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Article
Graphene-diatom silica aerogels for
efficient removal of mercury ions from water
Shervin Kabiri, Diana N.H. Tran, Sara Azari, and Dusan Losic
ACS Appl. Mater. Interfaces, Just Accepted Manuscript DOI: 10.1021/acsami.5b01159 Publication Date (Web): 02 Apr 2015
Downloaded from http://pubs.acs.org on April 7, 2015
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Page 1 of 31 ACS Applied Materials & Interfaces
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Graphene-diatom silica aerogels for efficient
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12 removal of mercury ions from water
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17 Shervin Kabiria, Diana N.H. Trana, Sara Azaria, and Dusan Losic*,a
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School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia
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KEYWORDS: graphene, diatomaceous earth, aerogel, adsorption, mercury
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29 ABSTRACT: A simple synthetic approach for the preparation of graphene-diatom silica
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32 composites in the form of self-assembled aerogels with three dimensional (3D) networks from
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34 natural graphite and diatomite rocks is demonstrated for the first time. Their adsorption
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36 performance for the removal of mercury from water was studied as a function of contact time,
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39 solution pH and mercury concentration to optimize the reaction conditions. The adsorption
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41 isotherm of mercury fitted well with the Langmuir model, representing a very high adsorption
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capacity of > 500 mg of mercury/g of adsorbent. The prepared aerogels exhibited outstanding
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46 adsorption performance for the removal of mercury from water, which is significant for
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48 environmental applications.
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1. INTRODUCTION
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7 Heavy metals have been excessively released into the environment due to rapid industrialization
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9 that has created serious global concerns. Mercury in particular, is recognized as one of the most
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12 harmful pollutants in the environment because of its high toxicity, volatility and
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14 bioaccumulation, which is often introduced to the environment through industrial wastewaters,
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16 electroplating and metal finishing, mining activities, fertilizers, and pharmaceuticals.1,2 The
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19 disposed mercury (both inorganic and organic forms) can be accumulated in the human body
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21 causing adverse effects by impairing mental and neurological functions.3,4 Therefore, preventing
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23 contamination and efficiently removing mercury from the environment is recognised as one of
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26 the top priorities by the World Health Organization (WHO).4
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28 Adsorption methods emerged as the most promising technologies for mercury removal
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from waters where numerous synthetic and natural porous materials have been explored and
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33 commercially used.5-7 Thus far activated carbons and synthetic silica mesoporous materials
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35 (MCM-41 and SBA-15) are the most successful adsorbents on the market. However, these
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38 adsorbents are very expensive and their laborious production involves the use and waste of toxic
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40 materials and high energy.8 To address these limitations, the development of new, cheaper and
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42 more advanced adsorbents based on natural or waste materials such as, zeolites, clays, starch, fly
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45 ash, chitosan, etc with sustainable and green production is recognized as a favourable approach.5-
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47 Two natural minerals such as graphite a source of graphene and diatomaceous earth (DE) as a
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source of porous silica from diatoms, fossilised single-cell algae are excellent choices with the
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52 potential to address these requirements.
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54 Graphene, since its discovery in 2005, has attracted global attention because of its
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outstanding structural, thermal, mechanical, electrical and adsorption properties.9 These
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properties have been utilised for numerous applications, such as for the enhancement of
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6 composite materials, supercapacitors, batteries, and drug delivery.9-12 Graphene has also been
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8 proven to be superior adsorbents for environmental applications in the removal of heavy metal
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ions and organic pollutants showing high adsorption capacity and selectivity due to its ultra-high
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13 surface area ( 1000 m2/g) and tailorable functionalities.10,11 In particular, graphene aerogels in
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15 the form of three-dimensional (3D) nanostructures combined with other materials (carbon
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18 nanotubes, nanoparticles, polymers) have attracted tremendous attention for the design of
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20 advanced adsorbents based on their combined properties.13,14
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22 Similarly, porous silica from DE has also been explored and practically demonstrated for
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25 many applications, such as water purification, beer and wine filtration, environmental
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27 remediation, optical sensing, and drug delivery due to its excellent properties, which include high
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porosity, surface area (20-100 m2/g), biocompatibility, chemical inertness, tailorable surface
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32 chemistry, and low cost ($ 300-500 per tonne).15-21 DE is composed of fossilised diatoms with
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34 unique 3-d hierarchical and hollow structure with specie specific pattern of nanopores build by
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37 amorphous silica.15 In our previous work, we showed several concepts using surface
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39 functionalization by different silanes (3-aminopropyl-triethoxysilane (APTES), 3-
