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Article
Preparation of MnO-modified graphite sorbents from spent Li-ion
2

batteries for lead, cadmium and silver contaminated water treatment

Tuo Zhao, Ying Yao, Meiling Wang, Renjie Chen, Yajuan Yu, Feng Wu, and Cunzhong Zhang
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b07882 • Publication Date (Web): 05 Jul 2017
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Page 1 of 26 ACS Applied Materials & Interfaces

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4 Preparation of MnO2-modified graphite sorbents from spent Li-ion batteries for
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6 lead, cadmium and silver contaminated water treatment
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9 Tuo Zhao1, 2, Ying Yao1, 2*, Meiling Wang1, 2, Renjie Chen1, 2, Yajuan Yu1, Feng Wu1, 2,
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11 Cunzhong Zhang1, 2
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17 1. School of Materials Science and Engineering, Beijing Key Laboratory of
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20 Environmental Science and Engineering, Beijing Institute of Technology, Beijing
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22 100081, China
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25 2. National Development Center of High Technology Green Materials, Beijing
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27 100081, China
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32 Keywords: spent Li-ion battery; recovery; adsorption; heavy metals; MnO2
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__________________________
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50 Corresponding Author
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*Dr. Y. Yao. Email: [email protected]. Tel: 86-10-68918766.
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4 Abstract
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6 A novel adsorbent was prepared via grafting MnO2 particles on graphite recovered
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9 from spent Lithium-ion batteries to treat lead, cadmium and silver contaminated water.
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11 It is the first time that spent LIBs anode material was recovered and applied to heavy
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14 metal contaminated wastewater treatment. Characterizations using SEM, EDX and
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16 FTIR showed that the adsorbent surface was coated with MnO2 ultrafine particles that
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19 served as sorption mechanism as to remove heavy metal ions. In comparison to the
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21 raw artificial graphite (AG) powder, the MnO2-modified AG (MnO2-AG) exhibited a
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24 markedly improved removal capacity toward Pb(II), Cd(II) and Ag(I), their removal
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26 rates reached as high as 99.9%, 79.7% and 99.8%, respectively. The removal of the
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29 heavy metals by MnO2-AG was mainly through ion exchange of hydroxyl groups.
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31 This study provides the possibility of synthesis efficient adsorbent by reusing the
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34 “waste” such as spent Li-ion batteries. It is an economic and environmental-friendly
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36 approach for both heavy metal contaminated water treatment and waste recycling.
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3 1. Introduction
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5 Heavy metal pollution which mainly results from rapid industrial development
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is a worldwide environmental concern in recent years1-3. The heavy metals existing in
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10 the environment, like Pb(II), Cd(II) and Ag(I), could be from natural sources (such as
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volcanic eruptions) as well as anthropogenic activities (e.g. metallurgical engineering,
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15 mine, battery manufacturing, metal plating)4. These harmful ions are always
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poisonous, non-biodegradable5, accumulative in living organism, and may lead to
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20 severe diseases and even death6-8. Thus, developing efficient and low-cost lead,
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23 cadmium and silver remediation technologies is meaningful. Current approaches that
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25 employed for heavy metals treatment mainly include chemical precipitation,
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28 coagulation, electrolysis, adsorption, and membrane filtration4, 9-12
. Among them,
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30 adsorption is widely considered as high efficient, economical choices even at trace
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33 heavy metal level. Recently environmental-friendly and cost-effective adsorbents
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35 raise much concern13. It is attractive to find an abundant feedstock and using low-cost
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38 method transform it into adsorbent for practical wastewater treatment. A number of
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40 suitable solid residues are selected as adsorbent precursors as they are abundant,
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43 easily available and low cost, such as apricot stone, pine cone shell, crab shell, egg
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45 shell, sewage sludge, potato peels, populus fiber, scrap tires8, 14-21.
