mg/L. The signal intensity of the MeCM was enhanced because of the charge-transfer complexation as reported elsewhere [24,25,29]. Therefore, enhancing the signal intensity corresponds to equilibrium color enhancement between the MeCM and V(III) ion implied the sensitive detection without using highly sophisticated instruments. The low detection limit clarifies the ultra-trace metal ion detection [51]. The detection limit was measured according to the linear response range based on the signal intensity measurement as define in preceding paragraph. With increasing concentration of V(III) ion, the signal intensity of the MeCM was increased, however; the low level was counted in the
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ACCEPTED MANUSCRIPT determination of the limit detection. The results are summarized in Fig. 4 (B), and the linear range was shown in the inset. The linear range was possible when the V(III) concentration was from 0.002–0.10 mg/L, with a correlation coefficient (R2) of 0.9996. The detection limit for V(III) was 0.27 μg/L. The observed detection limit is similar to the other authors reported for other metal ions with spectrophotometric detection, but its linear working range is more
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narrow [52]. The limit of detection for the determination of V(III) by the MeCM was
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revealed that the MeCM could detect the V(III) even in the ultra-trace level in the presence of
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several sample matrices.
The ion sensitivity is the key factor for the metal ion complexation by the functional
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ligand based material [24,29]. Then the foreign ion affinity to the MeCM was evaluated, and the data are shown in Fig. 5. The metal ion did not interfere when the signal intensity was
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lower than ±10%. For this reason, a series of solutions containing 20 mg/L of Na+, K+, Li+, Ca2+, Ba2+, Mg2+, Bi3+, Zn2+, Ni2+, Fe3+, Al3+ and some anion was also tested as indicated in
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the caption. To ensure the specific detection, the signal response of the MeCM was evaluated
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at pH 3.50. The data clarified that these foreign ions were not affected and did not show any
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measurable signal intensity except the V(III) ion. Therefore, the MeCM can be effective for V(III) ion detection with extreme sensitivity and selectivity.
3.3. V(III) adsorption
The pH control is an important experimental protocol during the removal of metal ion because it indicates the occurrence of parallel reactions as energy consumption increased, in addition to affecting on vanadium ion solubility [53-59]. The pH solution profile was measured during the V(III) adsorption by the MeCM as the data are shown in Fig. 6(A). It is obvious from the Fig. 6(A) that the MeCM was highly taken up the V(III) ion in the acidic region compared to the higher pH area. The basic pH region was not selected due to the
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ACCEPTED MANUSCRIPT hydroxide formation. The high adsorption efficiency was found at pH 3.50. Increasing or decreasing the pH of 3.50, the adsorption efficiency was decreased by the MeCM for V(III) ion. Similar trends are also observed by many ligand based material for heavy-metal ion adsorption [24]. Moreover, the ligand based material has specific adsorption efficiency at optimum solution acidity [25,29].
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The kinetic performance is measured based on the contact between the adsorbate and
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adsorbent [60]. The kinetic performance was evaluated where the initial V(III) concentration
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was fixed, and the reaction time was varied. The adsorption efficiency versus contact time is shown in Fig. 6(B). From the Fig. 6(B), the data emphasized that with increasing contact
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time the adsorption efficiency was increased and reaches the plateau. In the beginning, the abundant functional group was available and then slowly equilibrated. The V(III) was
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completely adsorbed by the MeCM within 50 min at this condition. The high kinetic performance will benefit a high efficient V(III) adsorption from aqueous media [61-63].
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Increasing the contact time further did not affect the V(III) adsorption. Then the equilibrium
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contact time of 3 h was sufficient to observe the maximum adsorption capacity by the MeCM
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in case of the high concentration of V(III) ion. The adsorption isotherm studies are important parameters to understand the nature of the material functionality [64-69]. To study the effect of initial concentration of V(III) on the adsorption capacity, the adsorption isotherm was undertaken. The results are shown in Fig. 7. The data was indicated that the adsorption capacity of V(III) was improved with increasing of initial concentration of V(III) ion until maximum adsorption was reached. With the further increase of V(III) concentration in solution, the adsorption capacity reached a plateau, indicating the saturation of the available active functional sites. The Langmuir isotherm model was used to interpret equilibrium isotherm data. The Langmuir isotherm is governed by the following relation and applied to the adsorption operation:
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Ce/qe = 1/(KLqm) + (1/qm)Ce
(linear form)
(5)
where Ce is the solution concentration at equilibrium (mg/L), qe the amount V(III) adsorbed at equilibrium (mg/g), KL the Langmuir constant (L/mg) which was considered as a measure
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of the adsorption energy and qm is the maximum adsorption capacity (mg/g) corresponding to
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complete monolayer coverage. A curve of Ce/qe versus Ce over the entire concentration
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range produces a straight line, which is an indication of the applicability of the Langmuir isotherm. The plot of V(III) adsorption by the PCM is single, smooth and continuous leading
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to saturation as shown in Fig. 7. The qm and KL are the Langmuir constants which are related to the adsorption capacity and energy of adsorption, respectively, and can be calculated from
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the intercept and slope of the linear plot, with Ce/qe versus Ce as shown in Fig. 7 (inset). The isotherms showed a sharp initial slope indicating high efficiency at low V(III) concentration,
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then the MeCM was saturated with increased V(III) levels. The V(III) adsorption onto the
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MeCM was taken onto the homogeneous surface, and adsorption was limited to the formation
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of the monolayer according to the Langmuir model. The coefficient value (R2=0.995) confirmed that the Langmuir adsorption was fitted with the adsorption behavior of the monolayer. The maximum adsorption capacity corresponding to complete monolayer coverage showed a mass capacity of 192.16 mg/g. The presence of co-existing ion may hinder the specific metal ion adsorption affinity by the adsorbent [70-76]. Therefore, the selective V(III) adsorption by the MeCM was also measured in this study. The ion selectivity was carried out from the multi-metal ions consisted solution, and the data are shown in shown Fig. 8(A). Here, the competing ions are Na(I), K(I), Li(I), Ca(II), Ba(II), Mg(II), Bi(III), Zn(II), Ni(II), Fe(III), Al(III) and each of the ion concentration were 20 mg/L while the V(III) ion concentration was 1.0 mg/L. The data
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ACCEPTED MANUSCRIPT also clarified that V(III) was adsorbed from the multi-mixture solutions with high selectivity. The data were evident that the V(III) adsorption was not significantly reduced in the presence of foreign ion by the MeCM. Then the newly prepared MeCM can effectively adsorb the V(III) ion from the waste sample by solid-liquid separation approach.