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41 mercaptopropyl-trimethoxysilane (MPTMS)) of porous DE microparticles to create very
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44 efficient adsorbents for the removal of heavy metals from polluted waters and the adsorption of
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46 gold and silver ions.22,23 A number of other studies has also demonstrated the use of DE as an
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48 absorbent for the removal of specific heavy metal ions (e.g. Pb(II), Zn(II), Hg(II), Cd (II) and
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51 Cu(II)) from wastewater.24-26 In our previous work, we also showed that by modifying DE
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53 particles with graphene nanosheets it is possible to combine these two materials and use them for
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pH selective drug delivery applications.27
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In the present work, we propose a biomimetic approach based on two distinctive natural
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6 materials: porous silica from diatoms and graphene from graphite, which are combined and
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8 engineered into a self-assembled and functionalized 3D aerogel composite.12,28 The concept is to
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synergize their exceptional adsorption properties, already proven for the removal of heavy metals
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13 and water contaminants. The preparation of the proposed graphene-DE aerogels is graphically
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15 presented in Figure 1. The enhanced adsorption of mercury (Hg) is proposed due to the
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18 combination of several factors, including the large 3D network surface area of the graphene
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20 nanosheets and diatom particles where the Hg ions can be physically trapped, and the presence of
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22 amino (at the modified diatom surface) and oxygen functional groups (on the edge of the
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25 graphene nanosheets), and iron oxide nanoparticles with their strong affinity for Hg ions.29-31 The
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27 structural characteristics of the prepared aerogel composite, their adsorption capacity, and
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influence of pH on adsorption performance and kinetics for Hg ions were evaluated. Finally, the
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32 prepared adsorbents for the removal of Hg from contaminated waters were explored to
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34 demonstrate their application for real water purification.
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34 Figure 1. A schematic diagram for the synthesis of graphene-DE aerogels. (a) Graphite rock, (b)
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diatom silica microparticles from diatomaceous earth (DE), (c) the mixture of graphene oxide
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39 (GO) sheets and APTES modified diatoms prepared for (d) the graphene-DE hydrogel, and (e)
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41 the formation of the graphene-DE aerogel after the freeze drying process. GO is reduced to
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graphene (rGO or GN) with the presence of some oxygen groups at the edges (defects) of the
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52 2. EXPERIMENTAL SECTION
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55 2.1. Materials and chemicals
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Natural graphite rocks (Uley, Eyre Peninsula, South Australia, Australia) is supplied from a local
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6 mining site and milled into a fine powder using a bench top ring mill (Rocklabs). DE rocks
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8 were obtained from a diatomite mining company (Mount Sylvia Pty. Ltd., Queensland,
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Australia). Diatom samples in the form of ultra-pure silica microcapsules (frustules) were
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13 prepared from the raw DE material using several purification steps as decribed in our
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15 previous work.18,21 Iron sulphate (FeSO4.7H2O, Sigma-Aldrich), 3-aminopropyl-
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18 trimethoxysilane (APTES, Sigma-Aldrich), potassium permanganate (KMnO4, Sigma-Aldrich),
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20 mecury chloride(II) (HgCl2, Sigma-Aldrich), 99.7 % isopropanol (Chem-Supply), 98 %
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22 sulphuric acid (H2SO4, Chem-Supply), phosphoric acid (H3PO4, Chem-Supply), 30 % hydrogen
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25 peroxide (H2O2, Chem-Supply), 35 % hydrochloric acid (HCl, Chem-Supply), 69 % nitric acid
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27 (HNO3, Chem-Supply), sodium hydroxide (NaOH, Chem-Supply) and ethanol (Chem-Supply)
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were used directly without further processing. High-purity milli-Q water (18.2 M.cm at 25 C,
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32 pH of 5.6) was used throughout the study, unless otherwise stated.
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37 2.2. Surface modification of diatomaceous earth (DE)
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40 Surface modification of the DE particles was performed by the typical silanization
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42 process.23,27 The DE sample (1.0 g) was suspended in 30 mL of toluene under a static dry
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45 nitrogen atmosphere. Subsequently, 0.32 mL of water was added to the mixture that was
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47 stirred for 1-2 h at room temperature. Then, 1.7 mL of APTES was added dropwise into
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the mixture and refluxed for 6 h. The APTES modified DE (APTES-DE) were collected
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52 by centrifugation and washed several times with isopropanol and toluene before drying in
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2.3. Preparation of graphene oxide (DE)
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7 Graphene oxide was prepared by the oxidation of natural graphite according to the improved
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9 Hummers method.32 Briefly, a 9:1 mixture of concentrated sulphuric acid and phosphoric acid
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12 (120:13 mL) was cooled to 4 C. Upon stirring at room temperature the cooled acid mixture was
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14 slowly added to the graphite powder (1 g) and potassium permanganate (6 g), then heated to 50
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16 C for about 12 h to form a thick paste. The finished reaction was cooled to room temperature
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19 and poured onto ice (150 mL) with 1 mL of hydrogen peroxide. The mixture was then washed
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21 with distilled water and 32 % hydrochloric acid followed by a repeated washing with ethanol.