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48 The use of rechargeable lithium-ion batteries (LIBs) has rapidly increased in the
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50 last decade. They are vastly used in portable devices and electronic automobiles
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53 because of their fantastic features including high energy density, high power density,
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55 and long life cycles22. The massive production and consumption of LIBs inevitably
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58 lead to vast quantities of spent batteries. Take China as an example, there will be 25
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4 billion units and 500 thousand metric tons of discarded LIBs by 202023. The spent
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6 batteries may become a serious problem if without appropriate treatment due to the
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9 existence of toxic metal or flammable compounds24, and in the meantime, recycling of
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11 some valuable waste materials including carbon powders may bring us economic
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14 benefits. There are many researches involved in the recovering of cathode metal
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16 materials while only few studies focused on the usage of anode carbon-based
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19 materials from spent LIBs25-27. Carbon residues from the spent LIBs might be a
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21 selectable feedstock for preparation of novel carbon adsorbent applied in heavy metal
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24 contaminated wastewater treatment, which hasn’t been studied yet, due to their
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26 intrinsic features such as large quantity, relatively pure components, unique carbon
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29 structure, and abundant surface functional groups.
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31 Recent studies have proven that manganese oxide is one of the most promising
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34 adsorbents for removing heavy metals from water owing to its characteristics, e.g.
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36 high surface area, good stability under acidic conditions and availability of hydroxy
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39 functional groups28-31. Qin et al. reported the maximum adsorption capacity of
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manganese dioxide formed in situ was 917 mg/g for Pb(II) and 176 mg/g for Cd(II)29.
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44 However, manganese oxide is unpractical to be applied independently owing to its
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easy conglomeration, poor dispersion and weak separation property32, 33. Therefore,
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49 MnO2 with an appropriate supporter together as sorbent has attracted considerable
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attention in the past few years. Generally, the supporting materials that recently
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54 studied mainly contained magnetic ferriferrous oxide and porous materials28.
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Manganese oxides show its best sorption capacity and selectivity toward heavy metal
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4 ions between pH 2-6, while the isoelectric point of ferriferrous oxide is above 6, thus
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6 the combination of manganese oxides and ferriferrous oxide will reduce usable pH
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9 range and weaken sorption ability of manganese oxides31, 34. On the other hand, the
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11 recovered LIBs anode shows large surface area and stable carbon structure and have
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14 the potential to be a desired porous supporting material for manganese oxides.
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16 MnO2-modified engineered carbon sorbents from waste LIBs should be efficient for
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19 heavy metal contaminated water treatment and also is an eco-friendly approach,
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21 which will benefit the economy as well as the environment.
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24 In this study, we used artificial graphite (AG) powder recovered from spent
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26 commercial LIBs anode as a supporting carbon materials to load MnO2 through a
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29 facile hydrothermal method for removal of Pb(II), Cd(II) and Ag(I) from aqueous
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31 solution. Because spent LIBs anode material, a solid waste, is abundant and
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34 inexpensive, and MnO2 has high adsorption capacity for heavy metals, the MnO2–
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36 modified AG (MnO2–AG) may simultaneously taking advantages from both of them.
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39 To the best of our knowledge, for the first time, spent LIBs anode material was
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recovered and applied to heavy metal wastewater treatment. The objectives of this
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44 study include: (1) preparation and characterization of MnO2–AG ; (2) evaluation of
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Pb(II), Cd(II) and Ag(I) removal ability by MnO2–AG; (3) determination of the
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49 effects of initial metal concentrations and initial solution pH on the sorption of the
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heavy metals onto MnO2–AG as well as sorption mechanisms.
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54 2. Methods
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2.1. Materials
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4 Chemicals used in this study were analytical grade (AR), including lead nitrate
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6 (Pb(NO3)2), cadmium nitrate tetrahydrate (Cd(NO3)2·4H2O), silver nitrate (AgNO3),
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9 potassium permanganate (KMnO4), sodium hydroxide (NaOH), nitric acid and
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11 hydrochloric acid were purchased from Beijing Chemical Works. All solutions were
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14 prepared by dissolving chemicals into deionized (DI) water throughout the
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16 experiments.