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3.4. Extraction, recovery and reuses
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The metal ion recovery by elution/desorption operation is an important parameter to
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evaluate the material as a cost-effective potential candidate in the real sample treatment [7781]. Then the extraction of V(III) from the MeCM was measured based on the elution
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operation. The elution experiment was carried out with 0.15 M HCl from the stand point of regeneration ability. By the using of this level of eluent, the MeCM was simultaneously
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regenerated into the initial form wand able use for nest operation without loss of cage cavities. In the elution stage, the V(III) was recovered as pure metal ion. Scheme 1 shows the
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possible bonding mechanism of V(III) with the MeCM. The reuse data are shown in Fig.
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8(B). Therefore, the MeCM showed better long–term stability and reusability towards V(III)
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ion and potential candidate for V(III) recovery from waste samples as well as environmental remediation.
4. Conclusions
The complete recovery, including detection and adsorption of vanadium (V(III)) from aqueous solution was investigated by mesoporous composite material (MeCM). The MeCM was fabricated by organic ligand of 2-methyl-8-quinolinol embedded onto the porous silica by the direct anchoring method. The porous silica and MeCM were characterized systematically to understand the material morphology as well as detection and adsorption behaviour. The MeCM was formed color corresponds to signal intensity upon addition of 16
ACCEPTED MANUSCRIPT V(III) even in the trace concentration. The low limit of detection was detected, and it was low as 0.27 µg/L. The effects of equilibrium pH, initial V(III) concentration, contact time, foreign ion and stripping agents were studied. The data presented that the MeCM was simple, rapid and immense sensitive to V(III) ion detection by the colorimetric method. The solution pH was influenced both in the detection and adsorption operation, and the MeCM were
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effectively captured the V(III) ion at pH 3.50. The presence of foreign ion was not affected
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the V(III) capturing by the MeCM. Therefore, the high selectivity of the MeCM was assumed
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to treat the V(III) containing waste samples. The adsorption data were well fitted to the Langmuir model, and the maximum adsorption capacity was also high as 192.16 mg/g with
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the monolayer coverage. The adsorbed V(III) was extracted with stripping agent of 0.15 M HCl, and the MeCM were subsequently regenerated into the initial form for next operation
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after washing with water. The MeCM was reused in several cycles without significant deterioration of the performances. Then the fabricated MeCM can be used as an alternative
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Acknowledgments
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material for efficient V(III) recovery from waste effluents.
This research was partially supported by the Grant-in-Aid for Research Activity Startup (24860070) from the Japan Society for the Promotion of Science. The part of the experimental works was carried out at Japan Atomic Energy Agency. The authors also wish to thanks to the anonymous reviewers and editor for their helpful suggestions and enlightening comments.
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4592–4600; (b) M.R. Awual, A. Jyo, S.A. El-Safty, M. Tamada, N. Seko, J. Hazard. Mater. 188 (2011) 164–171; (c) M.R. Awual, S.A. El-Safty, A. Jyo, J. Environ. Sci. 23 (2011) 1947–1954; (d) M.R. Awual, A. Jyo, Water Res. 43 (2009) 1229–1236.
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696; (b) M.R. Awual, M.A. Shenashen, A. Jyo, H. Shiwaku, T. Yaita, J. Ind. Eng. Chem. 20 (2014) 2840–2847; (c) M.R. Awual, A. Jyo, M. Tamada, A. Katakai, J. Ion
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Scheme 1. Possible bonding mechanism of V(III) with MQNL at pH 3.50 during detection and adsorption operation to exhibit the sensitivity and selectivity.
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Fig. 1. N2 adsorption-desorption isotherms of mesoporous silica (a) and ligand immobilized composite material (b) with specific surface area, pore size and pore volumes.
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Fig. 2. The TEM micrographs of the ordered mesoporous silica (A, B) and TEM images after organic ligand of MQNL embedded composite material (C, D).
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Fig. 3. Effect of solution pH for V(III) detection by the composite material under different pH solutions when V(III) concentration was 2.0 mg/L in 10 mL solution.
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Fig. 4. (A) Color optimization with increasing the V(III) concentration at λ = 365 nm and (B) Calibration curve with different signal intensity of different V(III) concentrations. The insets in the graph (B) show the limit of detection range with a linear fit line in the linear concentration range.
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Fig. 5. Ion selectivity of the composite material during 1.0 mg/L of V(III) ion detection. The interfering cations (Na+, K+, Li+, Ca2+, Ba2+, Mg2+, Bi3+, Zn2+, Ni2+, Fe3+, Al3+) concentration was 20.0 mg/L.
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Fig. 6. The V(III) adsorption indifferent solution pH (A) and effect of contact time for the measurement of equilibrium adsorption when V(III) concentration was 5.0 mg/ in 20 mL.
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Fig. 7. Langmuir adsorption isotherms for V(III) ion and the linear form (inlet) of the Langmuir plot (initial V(III) concentration from 2.02 to 80.0 mg/L; solution pH 3.50; composite material amount 10 mg; solution volume 30 mL; contact time for 3 h).
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Fig. 8. The V(III) adsorption in the presence of diverse competing ion while V(III) 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.
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Md. Rabiul Awual, Md. Munjur Hasan, Abdullah M. Asiri, Mohammed M. Rahman PII: DOI: Reference:
S0167-7322(19)30747-0 https://doi.org/10.1016/j.molliq.2019.03.119 MOLLIQ 10660
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
7 February 2019 19 March 2019 20 March 2019
Please cite this article as: M.R. Awual, M.M. Hasan, A.M. Asiri, et al., Novel optical composite material for efficient vanadium(III) capturing from wastewater, Journal of Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.03.119
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. 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.
ACCEPTED MANUSCRIPT Novel optical composite material for efficient vanadium(III) capturing from wastewater Md. Rabiul Awual
a,b, c *,
Md. Munjur Hasan d, Abdullah M. Asiri b, Mohammed M.
Rahman b, a
Material Science and Research Center, Japan Atomic Energy Agency (SPring–8), Hyogo
b
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679–5148, Japan
Center of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz
Department of Chemical Engineering, Curtin University, GPO BoxU1987, Perth, WA 6845,
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c
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University, Jeddah 21589, Saudi Arabia
Australia
Department of Petroleum and Mining Engineering, Faculty of Engineering and
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d
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Technology, Jessore University of Science and Technology, Bangladesh
* Corresponding author.