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23 For each successive wash the product was centrifuged at 4200 rpm for 2 h. The obtained GO was
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2.4. Synthesis of graphene-DE and graphene aerogels
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35 GO (20 mg) was added into 10 mL of water and sonicated for 1 h to obtain a well dispersed
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37 solution. Then 5 mg of APTES-DE was added to the mixture which, was further sonicated for
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40 another 1 h to form a uniform graphene-DE dispersion. Different ratios of GO and DE were used
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42 to prepare the graphene-DE aerogels but the most robust aerogel was prepared in the ratio of 4 to
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44 1 for GO and DE, respectively. FeSO4.7H2O (1 mM) was then quickly added into the graphene-
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47 DE dispersion and the solution was adjusted to acidic pH. The dispersion was poured into glass
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49 vials (25 mL) and sealed before placing into a 90 C oil batch for 6-8 h. The obtained 3D black
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monoliths were first washed with water to remove any outside residues, then freeze dried for 24
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54 h to obtain the corresponding graphene-DE aerogels. Graphene aerogels were also prepared
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10 The morphology of DE, GO and graphene-DE aerogels were characterized by scanning
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13 electron microscopy (FE-SEM, Quanta 450, FEI, USA) and transmission eletron microscopy
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15 (FEI, Tecnai, G2 spirit TEM, USA) to confirm the 3D aerogel structure and decoration of the
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17 iron nanoparticles (NPs) on the graphene sheets. The size distribution of the DE particles in the
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20 water solution (1 % w/v) was determined using the Mastersizer X (Malvern Instruments, UK).
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22 Fourier transform infrared (FTIR) spectroscopy (Nicolet 6700 Thermo Fisher) was used to
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identify the functional groups of GO and the reduction of GO to graphene by iron NPs recorded
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27 in the range of 500-4000 cm-1 in transmittance mode. The vibrational characteristics of GO and
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29 the graphene-DE aerogel were analysed by Raman spectroscopy (LabRAM HR Evolution,
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Horiba Jvon Yvon Technology, Japan) using a 532 nm laser (mpc 3000) as the excitation source
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34 in the range of 500-3500 cm-1. A 100x objective was used with a spot size of 100 m. The laser
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36 power was kept at or below approx. 50 % and all spectras were collected using an intergration
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39 time of 10 sec for 3 accumulations. The X-ray diffraction (600 Miniflex, Rigaco, Japan)
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41 measurement was performed to illuminate the composition of GO and the graphene-DE aerogel.
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43 Solution ICP-MS (7500cs, Alginate) was used to measure the final concentration of mercury(II)
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46 ions (Hg2+) in the adsorption experiments. The specific surface area (SSA) of the prepared
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48 graphene-DE aerogel was determined using the methylene blue (MB) adsorption method by UV-
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Vis spectroscopy (Shimadzu UV-1601, Japan). Details are provided in the Supporting
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2.6. Batch adsorption of mercury ions
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7 The adsorption capacity of the graphene-DE aerogels was determined using a series of
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9 known concentration of Hg2+ ions (from 50-400 mg/L) in water (pH 6.5) by placing the
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12 graphene-DE aerogels (10 mg) in 250 mL of the Hg solution at ambient temperature (25
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14 1 C). The adsorbent-solution mixture was stirred for 90 min then samples were taken
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16 every 5 min and measured with ICP-MS to determine the Hg concentration after
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19 centrifugation to separate the supernantant.
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21 For testing the effect of pH in the range of pH 2-10 on the removal of Hg, the pH of
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23 the Hg solution (200 mg/L) was adjusted to the targeted value by adding HCl or NaOH
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26 and was kept constant during the experiment. Kinetic experiments were performed at pH
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28 6.5. For each adsorption test performed, the supernatant was removed and immediately
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filtered through a cellulose acetate membrane with a pore size of 0.22 m, and the Hg
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33 concentration was determined via ICP-MS. Prior to the analysis, the samples were
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35 acidified with 2 % HNO3. The amount of heavy metal ions Qt (mg/g) adsorbed with the
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38 graphene-DE aerogel at time t, was calculated using the following equation (1):
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Q =
(1)
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43 where C0 and Ct are the initial and time t concentration of the heavy metal ions solution
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45 (mg/L), respectively. V is the volume of solution (L) and M is the mass of the aerogel
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48 used (g).