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19 2.2. Anode graphite recovery and synthesis of MnO2–AG
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21 The dismantled and separated anode of spent LIBs were collected from a local
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24 Lithium-ion battery company, CITIC GUOAN MGL, Beijing, China. The layer of
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26 carbon material (mainly graphite) coating on the copper foils were used as raw
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29 materials. The anodes were immersed into DI water at room temperature for 1 h to
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31 separate anode carbon materials from support substrates copper foil. The carbon
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34 powder was filtered off and dried in an oven at 80 ℃. The dry carbon powder was
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36 then heated in a tube furnace (T60/10, SGM, China) under N2 flow at a temperature
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39 of 600 ℃ for 1h to remove binder and other organic impurities. The obtained
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carbon material was artificial graphite (AG) powder.
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44 In order to graft MnO2 onto AG powder 5 g AG was immersed in 50 mL of 0.4
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M KMnO4 aqueous solution and adjusted pH to 2 with nitric acid. The mixture was
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49 stirred continuously at 60 ℃ for 4 h and oven dried at 80 ℃. The dry mixture was
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washed several times with DI water to neutral pH and then dried in an oven at 80 ℃
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54 to obtain MnO2-modified AG (MnO2–AG) powder.
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2.3. Characterization
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4 Elemental C, N, H and S compositions of MnO2-AG were analyzed through a
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6 CHNO/S Elemental Analyzer (vario MACRO cube, Elementar, Germany). Major
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9 metal elements contents of MnO2-AG were determined by inductively-coupled
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11 plasma atomic emission spectroscopy (ICP-OES, Optima 8300, PerkinElmer) after
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14 acid digestion of the sample. N2 adsorption-desorption tests onto MnO2-AG and AG
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16 were carried out at 77 K to obtain specific surface area and pore size distribution
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19 based on BET and BJH model, respectively, using a NOVA 2000e (Quantachrome,
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21 USA). The morphology and surface elemental composition of AG and MnO2-AG
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24 were examined by a scanning electron microscope (SEM, Hitachi S-4800, Japan)
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26 equipped with an energy dispersive X-ray fluorescence spectroscopy (EDS, Oxford
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29 instruments, England). A computer-controlled X-ray diffractometer (XRD, Rigaku
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31 UltimaⅣ, Japan) was used to investigate the crystallographic structures on the AG
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34 and MnO2-AG, and data were collected in the 2θ range of 10-90° at a scan rate of
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36 8°/min. The MnO2-AG before and after Pb(II) adsorption as well as AG were pressed
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39 into a disk with KBr powder and then analyzed by Fourier transform infrared
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spectrometer (FTIR, PerkinElmer, USA) in the range of 450-4000 cm-1.
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44 2.4. Adsorption experiments
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Batch adsorption experiments were carried out to investigate contact time, initial
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49 concentration and pH effects on adsorption performance of MnO2-AG. Briefly, 0.1 g
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of MnO2-AG was added to 50 mL of each heavy metal (Pb2+, Cd2+ or Ag+) solutions
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54 in a 50 mL plastic centrifuge tubes, and mixed in a mechanical shaker at 200 rpm.
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After stirring for 24 h at room temperature (23±1 ℃), the suspension was filtered
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4 with 0.22 μm mixed cellulose membrane filters. The initial and final aqueous
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6 concentrations were determined by ICP-OES. The effects of pH were investigated by
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9 varying solution pH 2-7 with an initial concentration of 50 mg/L of each heavy metal
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11 ions.
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14 Adsorption kinetics were conducted with an initial concentrations of 50 mg/L of
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16 each heavy metal ions. At predetermined time intervals (0–24 h), tubes were
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19 withdrawn for the determine of Pb(II), Cd(II) and Ag(I) concentration. Adsorption
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21 isotherms were performed with various initial concentrations. Pb(II) was in the range
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24 of 20-2000 mg/L, while Cd(II) and Ag(I) ranged from 10 to 1000 mg/L. Metal-loaded
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26 adsorbents were collected and dried at 80 ℃ for further characterization. The
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29 removal rate (R, %) and the amount of adsorbed heavy metals (qe, mg/g) were
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31 calculated as follows:
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33 ஼బ ି஼೐
34 ܴሺ%ሻ = × 100 (1)
஼బ
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36 ሺ஼బ ି஼೐ ሻ௏
‫ݍ‬௘ = (2)
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39 where C0, Ce, V and m are the initial adsorbate concentration (mg/L), final adsorbate
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concentration (mg/L), solution volume (mL) and adsorbent mass (g), respectively.