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E–mail address: [email protected] and [email protected] (M.R. Awual).
Research highlights:
Organic-inorganic based composite material was fabricated for V(III) capturing. The material was exhibited cavities and high functionality toward the V(III). The V(III) was captured by naked-eye observation with sensitivity & selectivity.
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ACCEPTED MANUSCRIPT Graphical Abstract
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ACCEPTED MANUSCRIPT ABSTRACT The high-efficient detection and recovery of vanadium (V(III)) using organic ligand embedded inorganic-organic mesoporous composite material (MeCM) was studied in this work. After 2-methyl-8-quinolinol immobilization onto the porous silica, the MeCM was confirmed the high surface area, large pore diameters and ordered morphological
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homogeneity. The MeCM was exhibited fast and specific signal response to V(III) ion, and
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the color was observed by naked-eye based on the charge-transfer stable complexation
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mechanism. The MeCM was influenced by the solution pH and pH 3.50 was selected for the highest detection and adsorption ability. The limit of detection was 0.27 µg/L, which was
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remarkably low as defined. The MeCM was also exhibited comparatively high kinetic performances as the equilibrium adsorption was observer within short contact time. The
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adsorption data were fitted with the Langmuir isotherm model as expected from the MeCM morphology. The maximum capacity was found to be 192.16 mg/g with the monolayer
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adsorption coverage. The presence of diverse metal ion was not affected significantly during
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the detection and adsorption operations. The V(III) ion desorbed from the MeCM using 0.15
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M HCl and then simultaneously regenerated into the initial functionality for next operation as revealed from the several cycles reuses study. Therefore, the proposed MeCM is allowed to the sensitive, selective, easy to use, cost-effective, high efficiency, fast kinetics and stable capturing of V(III) ion even in the presence of diverse competing ion. In addition, there was no more secondary sludge production due to the reusability and makes it a potential candidate in better replacement technology for capturing V(III) ion in a wide range of practical purposes.
Keywords: Composite material; Vanadium(III) ion; Detection and recovery; High adsorption; Immense selectivity.
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ACCEPTED MANUSCRIPT 1. Introduction Vanadium is existed naturally around 65 different minerals and also deposited in fossil-fuel [1,2]. Moreover, there is widely used in many industries due to the good performance [3,4]. Several uses are indicated and specially used to produce special steel alloys such as high-speed tool steel [5]. The oxides such as vanadium pentoxide have
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exhibited important industrial application as a suitable catalyst for the production of sulfuric
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acid and selective catalytic reaction as required [6]. In addition, the application of vanadium
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redox flow battery is enhancing a hot topic in hydrometallurgy, which broadens the application scope of vanadium. Therefore, the recovery of vanadium has a bright future
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nowadays. On the other hand, the vanadium is clearly a threat to the environmental impact, especially in natural waters, with the possibility to be included as a regulated contaminant in
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the near future by the US Environmental Protection Agency (USEPA), and it is presently registered in the Contaminant Candidate List (CCL) [7,8]. The Occupational Safety and
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Health Administration (OSHA) have given the permissible limit [9,10]. The most common
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oxidation states of vanadium are III, IV and V in aqueous solution, where vanadium(V) is the
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most toxic [11]. Vanadium can be frequently found in fuel oil, coal combustion, mineral ores, volcanic emissions, phosphorous ores and foods [12-14]. The chronic exposure to vanadium damages the integumentary, respiratory, central nervous and digestive system, as well as increases the risk of lung cancer [15]. Therefore, the detections and recovery of V(III) have great practical significance in research and establishment for many industries. Many techniques, including inductively coupled plasma mass spectrometry, inductively coupled plasma atomic emission spectrometry, and graphite furnace atomic absorption spectrometry have been reported for the determination of metal ion in water, food and environmental samples [16-23]. The determination of trace levels of vanadium desires the use of sensitive and selective techniques with cost-effective and easy to use methods. The
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ACCEPTED MANUSCRIPT level of vanadium in natural water samples is very low and then the accurate, reliable and sensitive materials are important to the analysis of vanadium. Recently, different organic and inorganic based composite materials are prepared for optical detection and monitoring of diverse metal ion based on the charge-transfer stable mechanism and naked-eye observation without using high-tech instrumentation [24,25]. This has led to design the ligand based
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material for efficient detection of vanadium. Then the optical composite material was
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designed for sensitive detection of V(III) in aqueous media. However, the problem with the
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solid material and stability remains unresolved. Then the designing of robust detection method that can detect the specific pollutants from wastewater with fast environmental
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analysis, easy to handle and cost-effective is always needed. In addition, this is the first approach for the capturing of V(III) in optical approach with naked-eye observation.
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Several materials have been reported for the adsorption of vanadium from aqueous solutions, including ion-exchange, activated carbon, waste metal sludge, sodium carbonate
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softening, calcium hydroxyapatite adsorption, modified chitosan, aluminum-pillared
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bentonite, and Fe(III)/Cr(III) hydroxide waste [26-30]. Various separation methods such as
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co-precipitation, cloud point extraction, flotation, solvent extraction; solid phase extraction has been developed [31-37]. However, the solid-liquid separation method is the suitable candidate as the promising in the second generation techniques. Several methods have many drawbacks such as high toxicity, requiring a high amount, operating complexity and costly. Adsorption has drawn attention based on the operational simplicity, high adsorption capacity and reusability. Then it is necessary to develop an efficient material to capture the ultra-trace vanadium from aqueous solutions that is not only cost effective, but also non-toxic to the environment and environment friendly. In this connection, we have used different ligand immobilized silica based material for various metal ion adsorptions from aqueous solution [38-40]. The materials have high surface area and an absence of internal diffusion resistance,
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ACCEPTED MANUSCRIPT and they have excellent performance to capture the metal ion at the optimum experimental protocol. Therefore, the present study was planned to develop ligand based functionalized mesoporous composite material (MeCM) for efficient V(III) detection and recovery from aqueous solution. In view of the environmental mitigation, we have designed the 2-methyl-8-quinolinol
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functionalized mesoporous composite material for V(III) ion detection and recovery from
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aqueous solutions. The MeCM was fabricated by direct anchoring of the organic ligand onto
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the porous silica. The material morphology of the porous silica and MeCM was characterized systematically to know the detail frameworks for V(III) capturing ability. After ligand
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immobilization, the MeCM was exhibited the high surface area and keep open the functionality for binding with the V(III) by the functional group of MeCM active sites. Here,
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the ligand molecule was played a molecular receptor, which transformed their chemical information into analytical signals upon binding to the V(III) ion. The usage of widely
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studied ligand in adsorbent gave an opportunity to save a lot of experimental efforts when
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studying the sensitivity, selectivity, cost, operational simplicity, and environment eco-
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friendly. The organic ligand was coated onto the porous silica by non-specific interaction via hydrogen bonding, Van der Waals forces and reversible covalent bonds. The performance of V(III) detection and recovery by the MeCM was carried out in batch-mode. Several experimental parameters such as solution pH, initial concentration, reaction time, counter-ion effects, and extraction or desorption were performed systematically. The material was displayed high selectivity toward the V(III) ion over foreign ion and is able V(III) capturing directly by naked-eye visualization.