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different sources of water, milli-Q, tap and river water (Torrens River, Adelaide,
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55 Australia) were spiked with Hg2+ to provide the desired Hg concentration (100 mg/L)
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57 using 10 mg of adsorbent. The model system (milli-Q water solution) was adjusted to pH
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6.5, whereas the natural water samples (tap and river water) were used as is (natural pH of
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6 solution already ~6-7). The adsorbent-solution mixture was stirred for 90 min then a
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average of three measurements was taken for all experiments.
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15 3. RESULTS AND DISCUSSION
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19 3.1. Structural and chemical characterization of graphene-DE aerogels
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22 A SEM image showing the structure of the diatom particles prepared from the raw DE material
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(rocks) is presented in Figure 2a. The image depicts a characteristic structure of Aulacoseira sp,
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27 (major diatom species, >90 %), with a perforated cylindrical shell and an opening at one end.
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29 Regularly spaced rows of pores of ~300-500 nm in diameter are located along the frustule shell
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wall. The size of the DE particles was measured by dynamic light scattering and a
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34 monodispersed distribution curve with the maximum peak at 15 m (Figure 2f) was obtained,
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28 Figure 2. SEM images of (a) a single DE particle, (b) the prepared graphene-DE aerogel
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31 showing low resolution image of the 3D network structure, (c-d) high resolution image of the
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33 graphene-DE aerogel, (e) TEM image of graphene (GN) sheets showing the presence of iron
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35 oxide nanoparticles (NPs), and (f) the particle size distribution of DE particles dispersed in
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38 water.
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The prepared graphene-DE aerogels after freeze drying show a black and spongy
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46 appearance as presented in Figure 1e. The cylindrical shape of the aerogel is a result of the glass
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48 mould used during the preparation. Other sizes and shapes of the aerogel can also be prepared if
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51 required. In Figure 2b, the aerogel structure reveals a characteristic 3D network composed of
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53 graphene and DE particles. Higher resolution of SEM images (Figures 2c and 2d) illustrates in
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55 more detail the interconnected porous structure. The pore walls consist of very thin layers of
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58 stacked graphene sheets with DE particles trapped in between, hence avoiding the agglomeration
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between them. Although, all the aerogel imaged under SEM showed that their surface is
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6 decorated by DE particles, the coverage was not homogeneous. As can be seen from the low
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8 magnification TEM image (Figure 2e), the graphene sheets (without DE) have a large number of
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iron oxide (FeOOH) nanoparticles (NPs) decorated on them.
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13 The calculated specific surface area of the prepared graphene-DE aerogel (368.0 2 m2/g)
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15 is higher compared to the graphene aerogel without DE (208.9 2 m2/g). The higher porosity
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18 and larger surface area of the graphene-DE aerogels compared to graphene aerogels without DE
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20 is due to the presence of the DE particles acting as spacers in the graphene sheets.
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22 Simultaneously, the reduced GO sheets and DE anchored with the FeOOH nanoparticles that
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25 self-assembled into the hydrogel is driven by the combined hydrophobic and stacking
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27 interactions, due to the decrease of oxygenated groups on the GO surface. Thus the functional
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groups on the surface of GO also plays an important role in the aerogel preparation.