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3. Results and discussion
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49 3.1 Characteristics of MnO2-AG
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The C, H, S, N and metal element contents of MnO2-AG are listed in Table 1.
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54 The sample exhibited high carbon content up to 79.02% while a very small amount of
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other elements were detected. The small amount of Mn (1.33%) was probably
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4 attributed to MnO2 loaded on the feedstock. After adsorption by MnO2-AG, the
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6 hazardous metal concentrations including Mn, Co, Ni, Cu, Li, Pb, Cd and Cr in the
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9 post-sorption solutions were very low or even under detection limit (Table 1). The
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11 leaching toxicity of the prepared MnO2-AG is within the secure level and will not lead
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14 to secondary water pollution35. The BET surface area and BJH pore size were 4.04
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16 m2/g and 28.37 nm for AG powder and 8.13 m2/g and 12.89 nm for MnO2-AG,
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19 respectively, which were relatively low. The surface area of MnO2-AG was two times
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21 higher than that of AG, and the obvious increase was possibly resulted from the
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24 presence of MnO2 particles on the surface of the graphite, which is in accordance with
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26 the finding from previous studies of MnO2 composites36.
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29 The SEM images of AG and MnO2-AG with different magnifications were
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31 shown in Figure 1. The shape of the MnO2-AG was irregular revealing the intrinsic
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34 nature of the AG powder (Figure 1 (b)). High-magnification SEM imaging indicated
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36 the surface roughness of MnO2-AG was significantly improved when large quantities
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39 of MnO2 particles were successfully loaded onto AG surface while the surface of
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original AG were relatively smooth (Figure 1 (a) and (c)). The EDX spectrum of
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44 MnO2-AG identified that the major element is carbon with low levels of oxygen,
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manganese and potassium as well which corresponded to elemental compositions
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49 results (Figure 1 (d)). Carbon, oxygen and manganese were distributed uniformly,
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which further confirmed the cladding of MnO2 particles on AG powder (Figure 2).
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54 The FTIR spectra of AG, MnO2-AG before and after heavy metals sorption
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were shown in Figure 3. In FTIR spectrum of AG, the band at around of 3430 cm-1
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4 was related to the stretching vibration of hydroxyl group and bending vibration of
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6 adsorbed molecular water, whereas the peaks at 2350 and 667 cm-1 is indicative of the
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9 existence of CO2. For MnO2-AG, the peaks at 1090 cm-1 is associated with the
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11 vibration of the hydroxyl group combined with Mn atoms present on the surface (Mn
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14 －O) and C－O stretching vibration . The peaks at 1640 and 1400 cm-1 may be
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16 assigned to C＝O stretching vibration and C－H bending vibration, respectively. In
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19 brief, the abundant functional groups present on the MnO2-AG are beneficial for
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21 adsorption of heavy metal ions. After adsorption of Pb(II), Cd(II) and Ag(I) by
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24 MnO2-AG, the peaks of hydroxyl groups and Mn－O were obviously shifted from
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26 3430 cm-1 and 1090 cm-1 to 3440 cm-1 and 1080 cm-1, respectively. This result
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29 illustrated that the adsorption may occur through ion exchange between the surface
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31 hydroxyl groups and heavy metal ions36. Furthermore, the noticeable shift of hydroxyl
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34 group bonds might result from formation of inner-sphere complexes between
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adsorbate and MnO2-AG, where Pb－O, Cd－O and Ag－O bonds have formed29, 37.
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39 As presented in Figure 4, the XRD patterns of raw AG and synthetic MnO2-AG
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were alike to each other. The diffraction peaks were indexed as graphite and no peaks
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44 coincided with the crystalline form of MnO2, which may due to the amorphous nature
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of the surface MnO2 layers31. The XRD spectrum of post-adsorption MnO2-AG
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49 loaded with Pb(II), Cd(II) and Ag(I) showed no indication of precipitates on the
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surface of MnO2-AG, revealing precipitation might be not the main mechanism for
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54 Pb(II), Cd(II) and Ag(I) removal38.