2. Materials and methods 2.1. Materials
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ACCEPTED MANUSCRIPT All
chemicals
were
used
as
purchased
for
the
experimental
works.
Tetramethylorthosilicate (TMOS), Pluronic F108, and 2-methyl-8-quinolinol (MQNL) were purchased from Sigma–Aldrich. The other chemicals were also obtained from in analytical grade. The pH adjustments in monitoring system, buffer solutions of 3–morpholinopropane sulfonic acid (MOPS), and N-cyclohexyl-3-aminopropane sulfonic acids (CAPS), potassium
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chloride (KCl), concentrated hydrochloric acid (HCl) and sodium hydroxide (NaOH) was
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purchased in analytical grade. The standard vanadium solution (1000 mg/L) and other metal
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salt reagents were purchased in analytical grade.
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2.2. Preparation mesoporous silica and composite material (MeCM) The preparation of mesoporous silica monolith procedure was involved by adding of
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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
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acidified aqueous solution and to promote hydrolysis of the TMOS around the liquid-crystal
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phase assembly of the triblock copolymer surfactants. However, the mesoporous silica
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monoliths were synthesized according to the reported methods with slight modification [41,42]. In typical conditions, the composition mass ratio of F108:TMOS:HCl/H2O was 1.3:2:1 respectively. The homogeneous Sol-gel synthesis was achieved by mixing F108/TMOS in a 200 mL beaker and then shaking at 60°C until homogeneous. The exothermic hydrolysis and condensation of 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 materials were dried at 45°C for 24 h to complete the drying process. The organic moieties were removed by calcination at 510°C for 6 h under the normal atmosphere. After calcinations, the material was grounded properly and ready to use as carrier material for the preparation of
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ACCEPTED MANUSCRIPT MeCM. The mesoporous composite material (MeCM) was fabricated by direct immobilization of MQNL (60 mg) in methanol solution into 1.0 g mesoporous silica. The anchoring procedure was performed under vacuum at 30°C until MQNL saturation was achieved. The methanol was removed by a rotary evaporator at 45°C and the resulting MeCM was rinsed
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with warm water to check the stability and leaching of MQNL from silica material. Finally,
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the MeCM was dried at 45°C for 8 h and ground to fine powder for V(III) ion detection and
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removal experiments under optimum conditions. The MQNL immobilization amount was calculated from the following equation:
(1)
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Q = (Ci – Cf) V/m
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 MQNL,
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respectively.
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2.3. V(III) ion detection, adsorption and recovery studies
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In order to detect V(III), the MeCM was immersed in a mixture of specific V(III) ion concentrations (2.0 mg/L) and adjusted at appropriate pH of 1.0, 2.50, 3.50 (0.2 M of KCl with 2.0 M HCl), 5.20 (0.2 M CH3COOHCH3COONa with 1.0 M HCl) and 7.01 (0.2 M MOPS with NaOH) at constant volume (10 mL) with shaking in a temperature-controlled water bath with a mechanical shaker at 25°C for 10 min at a constant agitation speed 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 materials were separated with filtration methods and used for color assessment and absorbance spectra for the qualitative and quantitative V(III) ion estimation. The MeCM was grounded properly into fine powder to achieve homogeneity in the absorbance spectra. The detection limit (LD)
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ACCEPTED MANUSCRIPT of V(III) ion using the MeCM was measured from the linear part of the calibration plot according to the following equation [43]: LD = KSb/m
(2)
where, K value is 3, Sb is the standard deviation for the blank and m the slope of the calibration graph in the linear range, respectively.
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In the removal process, the MeCM was added in V(III) ion containing solution and
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adjusted at specific pH values by adding of HCl or NaOH in 20 mL solution, and the amount
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of MeCM was 10 mg. After stirring for 1 h at room temperature, the solid materials were separated by filtration system and V(III) concentrations in before and after sorption
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operations were analyzed by the ICP–AES. During the removal operation, the amount of adsorbed V(III) was calculated according to the following equations:
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Mass balance qe = (C0 – Cf) V/M (mg/g)
(3)
(C0 – Cf)
and metal ion removal efficiency Re =
x 100 (%)
(4)
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C0
where, V is the volume of the aqueous solution (L), and M is the weight of the MeCM (g), C0
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and Cf are the initial and final concentrations of V(III) ion in solutions, respectively. To determine the equilibrium adsorption versus contact time, 10 mg of MeCM was added to 20 mL solution containing 5.0 mg/L concentrations of V(III) ion. The mixture was then stirred, and MeCM was filtered at different time intervals, and the filtrate solution was analyzed by ICP–AES. In the case of maximum removal capacity, 10 mg of MeCM was also added in various initial V(III) concentration and stirred for 3 h and filtrate solutions were analyzed by ICP–AES. In order to investigate the most efficient eluting agent, first 30 mL of 3.0 mM V(III) ion solution was adsorbed by the 40 mg MeCM and then desorption experiments were carried out using 0.15 M HCl acid. The adsorbed V(III) ion onto MeCM was washed with deionized 9
ACCEPTED MANUSCRIPT 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 V(III) ion released from the MeCM into aqueous phase was analyzed by ICP–AES. Then the MeCM was reused several cycles after washing with water to perform the reusability in several
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cycles.