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32 Figure 3a shows the X-ray diffraction (XRD) patterns of GO and the graphene-DE
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34 aerogel. The intensive peak at 2 = 10.8 (d-spacing = 0.86 nm) represents the (001) reflection of
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37 GO due to the presence of oxygen-containing groups during the oxidation of graphite. In
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39 contrast, the disappearance of the peak at 10.8 to 18.3 for the graphene-DE aerogel provides
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41 further evidence of the GO reduction.33 For the graphene-DE aerogels the major diffraction peak
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44 is assigned to the orthorhombic structure of the -FeOOH (JCPDS card No. 29-0713), and the
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46 broads peak around 15 and 35 present the existence of the amorphous silica (-SiO2) on the DE
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51 Raman analysis of the graphene-DE aerogel prepared by the synthesis route shown in
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53 Figure 3b provides further evidence for the attachment of DE and graphene. The spectra of GO
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and graphene-DE aerogel both display the two characteristic peaks (i.e. G and D band). The G
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band corresponds to the in-plane vibration of sp2 to sp3 hybridized carbon originating from the
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6 destruction of the sp2 structures of the graphite or due to the covalent attachment of functional
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8 groups. The D band is associated with the disorder in the graphitic structure.28 The G band of the
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graphene-DE aerogel (1594 cm-1) was slightly shifted compared to pure GO (1591 cm-1)
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13 revealing the charge transfer between the graphene sheets, DE and -FeOOH nanoparticles.34
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15 The intensity ratio of the D and G band (ID/IG) in the graphene-DE aerogel (1.07) also enhanced
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18 after the reduction compared with that of GO (1.02), representing the improvement of the
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43 Figure 3. (a) XRD patterns and (b) Raman spectra of the GO and graphene-DE (GN-DE)
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FTIR results of the modified DE further confirm the presence of the organic moieties on
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51 the DE surface, compared to bare DE used as the control, are presented in Figure 4a. The
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53 characteristic peak of the diatomite silica framework at wavenumber 1090 cm-1 was observed
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56 which, can be attributed to the stretching modes of SiOSi and SiOC, while the AlOSi
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stretching vibration is indicated at 796 cm-1. The hydroxyl (OH) peaks at 3340 and 1630 cm-1
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6 present the stretching vibrations of adsorbed water and zeolitic water sourced from the DE,
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8 respectively. The DE sample modified with APTES gave rise to a spectrum similar to that of the
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reference. However, an additional band for the CH2 asymmetric stretching mode was observed
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13 at 2970 cm-1 and the CH symmetric stretching mode appeared at 2880 cm-1 for APTES-DE,
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15 which is directly related to the carbon chain of organosilane molecules.18,22,27,36 Therefore,
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18 confirming the successful modification of the diatom surface by APTES.
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40 Figure 4. FTIR plots of (a) bare diatom (DE) and APTES modified DE (APTES-DE), and (b)
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42 graphene oxide (GO) and graphene-DE (GN-DE) aerogel.
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48 Furthermore, the FTIR spectra of GO presents the following absorbance bands, OH
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50 stretching vibrations at 3230 cm-1, C=C from unoxidized sp2 CC bonds at 1630 cm-1, CO
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53 vibrational at 1230 cm-1, C=O stretching of the COOH at 1730 cm-1, HC=C at 2950 cm-1 and
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55 COH at 1370 cm-1 (Figure 4c).32 The absorbance bands of the carbonyl and epoxy groups are
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not present in the graphene-DE aerogel indicating the effective reduction of the graphene sheets.
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The adsorption bands at 1580, 1040 and 812 cm-1 in the graphene-DE aerogel are the
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6 characteristic peaks of Fe containing FeOH and FeO groups, respectively.37,38 These results
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8 conclude that the hydrogels were formed by the co-assembly of graphene sheets, DE and
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FeOOH nanoparticles as shown from the above characterizations.
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17 3.2. Effect of pH
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The effect of pH on the Hg2+ ions removal was examined for the graphene-DE aerogel and is
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23 presented in Figure 5a. The graph presents the change in adsorption capacity of the graphene-DE
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25 aerogel on Hg2+ ions in the pH range of 2-10. The result indicates that during the adsorption
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28 process the solution pH has an influence on the adsorption of Hg by the graphene-DE aerogel.
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30 The adsorption capacities increased from pH 2 to 6.5 and then slightly decreased with pH above
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32 6.5. We propose two major mechanisms for the capturing of Hg ions by the aerogel, which is
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35 physical trapping and binding with available amino and oxygen groups on the graphene-DE
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37 aerogel. To better understand this process and the influence of pH on the adsorption capacity the
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zeta potential of the graphene-DE aerogel is explored and presented in Figure 5b.
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Figure 5. (a) Adsorption capacity and (b) zeta potential of graphene-DE aerogel measured in the
4
5
6 range of pH 2 to 10. Condition: Hg concentration = 200 mg/L.