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3.2. Adsorption of Pb(II), Cd(II) and Ag(I)
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4 3.2.1. Effects of MnO2 modification of graphite on Pb(II), Cd(II) and Ag(I) removal
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6 The sorption ability of AG and MnO2-AG to three heavy metal ions were tested
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9 and revealed MnO2-AG exhibited significantly higher removal rate of Pb(II), Ag(I)
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11 and Cd(II) than AG (Figure 5). The removal rates of MnO2-AG to Pb(II), Cd(II) and
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14 Ag(I) were 99.9%, 79.7% and 99.8%, respectively, which were about 2.6, 52.6 and
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16 4.3 times greater than that of raw AG. The outcome indicated MnO2 modification
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19 greatly improved the adsorption performance of AG to Pb(II), Ag(I) and Cd(II) in
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21 water, which may be attributed to abundant hydroxyl on the MnO2-AG surface and
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24 combine between heavy metals and MnO2-AG.
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26 3.2.2. Adsorption kinetics
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29 Figure 6 shows the sorption kinetic data of Pb(II), Cd(II) and Ag(I) onto
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31 MnO2-AG. Adsorption of three metal ions were rapid in the first ten minutes, with
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34 most of the heavy metal ions being removed. This phenomenon may due to the strong
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36 electrostatic attraction between positively charged metal ions and the negatively
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39 charged surface of MnO2-AG. With increasing contact time, the adsorption rate
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gradually decreased until equilibrium with the decrease in active sites. In this work,
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44 four general sorption kinetics models were chosen to fit the kinetics data as shown in
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Table 2 and also in Figure 6. The n-th-order model fitted Cd(II) and Ag(I) adsorption
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49 on MnO2-AG the best with R2﹥0.9966 and SE﹤0.3748 (Table 2). For the Pb(II)
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sorption, the pseudo-second-order fitted the data slightly better than other models with
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54 the highest R2 (1) and lowest SE (0.015). The results indicate sorption of heavy metal
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on as-prepared MnO2-AG was probably controlled by multiple mechanisms38. This
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4 may due to both the functional groups on MnO2-AG surface and the MnO2 particles
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6 that could serve as the active sorption sites for heavy metals38.
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9 3.2.3. Adsorption isotherms
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11 Sorption isotherms of Pb(II), Cd(II) and Ag(I) onto MnO2-AG were investigated
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14 to describe how the heavy metals distribute between the solid and liquid phases under
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16 the equilibrium state39. As shown in Figure 7, MnO2-AG showed relatively good
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19 sorption ability to Pb(II), Cd(II) and Ag(I) of over 99.88, 29.49 and 67.80 mg/g,
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21 respectively. Five commonly used isotherm models were used to simulate and analyze
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24 the experimental data as shown in Table 3. Except Temkin model, another four models
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26 fitted well with the experimental data with most of R2 over 0.94. The
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29 Langmuir-Freundlich and Redlich-Peterson equations fitted the data better than others
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31 with R2 ﹥ 0.98. Langmuir-Freundlich model assumes that a certain number of
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34 adsorption sites on heterogeneous surface and each site can interact with only one
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36 adsorbate molecule, while Redlich-Peterson model is based on supposition that
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39 multilayer adsorption36. Thus, the sorption of heavy metals on the MnO2-AG might be
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onto a heterogeneous surface with multilayer adsorption, which accord with the
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44 kinetics results. The Langmuir maximum sorption capacities of Pb(II), Cd(II) and
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Ag(I) were 92.35, 23.25 and 62.7 mg/g, respectively. The maximum sorption
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49 capacities of MnO2-AG are higher than or comparable to that of many adsorbents in
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previous studies (Table 4), indicating the MnO2-AG has a high potential to efficiently
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54 treat Pb(II), Cd(II) and Ag(I) contaminated wastewater.