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2.4. Analyses
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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) method. Both silica and MeCM were preheated at 110 0C for 3 h. The TEM micrographs
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were received by using JEOL (JEM-2100F). To detect the color form of V(III) ion by UV–vis in the solid state was utilized for color optimization and their corresponding signal
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absorbance spectra measurement. The V(III) ion determination was analysed using the ICP-
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AES (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. Mesoporous silica and composite material The porosity of the porous silica and MeCM was measured by the N2 adsorptiondesorption isotherms. The N2 adsorption-desorption isotherms of the porous silica and the MeCM are shown in Fig. 1. The data clarified that both materials are exhibited high surface areas, large pore size and high pore volumes. These are advantages that after ligand immobilization, the MeCM was shown high surface but lower than the porous silica. A
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ACCEPTED MANUSCRIPT typical IV-type with broad H2 hysteresis loop was observed in both material [42,43]. The pore distribution was a regular framework with inter-particle as depicted from the textural porosity of the porous silica and MeCM. The surface areas were found to be 573 m2/g for porous silica and 417 m2/g for MeCM, respectively. The material also exhibited large pore volumes, and adsorption branch was shifted towards the lower relative pressure. The surface
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area, pore size and pore volume of the MeCM was lower than porous silica as expected
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because of the presence of ligand molecules onto the silica surface and a significant amount
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MQNL was embedded on the inner and outer surfaces of the silica monolith. The mesoporous structure was also measured by the TEM images. The TEM
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micrographs show (Fig. 2(A, B) the high ordered mesoporous structure in their frameworks, where the pores were well arranged as mesocage structures, which clarified that the direct
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interaction between MQNL and silica into the rigid condensed pore surfaces with retention of the ordered structures. The framework using TEM confirmed the hexagonal arrangement of
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mesopores in all directions [44]. These images show uniformly sized pores arranged and
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clarified the high accessibility of specific ion accumulation after modification by successful
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ligand anchoring. In the fabrication of MeCM, the hydrogen bonding or hetero atoms bonding might be happened between the abundant hydroxyl groups of pore surface silicates and the heteroatoms of the MQNL functional molecule. After successful MQNL anchoring, the appreciable mesopores were measured as shown in Fig. 1 (C, D).
3.2. V(III) detection The solution pH is the most affection parameters for metal ion detection by the ligand based material [45]. This is possible due to the functional group affinity to the specific metal in the pH regions [41,43]. Then the performance of the significant color change and corresponding signal intensity was measured at different pH regions for V(III) ion detection
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ACCEPTED MANUSCRIPT by the MeCM. The data are shown in Fig. 3. The color change and significant signal intensity compared to the blank sample were evaluated where the V(III) concentration was fixed to 2.0 mg/L and the pH ranges from 1.0–7.0. Fig. 3 shows that the maximum signal intensity was observed at pH 3.5. The data also clarified that the amount of MeCM was sufficient to observe the good color separation between the MeCM ‘‘blank’’ and V(III)–MeCM “sample”
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even in the trace V(III) levels. In the highly acidic region, the hydronium ion was high and
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hindered the V(III) ion accumulation. On the other hand, pH 3.50 was suitable for making the
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significant color for maximum charge-transfer mechanism. Then the pH 3.50 was chosen as the optimum experimental condition for V(III) detection, and all other affecting parameters
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on the detection process were carried at this pH area.
The sensitive detection is the advantages of the ligand functional material [46-50].
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Then the V(III) detection was carried from low to high concentration levels and the data shown in Fig. 4(A). The data revealed that the signal intensity was increased with increasing
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the V(III) concentration, and the color optimization was observed. At higher V(III)
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concentrations, the functional group of the MeCM was connected tightly with V(III) ion as
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stated by the color optimization and signal intensity enhancement. The color change during different concentration of V(III) ion was measured, and color formation was developed up to the concentration at 2.0 mg/L. The signal intensity of the MeCM was enhanced because of the charge-transfer complexation as reported elsewhere [24,25,29]. Therefore, enhancing the signal intensity corresponds to equilibrium color enhancement between the MeCM and V(III) ion implied the sensitive detection without using highly sophisticated instruments. The low detection limit clarifies the ultra-trace metal ion detection [51]. The detection limit was measured according to the linear response range based on the signal intensity measurement as define in preceding paragraph. With increasing concentration of V(III) ion, the signal intensity of the MeCM was increased, however; the low level was counted in the
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ACCEPTED MANUSCRIPT determination of the limit detection. The results are summarized in Fig. 4 (B), and the linear range was shown in the inset. The linear range was possible when the V(III) concentration was from 0.002–0.10 mg/L, with a correlation coefficient (R2) of 0.9996. The detection limit for V(III) was 0.27 μg/L. The observed detection limit is similar to the other authors reported for other metal ions with spectrophotometric detection, but its linear working range is more
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narrow [52]. The limit of detection for the determination of V(III) by the MeCM was
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revealed that the MeCM could detect the V(III) even in the ultra-trace level in the presence of
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several sample matrices.
The ion sensitivity is the key factor for the metal ion complexation by the functional
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ligand based material [24,29]. Then the foreign ion affinity to the MeCM was evaluated, and the data are shown in Fig. 5. The metal ion did not interfere when the signal intensity was
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lower than ±10%. For this reason, a series of solutions containing 20 mg/L of Na+, K+, Li+, Ca2+, Ba2+, Mg2+, Bi3+, Zn2+, Ni2+, Fe3+, Al3+ and some anion was also tested as indicated in
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the caption. To ensure the specific detection, the signal response of the MeCM was evaluated
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at pH 3.50. The data clarified that these foreign ions were not affected and did not show any
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measurable signal intensity except the V(III) ion. Therefore, the MeCM can be effective for V(III) ion detection with extreme sensitivity and selectivity.
3.3. V(III) adsorption
The pH control is an important experimental protocol during the removal of metal ion because it indicates the occurrence of parallel reactions as energy consumption increased, in addition to affecting on vanadium ion solubility [53-59]. The pH solution profile was measured during the V(III) adsorption by the MeCM as the data are shown in Fig. 6(A). It is obvious from the Fig. 6(A) that the MeCM was highly taken up the V(III) ion in the acidic region compared to the higher pH area. The basic pH region was not selected due to the
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ACCEPTED MANUSCRIPT hydroxide formation. The high adsorption efficiency was found at pH 3.50. Increasing or decreasing the pH of 3.50, the adsorption efficiency was decreased by the MeCM for V(III) ion. Similar trends are also observed by many ligand based material for heavy-metal ion adsorption [24]. Moreover, the ligand based material has specific adsorption efficiency at optimum solution acidity [25,29].