7
8
9
10
11
12
13 The zeta potential of the graphene-DE aerogel in different pH shows that the prepared
14
15 aerogel is positively charged (+ 10 mV) below pH 6, which repulses the Hg2+ cations resulting in
16
17 the low mercury uptake compared to pH 6 and above. With increasing pH >6, the graphene-DE
18
19
20 aerogel surface becomes more negative (> -10 mV) which increases the attraction of Hg ions and
21
22 their adsorption. The surface charge of the graphene-DE aerogels depends on the surface charge
23
24
of both the graphene sheets and the FeOOH nanoparticles anchored on its surface. Several
25
26
27 reports have shown that graphene is negatively charged in the pH range of 2-14, while the
28
29 oxyhydroxide surface becomes positive at pH lower than 6 and slightly negative at pH higher
30
31
32
than 6.39-41 Although the surface charge of the aerogel becomes more negative at higher pH, the
33
34 mercury uptake slightly decreases. Such behaviour is likely attributed to the formation of
35
36 Hg(OH)3- due to the increase in concentration of OH-,41,42 which are repulsed by the negatively
37
38
39 charged graphene-DE aerogel surface and consequently lowering the Hg adsorption. This
40
41 observation is in agreement with previous studies showing that the Hg adsorption has been
42
43 monotonically decreased on an activated carbon surface by increasing pH, due to the competitive
44
45
46 adsorption between the mercury ions and increased OH-, resulting in the active sites being
47
48 occupied by OH- on the adsorbent.4 In addition, the mercurys speciation at different pH could
49
50
also play a role, especially at higher pH where some Hg2+ ions can be blocked in the presence of
51
52
53 high concentrations of chloride ions by association with OH (HgClOH) and therefore reducing
54
55 their adsorption.3
56
57
58
59
60
16
1
2
3
4
5
6
7 3.3. Adsorption kinetics
8
9
10 The adsorption performance of the prepared graphene-DE compared with the graphene aerogel
11
12
13 for adsorption of Hg2+ ions is summarized in Figure 6. The graph shows that the rate of Hg2+
14
15 uptake was initially high for the graphene-DE aerogels with about 60 % removed during the first
16
17 5 min. There was a gradual reduction in the rate of removal afterwards, but about 90 % of Hg2+
18
19
20 ions were removed within 30 min before reaching equilibrium. The fast kinetics and ability to
21
22 remove Hg ions is attributed to the combination of three factors, (1) the electrostatic attraction
23
24
between the oxides (FeOOH nanoparticles and graphene edges) and Hg ions, (2) the ion
25
26
27 exchange in the aqueous solution, and (3) the amino functional groups present on the APTES
28
29 modified DE.23,28 To confirm this conclusion the influence of the graphene-FeOOH and
30
31
32
APTES-DE for Hg adsorption is explored by control experiments to determine separately the
33
34 adsorption efficiency for both components (Figure 6). The results show that both substrates have
35
36 considerable adsorption capacity for Hg, which confirms that both proposed adsorption
37
38
39 mechanisms is via interaction with oxygen and amino functional groups. Interestingly, the
40
41 adsorption performance of the graphene-DE aerogel is lower than the combined performance of
42
43 the graphene-FeOOH and APTES-DE from the individual experiments. This can be explained
44
45
46 by the blocking of some active sites (O and NH2) in the interconnected 3D network structure of
47
48 the graphene-DE aerogel and also by the lowering of its surface area.
49
50
51
52
53
54
55
56
57
58
59
60
17
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 Figure 6. Time dependence of Hg2+ adsorption on the graphene-DE (GN-DE) aerogel, graphene
25
26 (GN) aerogel (with FeOOH nanoparticles), and APTES modified diatom (APTES-DE).
27
28
29
Conditions: Hg concentration = 200 mg/L; pH = 6.5.
30
31
32
33
34
35 The adsorption kinetics of the graphene-DE aerogel compared to the graphene aerogel
36
37 control was analysed using the Lagergren pseudo-first-order and pseudo-second-order kinetic
38
39
40 models. Pseudo-first-order rate expression of the Lagergen equation43 is given as:
41
42 logQ Q = log Q k t
43
44
where Qe and Qt are the amount of mercury adsorbed in mg/g at equilibrium and at time t (min),
45
46
47 respectively, and k1 (min-1) is the rate constant of the pseudo-first-order adsorption. The
48
49 adsorption rate constant can be determined from the slope of the linear plot of log (Qe Qt)
50
51
52 versus t.
53
54 Pseudo-second-order rate expression41 is given as:
55
56 t 1 t
57 =
58 Q Q k Q
59
60
18
1
2
3
where k2 (kg mg/min) is the pseudo-second-order rate constant. k2 can be calculated from the
4
5
6 slope and intercept of the plot t/Qt versus t.
7
8 The kinetics data obtained from the linearized plots for pseudo-first and pseudo-second
9
10
11
order kinetic models are presented in Table 1. The linear correlation coefficient R2 values for the
12
13 pseudo-first-order kinetic model were 0.85 and 0.94, for the graphene-DE and graphene aerogels,
14
15 respectively (Figure S1). However, greater linear fits with a correlation of 0.98 were achieved for
16
17
18 both types of aerogels when the pseudo-second order kinetic model was applied. This suggests
19
20 that the adsorption data for the kinetics studies are well represented by the pseudo-second order
21
22 kinetic model.