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3.2.4. Effect of solution pH
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4 The solution pH is one of key factors in sorption process. As shown in Figure 8,
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6 when initial pH varied from 2.0 to 4.0, the sorption of Cd(II) and Ag(I) onto
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9 MnO2-AG depended on solution pH, while adsorption of Pb(II) didn’t change much
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11 with pH increase. The removal of Cd(II) and Ag(I) increased gradually by MnO2-AG
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14 and reached their maximum at 79.7%, 99.8%, respectively. Further increases in pH up
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16 to 7.0 hardly affect their removal rates. This result was in line with the proposed
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19 adsorption mechanism that ion exchange between the surface hydroxyl groups and
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21 heavy metal ions. Under low pH conditions, the sufficient hydrogen ions (H+) resulted
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24 in the protonation of adsorbent surface and weaken the electrostatic interaction
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26 between heavy metal ions and the surface of adsorbent. When pH increased, the
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29 growing deprotonation leaded to more negatively charged sites available for
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31 combining with the heavy metal ions on the surface of MnO2-AG40. In summary, the
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34 chemical ion exchange between –OH and the heavy metal ions might be the main
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36 sorption mechanism for MnO2-AG, which is demonstrated by the FTIR results as well.
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39 The main reactions on the surface of MnO2-AG was described as follows:
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2SAC—Mn—OH + Pb2+ ↔ (SAC—Mn—O)2 Pb2+ + 2H+
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44 2SAC—Mn—OH + Cd2+ ↔(SAC—Mn—O)2 Cd2+ + 2H+
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SAC—Mn—OH + Ag+ ↔ SAC—Mn—O Ag+ + H+
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49 where SAC denotes the graphite surface.
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54 4. Conclusions
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In this work, a novel adsorbent MnO2-AG was derived from the spent anode
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4 materials in LIBs modified with KMnO4. The results from the characterization and
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6 adsorption experiments indicated that MnO2 particles were loaded on the surface of
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9 AG successfully which exhibited much better adsorption capability to Pb(II), Cd(II)
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11 and Ag(I) than the pristine AG. The modification of LIBs anode materials thus could
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14 be applied as an environmental-friendly and cost-effective adsorbent to treat heavy
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16 metals from aqueous solutions.
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21 Acknowledgements
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24 This research was supported by the National Natural Science Foundation of
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26 China (NSFC) by Grant 51402018 and the National Key Program for Basic Research
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29 of China by Grant 2015CB251100.
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31
32
33 References
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Lead. Bioresour. Technol. 2015, 181, 13-17.
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4 Figure Captions
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6 Figure 1. SEM images of (a) AG and (b-c) MnO2-AG and (d) corresponding EDX
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9 spectrum of MnO2-AG.
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11 Figure 2. EDX mapping elements of carbon, oxygen and manganese of the
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14 MnO2-AG.
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16 Figure 3. FTIR spectra of AG, MnO2-AG before and after Pb(II), Cd(II) and Ag(I)
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19 adsorption.
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21 Figure 4. XRD patterns of AG, MnO2-AG before and after Pb(II), Cd(II) and Ag(I)
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24 adsorption.
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26 Figure 5. Removal rates of Pb(II), Cd(II) and Ag(I) by AG and MnO2-AG (adsorbent
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29 dose= 0.2 g/L, concentration of metal ions= 50 mg/L, contact time= 24 h, initial
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31 pH=6.0l).
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34 Figure 6. Sorption kinetics data and fitted models of heavy metals onto MnO2-AG: (a)
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36 Pb(II), (b) Cd(II), (c) Ag(I).
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39 Figure 7. Sorption isotherm data and fitted models of heavy metals onto MnO2-AG:
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(a) Pb(II), (b) Cd(II), (c) Ag(I).
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44 Figure 8. Effects of solution pH on sorption of heavy metals onto MnO2-AG.
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4 Table 1. Elemental Compositions of MnO2-AG powder and post-sorption solution.
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6 Sample C H S N Mn K Ca Li Pb Zn Ag Cr Co Ni Cu Cd
7 MnO2-AG (mass%) a
79.02 0.45 0.10 0.04 1.33 0.93 0.33 0.12 0.16 0.03 - b
- - - - -
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Post-sorption
9 0.03 2.53 - 0.14 - - - - - - - -
solution (mg/L)
10 a
11 Expressed on a total dry weight basis.
b
12 Below 0.01%.
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Table 2. Parameters of kinetics models for heavy metals adsorption on MnO2-AG.