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The kinetic performance is measured based on the contact between the adsorbate and
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adsorbent [60]. The kinetic performance was evaluated where the initial V(III) concentration
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was fixed, and the reaction time was varied. The adsorption efficiency versus contact time is shown in Fig. 6(B). From the Fig. 6(B), the data emphasized that with increasing contact
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time the adsorption efficiency was increased and reaches the plateau. In the beginning, the abundant functional group was available and then slowly equilibrated. The V(III) was
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completely adsorbed by the MeCM within 50 min at this condition. The high kinetic performance will benefit a high efficient V(III) adsorption from aqueous media [61-63].
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Increasing the contact time further did not affect the V(III) adsorption. Then the equilibrium
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contact time of 3 h was sufficient to observe the maximum adsorption capacity by the MeCM
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in case of the high concentration of V(III) ion. The adsorption isotherm studies are important parameters to understand the nature of the material functionality [64-69]. To study the effect of initial concentration of V(III) on the adsorption capacity, the adsorption isotherm was undertaken. The results are shown in Fig. 7. The data was indicated that the adsorption capacity of V(III) was improved with increasing of initial concentration of V(III) ion until maximum adsorption was reached. With the further increase of V(III) concentration in solution, the adsorption capacity reached a plateau, indicating the saturation of the available active functional sites. The Langmuir isotherm model was used to interpret equilibrium isotherm data. The Langmuir isotherm is governed by the following relation and applied to the adsorption operation:
14
ACCEPTED MANUSCRIPT
Ce/qe = 1/(KLqm) + (1/qm)Ce
(linear form)
(5)
where Ce is the solution concentration at equilibrium (mg/L), qe the amount V(III) adsorbed at equilibrium (mg/g), KL the Langmuir constant (L/mg) which was considered as a measure
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of the adsorption energy and qm is the maximum adsorption capacity (mg/g) corresponding to
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complete monolayer coverage. A curve of Ce/qe versus Ce over the entire concentration
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range produces a straight line, which is an indication of the applicability of the Langmuir isotherm. The plot of V(III) adsorption by the PCM is single, smooth and continuous leading
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to saturation as shown in Fig. 7. The qm and KL are the Langmuir constants which are related to the adsorption capacity and energy of adsorption, respectively, and can be calculated from
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the intercept and slope of the linear plot, with Ce/qe versus Ce as shown in Fig. 7 (inset). The isotherms showed a sharp initial slope indicating high efficiency at low V(III) concentration,
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then the MeCM was saturated with increased V(III) levels. The V(III) adsorption onto the
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MeCM was taken onto the homogeneous surface, and adsorption was limited to the formation
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of the monolayer according to the Langmuir model. The coefficient value (R2=0.995) confirmed that the Langmuir adsorption was fitted with the adsorption behavior of the monolayer. The maximum adsorption capacity corresponding to complete monolayer coverage showed a mass capacity of 192.16 mg/g. The presence of co-existing ion may hinder the specific metal ion adsorption affinity by the adsorbent [70-76]. Therefore, the selective V(III) adsorption by the MeCM was also measured in this study. The ion selectivity was carried out from the multi-metal ions consisted solution, and the data are shown in shown Fig. 8(A). Here, the competing ions are Na(I), K(I), Li(I), Ca(II), Ba(II), Mg(II), Bi(III), Zn(II), Ni(II), Fe(III), Al(III) and each of the ion concentration were 20 mg/L while the V(III) ion concentration was 1.0 mg/L. The data
15
ACCEPTED MANUSCRIPT also clarified that V(III) was adsorbed from the multi-mixture solutions with high selectivity. The data were evident that the V(III) adsorption was not significantly reduced in the presence of foreign ion by the MeCM. Then the newly prepared MeCM can effectively adsorb the V(III) ion from the waste sample by solid-liquid separation approach.
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3.4. Extraction, recovery and reuses
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The metal ion recovery by elution/desorption operation is an important parameter to
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evaluate the material as a cost-effective potential candidate in the real sample treatment [7781]. Then the extraction of V(III) from the MeCM was measured based on the elution
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operation. The elution experiment was carried out with 0.15 M HCl from the stand point of regeneration ability. By the using of this level of eluent, the MeCM was simultaneously
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regenerated into the initial form wand able use for nest operation without loss of cage cavities. In the elution stage, the V(III) was recovered as pure metal ion. Scheme 1 shows the
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possible bonding mechanism of V(III) with the MeCM. The reuse data are shown in Fig.
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8(B). Therefore, the MeCM showed better long–term stability and reusability towards V(III)
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ion and potential candidate for V(III) recovery from waste samples as well as environmental remediation.
4. Conclusions
The complete recovery, including detection and adsorption of vanadium (V(III)) from aqueous solution was investigated by mesoporous composite material (MeCM). The MeCM was fabricated by organic ligand of 2-methyl-8-quinolinol embedded onto the porous silica by the direct anchoring method. The porous silica and MeCM were characterized systematically to understand the material morphology as well as detection and adsorption behaviour. The MeCM was formed color corresponds to signal intensity upon addition of 16
ACCEPTED MANUSCRIPT V(III) even in the trace concentration. The low limit of detection was detected, and it was low as 0.27 µg/L. The effects of equilibrium pH, initial V(III) concentration, contact time, foreign ion and stripping agents were studied. The data presented that the MeCM was simple, rapid and immense sensitive to V(III) ion detection by the colorimetric method. The solution pH was influenced both in the detection and adsorption operation, and the MeCM were
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effectively captured the V(III) ion at pH 3.50. The presence of foreign ion was not affected
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the V(III) capturing by the MeCM. Therefore, the high selectivity of the MeCM was assumed
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to treat the V(III) containing waste samples. The adsorption data were well fitted to the Langmuir model, and the maximum adsorption capacity was also high as 192.16 mg/g with
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the monolayer coverage. The adsorbed V(III) was extracted with stripping agent of 0.15 M HCl, and the MeCM were subsequently regenerated into the initial form for next operation
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after washing with water. The MeCM was reused in several cycles without significant deterioration of the performances. Then the fabricated MeCM can be used as an alternative
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Acknowledgments
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material for efficient V(III) recovery from waste effluents.
This research was partially supported by the Grant-in-Aid for Research Activity Startup (24860070) from the Japan Society for the Promotion of Science. The part of the experimental works was carried out at Japan Atomic Energy Agency. The authors also wish to thanks to the anonymous reviewers and editor for their helpful suggestions and enlightening comments.
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Ind. Eng. Chem. 21 (2015) 405–413; (c) M.R. Awual, M.M. Hasan, J. Ind. Eng. Chem. 21 (2015) 507–515; (d) M.R. Awual, M.M. Hasan, H. Znad, Chem. Eng. J.