23
24
25
26 Table 1. Lagergren pseudo-first-order and pseudo-second-order kinetics parameters of Hg2+
27
28 adsorption onto graphene-DE and graphene aerogels, and APTES-DE.
29
30
31 Pseudo-first order Pseudo-second order
32 Adsorbent
33 R2 K1 R2 K2 (x10-3)
34
35 0.848 0.048 0.981 3.90
Graphene-DE
36
37
38
Graphene 0.938 0.034 0.980 1.82
39
40 APTES-DE 0.941 0.030 0.979 2.40
41
42
43
44
45 The pseudo-second-order has been widely used to explain the removal of different
46
47 contaminants from the water, which assumes a chemisorption process involving covalent forces
48
49
50 and ion exchange.41,44 The corresponding rate constants (k2) for the graphene-DE and graphene
51
52 aerogels calculated from the slopes of the plots are 3.90 x 10-3 and 1.82 x 10-3 kg mg/min,
53
54
55
respectively. The reactivity of the graphene-DE aerogel is two times higher than the graphene
56
57 aerogel hence the graphene-DE aerogel achieved a greater mercury adsorption capacity.
58
59
60
19
1
2
3
4
5
6 3.4. Adsorption isotherm
7
8
9 At initial mercury concentration of ~400 mg/L an adsorption capacity of 528 mg/g was
10
11
12 obtained for the graphene-DE aerogel, which can be described as outstanding compared
13
14 with other adsorbents. The plot of equilibrium concentration versus adsorption capacity
15
16 (Figure 7) indicated that the adsorption process was a function of the initial concentration.
17
18
19 However, this concentration-dependent adsorption is applicable only to a certain extent,
20
21 as the adsorption becomes a concentration-independent process as soon as it reaches the
22
23 maximum adsorption capacity. It is obvious that for the range of the examined Hg
24
25
26 concentrations the adsorption saturation occurs.
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Figure 7. Adsorption performance of graphene-DE (GN-DE) aerogel at different Hg
49
50 concentrations fitted with equilibrium models. Condition: pH = 6.5
51
52
53
54
55
56
57
58
59
60
20
1
2
3
To analyse the adsorption behaviour of the graphene-DE aerogel, the data in Figure 7 was
4
5
6 plotted using the sorption Freundlich and Langmuir isotherm models.22,45
7
8 The Langmuir isotherm is expressed as follows (3):
9
10
11 = (3)

12
13
14 where, Qe is the adsorption capacity (mg/g), Ceq is Hg2+ concentration (mg/L) at equilibrium, b
15
16 and Qmax are the Langmuir constant (l/mg) determined by the intercept and slope of the linear
17
18
plot of Qe versus Ceq, respectively.
19
20
21
22
23 The Freundlich isotherm is presented by equation (4):
24
25
26 !"# = !"#$ % & !"# (4)
27
28
29
where Kf represents the Freundlich adsorption constant (l/mg) and 1/n is the adsorption intensity.
30
31 These parameters can be calculated from the intercept and slope of the plot logQe versus logCeq,
32
33 respectively.
34
35
36
37
38
39 Correlation coefficients of R2= 0.87 and 0.95 were achieved for the Freundlich and
40
41 Langmuir models, respectively (Figure S2 and Table S1). This result indicates that the
42
43
44 adsorption fits well with the Langmuir model, suggesting monolayer coverage sorption of Hg2+
45
46 ions on the surface of the graphene-DE aerogels. The calculated maximum adsorption capacity
47
48
for Hg2+ removal by the graphene-DE aerogels in this work was found to be higher than carbon
49
50
51 aerogels (35 mg/g),46 APTES-activated carbon (121 mg/g),47 thiol functionalized magnetic
52
53 mesoporous silica,48 and our previous work with 3-mercaptopropyl-trimethoxysilane-DE
54
55
56 (MPTMS-DE) material (185.5 mg/g).23 However, most of the adsorption results for metal ions
57
58
59
60
21
1
2
3
removal in the literature were recorded at optimal pH values, which had a significant effect on
4
5
6 the adsorption capacities of the adsorbent. Furthermore, the SEM images of our graphene-DE
7
8 aerogels after Hg adsorption showed that its 3D structure is preserved during the adsorption
9
10
11
process (Figure S3).