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Kinetics models/ equations Parameters Pb(II) Cd(II) Ag (I)
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-1
22 First-order k1 (h ) 139.6 4.476 213.5
23 qe (mg/g) 23.05 16.07 25.12
24 ௗ௤೟ 2
25 ௗ௧
= ݇ଵ ሺ‫ݍ‬௘ − ‫ݍ‬௧ ሻ R 1 0.8895 1
26 SE 0.016 1.996 0.0023
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28 Second-order k2 (g/mg·h) 132.6 0.3811 1384
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30 qe (mg/g) 23.07 16.95 25.12
31 ௗ௤೟ 2
= ݇ଶ ሺ‫ݍ‬௘ − ‫ݍ‬௧ ሻଶ R 1 0.953 1
32 ௗ௧
33 SE 0.015 1.301 0.0014
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35 nth-order kn (gn-1·mg1-n/h) 5×109 14.05 5840
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37 qe (mg/g) 2.5×109 41.17 25.12
38 n 5×10 9
14.93 1.684
ௗ௤೟
39
ௗ௧
= ݇௡ ሺ‫ݍ‬௘ − ‫ݍ‬௧ ሻ௡ 2
40 R 0.9787 0.9966 1
41 SE 1.205 0.3748 0.0009
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43 Elovich β (g/mg) 0.0214 1.966 0.002
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45 α (mg/g·h) 23.03 12.77 25.11
46 ௗ௤೟ 2
= ߙ݁‫݌ݔ‬ሺ−ߚ‫ݍ‬௧ ሻ R 0.4179 0.99 0.3937
47 ௗ௧
48 SE 0.0609 0.4253 0.0059
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4 Table 3. Parameters of isotherm models for heavy metals adsorption on MnO2-AG.
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Isotherm models/ equations Parameters Pb(II) Cd(II) Ag(I)
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7 Langmuir K (L/mg) 1.509 0.2533 5.989
8
‫ݍ‬௘ =
௄ொ஼೐ Q (mg/g) 92.35 23.25 62.7
9 ଵା௄஼೐ 2
10 R 0.9571 0.9483 0.9668
11
12 Freundlich Kf (mg1-n·Ln/g) 49.48 12.8 33.83
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14 ‫ݍ‬௘ = ݇௙ ‫ܥ‬௘௡ n 0.09664 0.1038 0.113
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16 R2 0.9593 0.9832 0.9468
17 Langmuir-Freundlich n
Klf (L /mg )n
1.098 0.667 1.378
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19 ௄೔೑ ொ஼೐೙ Q (mg/g) 99.09 33.53 69.11
‫ݍ‬௘ = ଵା௄೔೑ ஼೐೙
20
n 0.4484 0.2097 0.459
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2
22 R 0.988 0.9958 0. 9962
23
Redlich-Peterson Kr (L/g) 8.765 8.765 14.6
24
25 ௄ ஼
ೝ ೐
‫ݍ‬௘ = ଵା௔஼ α (L /mg )
n n
553.4 553.4 685.8
26 ೙
೐
27 n 0.9402 0.9402 0.9437
28 2
R 0.9801 0.9801 0.9944
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30 Temkin b (J·g/mg) 597.6 597.6 600.8
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32 ܴܶ A (L/mg) 3.3×106 3.3×106 1.771×104
33 ‫ݍ‬௘ = lnሺ‫ܥܣ‬௘ ሻ
34
ܾ R2 0.8656 0.8656 0.9309
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4 Table 4. Comparison of maximum heavy metal adsorption capacities of different
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6 adsorbents
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9 Adsorbate Adsorbent Capacities(mg/g) References
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11 Ag(I) clinoptilolite 33.2 41
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14 Expanded perlite 8.46
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16 MG clinoptilolite 22.57 43
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19 Rice Husk 1.62
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21 MnO2-AG 67.80 This study
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24 Cd(II) Miscanthus sacchariflorus char 11.4
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manganoxide minerals 6.8
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29 Chitosan 1.84
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Chitosan 6.07
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MnO2-AG 29.49 This study
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39 Pb(II) coffee residue carbon 63.29
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42 Polystyrene-alumina activated carbon 22.47
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44 chitosan-modified biochars 14.3
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46 53
47 BPB 47.1
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49 Mn-BC 55.56
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52 Hazelnut shell 28.18
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54 MnO2-AG 99.88 This study
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