Li 2015

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Article
Surface functionalized porous lignin for fast and
efficient lead removal from aqueous solution
Zhili Li, Duo Xiao, Yuanyuan Ge, and Stephan Koehler
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b03994 • Publication Date (Web): 22 Jun 2015
Downloaded from http://pubs.acs.org on July 2, 2015
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Page 1 of 39 ACS Applied Materials & Interfaces
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4 Surface functionalized porous lignin for fast and efficient lead
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6 removal from aqueous solution
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9 Zhili Li 1, 2, Duo Xiao 1, Yuanyuan Ge 1∗, Stephan Koehler 2
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School of Chemistry and Chemical Engineering, Guangxi University, Nanning, 530004, China
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School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, 02138, USA
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18 Abstract
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20 Development of ecofriendly sorbents for fast and efficient decontamination of
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22 heavy metals from aqueous media remains still a big challenge. Here we report
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25 that this task can be addressed by creating a porous natural-occurring polymer
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27 as illustrated by functionalizing lignin with a large number of mesopores and
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plenty of functional groups. We show that the surface functionalized porous lignin
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32 (SFPL) obtained from a two-step process has a large surface area of 22.3 m2/g,
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34 12 times of lignin, and a high density of dithiocarbamate groups (2.8 mmol/g).
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The SFPL exhibits excellent adsorption performance towards lead ions dissolved
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39 in water. For example, 99 % lead ions can be removed in just 30 min by 0.01 g
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41 SFPL from a 50 mL solution containing 20 mg/L lead ions. The saturated
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44 adsorption capacity of SFPL for lead ions is 188 mg/g, which is 13-fold higher
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46 than the original lignin, and 7 times of activated carbon. The adsorption process
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48 is endothermic and is involved with intraparticle diffusion and chemical
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51 adsorption between lead ions and the functional groups of SFPL. The cost-
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53 effectiveness and environmental friendliness of SFPL makes it being a promising
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∗
57 Corresponding author: School of Chemistry and Chemical Engineering, Guangxi University, Nanning, 530004, China
58 geyy@gxu.edu.cn (Y. Ge).
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ACS Paragon Plus Environment
ACS Applied Materials & Interfaces Page 2 of 39
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material for removing lead and other heavy metals from wastewater.
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6 Keywords: lignin; porous; surface functionalization; lead; adsorption
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11 1. Introduction
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13 Water pollution by heavy metals poses a major environmental threat because
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16 these materials tend to bio-accumulate and cause ecological damage 1. To
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18 minimize the amount of heavy metals released into the environment, the
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20 development of high performance sorbents is an essential pursuit for industrial
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23 applications and environmental remediation. Porous silica 2, porous carbon 3-4
,
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25 5-6 7-8
porous MOF , and porous gels have all been investigated for cleanup of
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heavy metals from aqueous solution thanks to their high surface area and high
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30 stability. Nowadays, the research of cost-effective and ecofriendly sorbents
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32 concerning the structure design, synthesis method and intriguing properties has
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35 been widely carried out. Biomass, such as cellulose, lignin, chitosan, as well as
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37 agricultural waste material, have attracted a great deal of attention for heavy
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39 metal removal on account of their natural abundance, low cost, biocompatibility
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42 and low environmental impact 9-12.
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44 Lignin is the second most abundant biomass next to cellulose on earth . It is
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commonly generated as a by-product from pulp & paper industry and is
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48 13
49 considered as a waste . Lignin is a complex, amorphous natural polymer
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51 containing phenolic hydroxyl, methoxyl, ether, which have but low ability to
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53 14-15
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adsorb metal ions . More recently, progressive results by introducing
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56 additional functional groups like amine, sulfonic and xanthate groups onto lignin
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matrix have been obtained by our group . Unfortunately, slow adsorption
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6 rates and low adsorption capacity significantly diminish the practical usage for all
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8 these lignin-based sorbents. The ideal adsorbent must contain high porosity,
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large surface area, and strong binding-site accessibility for adsorbates to achieve
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13 both rapid and high adsorption capacity . However to date, porous lignin-
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15 based materials containing strong binding-sites for heavy metals have yet to be
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18 synthesized.