12
13
14
15
16 3.5. Removal of mercury from different water sources
17
18
19
20 In a practical application for the removal of mercury by the graphene-DE aerogel (10 mg
21
22 dosage), adsorption experiments were conducted on natural water samples (tap and river water)
23
24
that were spiked with 100 mg/L of Hg2+ solution compared with milli-Q water as the model
25
26
27 system and is presented in Figure 8. The maximum adsorption capacity of the graphene-DE
28
29 aerogel achieved was 362, 308 and 336 mg/g ( 0.5 mg/g) in milli-Q, river and tap water,
30
31
32
respectively.
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 Figure 8. Batch tests of graphene-DE aerogel for Hg2+ ions removal in different water sources.
56
57 Condition: Hg concentration = 100 mg/L, pH ~ 6-7.
58
59
60
22
1
2
3
4
5
6
7 The results show that the Hg concentration remaining in the river water is slightly higher
8
9 compared to milli-Q water. This might be attributed to the complicated matrices of the river
10
11
12 water, which contains various inorganic and organic substances. These ions are in competition
13
14 with Hg2+ adsorption and the saturation of binding sites of the adsorbent justifies the difference
15
16 in mercury uptake for the difference water sources. However, there is no major interference for
17
18
19 the removal efficiency of the graphene-DE aerogels in the different waters. The slightly higher
20
21 efficiency obtained for tap water compared to river water is likely due to the higher
22
23 concentrations of competitive ions in the river water, as explained earlier.
24
25
26
27
28
29 4. CONCLUSIONS
30
31
32
33
We demonstrated for the first time the synthesis of a self-assembled aerogel composed of
34
35 graphene sheets and DE particles decorated with FeOOH nanoparticles within a robust and
36
37 interconnected 3D network. The prepared aerogel is an effective adsorbent for mercury removal
38
39
40 from high concentration levels, which showed an outstanding adsorption performance with an
41
42 adsorption capacity of > 500 mg/g (at 400 mg/L Hg2+) of Hg ions exceeding many competing
43
44 adsorbents. This new adsorbent prepared by a simple process from two low cost natural materials
45
46
47 widely available from the mining industry (graphite and DE) and based on its excellent
48
49 adsorption performance, is a promising solution for the development of efficient and cost-
50
51
52
competitive adsorbents. The adsorbents can be prepared into different structural shapes
53
54 (depending on the reaction vessel) and utilised in different forms (flat, circular, cube, etc.) for
55
56
57
58
59
60
23
1
2
3
different scenarios for the removal of mercury and other toxic contaminants from the water
4
5
6 (industrial, environmental and drinking).
7
8
9
10
11
12 ASSOCIATED CONTENT
13
14
15 Supporting Information
16
17
18 The information for measuring the specific surface area of the aerogel with the methylene blue
19
20
21 adsorption method; figures and tables showing the pseudo-first and second order kinetics, and
22
23 Langmuir and Freundlich plots for the adsorption of Hg; low and high resolution SEM images
24
25
and EDAX of graphene-DE aerogels after mercury adsorption, respectively. This material is
26
27
28 available free of charge via the Internet at http://pubs.acs.org
29
30
31 Corresponding Author
32
33
34 * dusan.losic@adelaide.edu.au
35
36
37 Author Contributions
38
39
40 The manuscript was written through contributions of all authors. All authors have given approval
41
42 to the final version of the manuscript.
43
44
45
46 Notes
47
48 The authors declare no competing nancial interest.
49
50
51
52
53
54 ACKNOWLEDGMENT
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56
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60
24
1
2
3
This work was supported by The Australian Research Council (FT110100711), The
4
5
6 University of Adelaide, School of Chemical Engineering, Valence Industries Ltd. and
7
8 Archer Exploration Ltd. The authors also thank Mount Sylvia Diatomite Pty. Ltd. for
9
10
11
providing the DE materials and to Ms Aoife McFadden (Adelaide Microscopy) for her
12
13 technical support for ICP-MS measurement.
14
15
16
17
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25 [48] O. Hakami, Y. Zhang, C.J. Banks, Thiol-functionalised mesoporous silica-coated magnetite
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27 nanoparticles for high efficiency removal and recovery of hg from water, Water Res. 46 (2012)
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Table of Contents Graphic and Synopsis
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23 The synthesis of a 3D self-assembled aerogel composite based on two natural materials;
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26 graphene nanosheets extracted from graphite rocks and diatom silica from diatomaceous earth is
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28 described for the first time. It is based on a simple, green, waste-free and scalable process. The
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application of this new adsorbent for the removal of ionic mercury is demonstrated showing
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33 outstanding performance (> 500 mg/g) and great potential for addressing the concerning
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