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ACCEPTED MANUSCRIPT (d) M.R. Awual, T. Kobayashi, Y. Miyazaki, R. Motokawa, H. Shiwaku, S. Suzuki, Y. Okamoto, T. Yaita, J. Hazard. Mater. 252–253 (2013) 313–320; [31] M. Naushad, G. Sharma, A. Kumar, S. Sharma, AA. Ghfar, A Bhatnagar, F.J. Stadler, M.R. Khan, Int. J. Biolog. Macromol. 106 (2018) 1–10. [32] M. Naushad, S. Vasudevan, G. Sharma, A. Kumar, Z.A. AlOthman, Desalin. Water
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[34] M. Naushad, Z.A. Alothman, Desalin. Water Treat. 53 (2015) 2158–2166. [35] A.A. Alqadami, Mu. Naushad, M.A. Abdalla, T. Ahmad, Z.A. ALOthman, S.M.
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[36] G. Sharma, M. Naushad, A. Kumar, S. Rana, Shweta, A. Bhatnagar, F.J. Stadler, A.A. Ghfar, M.R. Khan, Proc. Saf. Environ. Prot. 109 (2017) 301–310.
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Awual, N.H. Alharthi, M.M. Hasan, M.R. Karim, A. Islam, H. Znad, M.A. Hossain, M.E. Halim, M.M. Rahman, M.A. Khaleque, Chem. Eng. J. 324 (2017) 130–139; (c) M.R. Awual, N.H. Alharthi, Y. Okamoto, M.R. Karim, M.E. Halim, M.M. Hasan, M.M. Rahman, M.M. Islam, M.A. Khaleque, M.C. Sheikh, Chem. Eng. J. 320 (2017) 427–435; (d) S.A. El-Safty, M.A. Shenashen, M. Ismael, M. Khairy, M.R. Awual, Micropor. Mesopor. Mater. 166 (2013) 195–205. [39] (a) M.R. Awual, Chem. Eng. J. 266 (2015) 368–375; (b) M.R. Awual, T. Yaita, S.A. ElSafty, H. Shiwaku, S. Suzuki, Y. Okamoto, Chem. Eng. J. 221 (2013) 322–330; (c) M.R. Awual, M. Ismael, T. Yaita, S.A. El-Safty, H. Shiwaku, Y. Okamoto, S. Suzuki, Chem. Eng. J. 222 (2013) 67–76; (c) S.A. El-Safty, M.R. Awual, M.A. Shenashen, A. Shahat, Sensor. Actuat. B: Chem. 176 (2013) 1015–1025. [40] (a) M.R. Awual, A.M. Asiri, M.M. Rahman, N.H. Alharthi, Chem. Eng. J. 363 (2019) 64–72; (b) M.R. Awual, T. Yaita, H. Shiwaku, S. Suzuki, Chem. Eng. J. 276 (2015)
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ACCEPTED MANUSCRIPT 1–10; B.C. Roy, M.R. Awual, M. Goto, J. App. Sci. 7 (2007) 1053–1060; (d) B.C. Roy, M.R. Awual, M. Goto, J. App. Sci. 6 (2006) 411–415. [41] (a) S.A. El-Safty, A. Shahat, M.R. Awual, M. Mekawy, J. Mater. Chem. 21 (2011) 5593–5603; (b) M.R. Awual, M.M. Hasan, Sensor. Actuat. B: Chem. 202 (2014) 395– 403; (c) M.R. Awual, M.M. Hasan, Sensor. Actuat. B: Chem. 206 (2015) 692–700; (d) M.R. Awual, T. Yaita, Y. Miyazaki, D. Matsumura, H. Shiwaku, T. Taguchi, Sci.
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Rep. 6 (2016) 19937 http://dx.doi.org/10.1038/srep19937. [42] (a) S.A. El-Safty, M.A. Shenashen, M. Ismael, M. Khairy, M.R. Awual, Analyst 137 (2012) 5278–5290; (b) M.R. Awual, T. Yaita, S.A. El-Safty, H. Shiwaku, Y.
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Okamoto, S. Suzuki, Chem. Eng. J. 222 (2013) 172–179; (c) M.R. Awual, T. Yaita,
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H. Shiwaku, Chem. Eng. J. 228 (2013) 327–335; (d) M.R. Awual, M. Ismael, M.A. Khaleque, T. Yaita, J. Ind. Eng. Chem. 20 (2014) 2332–2340.
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[43] (a) M.R. Awual, Chem. Eng. J. 307 (2017) 85–94; (b) M.R. Awual, Chem. Eng. J. 307 (2017) 456–465; (c) M.R. Awual, Chem. Eng. J. 303 (2016) 539–546; (d) M.R. Awual, M. Hasan, A. Shahat, Sensor Actuat B: Chem. 203 (2014) 854–863.
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[44] (a) M.R. Awual, T. Kobayashi, H. Shiwaku, Y. Miyazaki, R. Motokawa, S. Suzuki, Y. Okamoto, T. Yaita, Chem. Eng. J. 225 (2013) 558–566; (b) M.R. Awual, G.E.
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J. 279 (2015) 639–647; (c) M.R. Awual, S. Suzuki, T. Taguchi, H. Shiwaku, Y. Okamoto, T. Yaita, Chem. Eng. J. 242 (2014) 127–135; (d) M.R. Awual, T. Yaita, T. Taguchi, H. Shiwaku, S. Suzuki, Y. Okamoto, J. Hazard. Mater. 278 (2014) 227–235.