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20 Here we develop a cost-effective and environmentally safe two-step process to
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22 synthesize a surface functionalized porous lignin (SFPL) with strong
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25 dithiocarbamate and amine/imine functional groups from an alkaline lignin, a by-
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27 product from pulp & paper industry, for the removal of heavy metals from
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29 20
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aqueous solution. We use a Mannich reaction to graft polyethylenimine (PEI)
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32 onto an alkaline lignin matrix (Scheme 1. (a)). PEI is a high-branched polymer
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34 that contains plenty of primary/secondary amine groups which can be esterified
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36 21
37 with CS2 to introduce dithiocarbamate groups (Scheme 1. (b)) and forms a
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39 porous structure. Although there have been a few reports on PEI incorporation in
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41 silica materials and metal organic frameworks 22-24 developed for CO2 separation,
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44 to the best of our knowledge, incorporation of branched PEI into lignin for heavy
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46 metal capture is unprecedented. We thus expect that the PEI grafted lignin
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48 dithiocarbamate composite will provide a large surface with plenty of pores for
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51 interacting with heavy metal ions. Furthermore, numerous amine/imine and
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53 dithiocarbamate functional groups on this ecofriendly biopolymer will strongly
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55 25
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chelate with heavy metal ions , which should increase the capacity and rate of
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heavy metal ions adsorption. Among various heavy metals, lead has been
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6 recognized as one of the most toxic metals. Due to its high toxicity, damage to
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kidneys, liver, nervous system, and reproductive system , lead must be
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extremely removed from the environment. Therefore, we choose lead as a model
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13 heavy metal to investigate the adsorption performance of SFPL. The influences
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15 of several operating parameters, such as solution pH, adsorbent dosage, contact
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18 time, and initial ion concentration, and temperature on the adsorption of lead by
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20 SFPL are investigated. Kinetic models are used to identify the possible
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22 mechanisms of such adsorption process. The Langmuir and Freundlich models
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25 are used to analyze the adsorption equilibrium isotherms.
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27 2. Experimental Section
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30 2.1. Materials
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32 Alkaline lignin was obtained by precipitation from black liquor (Nanpu Pulp Mill,
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35 Nanning, China) with H2SO4 at pH 2.0. Polyethylenimine (PEI, MW=7000 Da, 50
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37 wt. % aqueous solution, (C2H5N)n, N content=32.56 wt.%), copper nitrate, lead
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39 nitrate, cadmium nitrate, nickel nitrate, and zinc nitrate were purchased from
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42 Aladdin Co. LTD., Beijing, China. Carbon disulfide, formaldehyde, sodium
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44 hydroxide and hydrochloric acid were purchased from Shantou Xilong Chemicals.
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LTD., China, which were all of reagent grade. Metal nitrates are dissolved in
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49 deionized water as the metal ion solution samples. Deionized water from a Milli-
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51 Q Plus water purification system (Millipore) is used throughout the experiments.
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2.2. Synthesis of SFPL
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56 The SFPL was synthesized by a two-step method. In a typical experiment, 2.0 g
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alkaline lignin, 4.0 g PEI solution and 150 mL deionized water were added into a
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6 250 mL three-neck flask, and was continuously stirred for 30 min. 8 mL of
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8 formaldehyde was added drop-wise to this mixture, and then the temperature
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11 was elevated to 90 ℃ for 5 h to enable the Mannich reaction (Scheme 1. (a)).
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After that the mixture was cooled to 40 ℃, 10 mL carbon disulfide was added
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18 drop-wise into the flask and kept for 2 h to complete the esterification (Scheme 1.
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20 (b)). Finally, the mixture was filtered and washed with ethanol and deionized
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23 water several times. After drying in vacuum at 50 ℃ for 24 h, we collected the
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26 red-brown powder, i.e. SFPL.