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[45] (a) M.R. Awual, M. Khraisheh, N.H. Alharthi, M. Luqman, A. Islam, M.R. Karim, M.M. Rahman, M.A. Khaleque, Chem. Eng. J. 343 (2018) 118–127; (b) A. Shahat, H.M.A. Hassan, M.F. El-Shahat, O. El Shahawy, M.R. Awual, Chem. Eng. J. 334 (2018) 957–967; (c) M.R. Awual, I.M.M. Rahman, T. Yaita, M.A. Khaleque, M. Ferdows, Chem. Eng. J. 236 (2014) 100–109; (d) A. Shahat, H.M.A. Hassan, H.M.E. Azzazy, E.A. El-Sharkawy, H.M. Abdou, M.R. Awual, Chem. Eng. J. 332 (2018) 377–386. [46] M.M. Rahman, V.G. Alfonso, F.F. Santiago, J. Bisquert, A.M. Asiri, A.A. Alshehri, H.A. Albar, Microchim. Acta 184 (2017) 2123-2129. [47] M.M. Hussain, M.M. Rahman, M.N. Arshad, A.M. Asiri, ACS Omega 2 (2017) 420431. [48] M.M. Rahman, M.M. Alam, A.M. Asiri, M.A. Islam, RSC Adv. 7 (2017) 22627-22639. [49] M.M. Rahman, M.M. Alam, A.M. Asiri, M.A. Islam, Talanta 170 (2017) 215-223. 21
ACCEPTED MANUSCRIPT [50] A. Umar, M.M. Rahman, S.H. Kim, Y.B. Hahn, Chem. Comm. 2 (2008) 166-168. [51] (a) T.A. Sheikh, M.N. Arshad, M.M. Rahman, A.M. Asiri, H.M. Marwani, M.R. Awual, W.A. Bawazir, Inorg. Chim. Acta 464 (2017) 157–166; (b) S.H. Teo, A. Islam, E.S. Chan, S.Y.T. Choong, N.H. Alharthi, Y.H. Taufiq-Yap, M.R. Awual, J. Clean. Prod. 208 (2019) 816–826; (c) M. Ali, A.J. Mian, M.N. Islam, M.R. Awual, S.F. E-Karim, A.M.S. Chowdhury, Indian J. Fibre Text. Res. 26 (2001) 414–417; (d) T.A. Sheikh,
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[52] (a) A. Shahat, M. R. Awual, M. A. Khaleque, M. Z. Alam, M. Naushad, A. M. S.
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Naushad, Chem. Eng. J. 271 (2015) 155–163; (c) M.R. Awual, T. Yaita, S. Suzuki, H. Shiwaku, J. Hazard. Mater. 291 (2015) 111–119; (d) M.R. Awual, M. Ismael, T.
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Yaita, Sensor. Actuat. B: Chem. 191 (2014) 9–18.
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ACCEPTED MANUSCRIPT [61] (a) A. Shahat, H.M.A. Hassan, H.M.E. Azzazy, M. Hosni, M.R. Awual, Chem. Eng. J. 331 (2018) 54–63; (b) M.R. Awual, M.A. Hossain, M.A. Shenashen, T. Yaita, S. Suzuki, A. Jyo, Environ. Sci. Pollut. Res. 20 (2013) 421–430; (c) M.R. Awual, M.A. Shenashen, T. Yaita, H. Shiwaku, A. Jyo, Water Res. 46 (2012) 5541–5550; (d) M.R. Awual, A. Jyo, Desalination 281 (2011) 111–117. [62] (a) M.R. Awual, A. Jyo, T. Ihara, N. Seko, M. Tamada, K.T. Lim, Water Res. 45 (2011)
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4592–4600; (b) M.R. Awual, A. Jyo, S.A. El-Safty, M. Tamada, N. Seko, J. Hazard. Mater. 188 (2011) 164–171; (c) M.R. Awual, S.A. El-Safty, A. Jyo, J. Environ. Sci. 23 (2011) 1947–1954; (d) M.R. Awual, A. Jyo, Water Res. 43 (2009) 1229–1236.
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[63] (a) M.R. Awual, S. Urata, A. Jyo, M. Tamada, A. Katakai, Water Res. 42 (2008) 689–
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696; (b) M.R. Awual, M.A. Shenashen, A. Jyo, H. Shiwaku, T. Yaita, J. Ind. Eng. Chem. 20 (2014) 2840–2847; (c) M.R. Awual, A. Jyo, M. Tamada, A. Katakai, J. Ion
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Exchange 18 (2007) 422–427; (d) A. Jyo, M.R. Awual, K. Kobayashi, Soc. Chem. Ind. (2008) 487–494.
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ACCEPTED MANUSCRIPT [75] Q. Hu, H. Paudyal, J. Zhao, F. Huo, K. Inoue, H. Liu, Chem. Eng. J. 248 (2014) 79–88. [76] V. Cappuyns, R. Swennen, Environ. Sci. Pollut. Res. 21 (2014) 2272–2282. [77] T. Leiviskfa, M.K. Khalid, A. Sarpola, J. Tanskanen, J. Environ. Manage. 190 (2017) 231–242. [78] N. Panichev, K. Mandiwana, D. Moema, P. Molatlhegi, P. Ngobeni, J. Hazard. Mater.
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A137 (2016) 649–653.
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[79] M. Naushad, Z.A. ALOthman, G. Sharma, Inamuddin, Ionics 21 (2015) 1453–1459. [80] A.A. Alqadami, Mu. Naushad, Z.A. ALOthman, Ayman A. Ghfar, ACS App. Mat.
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Interf. 9 (2017) 36026−36037.
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[81] M. Naushad, Z.A. ALOthman, M. R. Awual, S.M. Alfadul,T. Ahamad, Desalin. Water
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Scheme 1. Possible bonding mechanism of V(III) with MQNL at pH 3.50 during detection and adsorption operation to exhibit the sensitivity and selectivity.
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Fig. 1. N2 adsorption-desorption isotherms of mesoporous silica (a) and ligand immobilized composite material (b) with specific surface area, pore size and pore volumes.
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Fig. 2. The TEM micrographs of the ordered mesoporous silica (A, B) and TEM images after organic ligand of MQNL embedded composite material (C, D).
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Fig. 3. Effect of solution pH for V(III) detection by the composite material under different pH solutions when V(III) concentration was 2.0 mg/L in 10 mL solution.
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Fig. 4. (A) Color optimization with increasing the V(III) concentration at λ = 365 nm and (B) Calibration curve with different signal intensity of different V(III) concentrations. The insets in the graph (B) show the limit of detection range with a linear fit line in the linear concentration range.
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Fig. 5. Ion selectivity of the composite material during 1.0 mg/L of V(III) ion detection. The interfering cations (Na+, K+, Li+, Ca2+, Ba2+, Mg2+, Bi3+, Zn2+, Ni2+, Fe3+, Al3+) concentration was 20.0 mg/L.
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Fig. 6. The V(III) adsorption indifferent solution pH (A) and effect of contact time for the measurement of equilibrium adsorption when V(III) concentration was 5.0 mg/ in 20 mL.
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Fig. 7. Langmuir adsorption isotherms for V(III) ion and the linear form (inlet) of the Langmuir plot (initial V(III) concentration from 2.02 to 80.0 mg/L; solution pH 3.50; composite material amount 10 mg; solution volume 30 mL; contact time for 3 h).
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Fig. 8. The V(III) adsorption in the presence of diverse competing ion while V(III) 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.
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