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28 2.3. Characterizations
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31 Elemental analysis of C, H, N and S for SFPL was subjected to be analyzed by
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33 an Element Analyzer (PE 2400 II). Fourier transform infrared spectroscopy (FT-
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35 IR) was recorded with a Nexus 470 spectrometer using a KBr pellets method and
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38 the scan region was between 400 and 4000 cm-1. Morphological measurement
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40 was recorded by a field emission scanning electron microscope (SEM, SU8020,
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Hitachi). X-ray photoelectron spectroscopy (XPS) was acquired by A Kratos Axis
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45 Ultra DLD x-ray photoelectron spectrometer using monochromatic Al Kα (1486.6
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47 eV) X-ray and an analytical chamber with a base pressure of 10-9 torr. Nitrogen
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adsorption isotherms were measured with a Micromeritics Gemini VII 2390
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52 Instrument. Before the measurements, the samples were degassed in vacuum at
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373 K for 12 hr. The Brunauer-Emmett-Teller (BET) method was utilized to
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57 calculate the specific surface areas (SBET, m2/g) from the N2 adsorption isotherm
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in the relative pressure range of p/p0=0.05~0.3. The total pore volume (Vp, cm3/g)
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6 was calculate at p/p0=0.99. The average pore size (dp, nm) is determined by
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8 using dp=4Vp/SBET.
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2.4. Batch adsorption studies
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13 The batch adsorption was performed in conical flasks with a magnetic stirrer at
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16 100 rpm to guarantee a good dispersion and placed in a water bath at 25±0.5 ℃
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19 for a suitable time (t=180 min except the kinetic adsorption) to allow complete
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21 equilibration (C0=10~110 mg/L, adsorbent dosage 0.01 g/50 mL, pH=5). The pH
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value of the solution was adjusted by 0.1 mol/L HCl or NaOH. We varied SFPL
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26 dosages for solutions with initial metallic ion concentration of 20 mg/L to
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28 determine the influence of dosage on adsorption. Kinetic adsorption was
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31 conducted at a lead ion concentration of 20 mg/L, pH=5 with a SFPL dosage of
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33 0.01 g/50 mL, at predetermined time intervals, the solutions were pipetted from
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35 the conical flask and filtered for concentration detection. At the end of each
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38 experiment, the solutions were separated by filtration using 0.22 µm pore-size
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40 filters. The filtrate was analyzed for residual lead ions by inductively coupled
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plasma optical emission spectrometry (ICP-OES, optima 5300DV, Perkin-Elmer),
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45 with a plasma gas flow of 15 L/min and a nebulizer gas flow of 0.6 L/min. The
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47 pump rate was 100 rpm and the sample uptake rate was 1.2 mL/min for 30 s.
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50 The wavelengths for Cd, Cu, Zn and Pb were 226.5, 324.7, 213.9, and 220.4 nm,
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52 respectively. All tests were conducted in triplicate, and their mean values were
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54 used in analyzing the data. The removal efficiency (E) and adsorption amount
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57 (Qe) can be accordingly calculated.
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4 3. Results and discussion
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6 3.1. Synthesis and Structural Characteristics of SFPL
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9 SFPL are prepared by functionalization of lignin using a two-step process. In the
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11 first step, amine groups are attached to the lignin matrix via a Mannich reaction
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13 involving the active hydrogen near phenolic hydroxyl group (Ph-OH) of lignin and
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16 PEI in the presence of a cross-linker such as formaldehyde. In the second step,
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18 the amine groups are reacted with carbon disulfide to produce SFPL with
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20 dithiocarbamate groups (as shown in Scheme 1). Both reactions are facile
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23 reactions . In our efforts to develop a modified lignin with high efficiency for
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25 adsorption of lead ions, we selected branched PEI as grafting agent both for its
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high content of reactive primary/secondary amine groups and high-branched
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30 structure 21. We measured the N contents of the product to investigate the effects
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32 of the amounts of PEI, formaldehyde, and Mannich reaction temperature on PEI
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35 loading, the results are represented in SI. Fig. S1 (a) shows the important impact
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37 of the amount of PEI on the N content of SFPL. As the amount of PEI increases,
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39 the N content definitely increases. However, when the amount of PEI is
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42 excessive, the side-reaction with formaldehyde occurs 20, 30, and thus no increase
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44 of N contents can be seen. Fig. S1 (b) reveals the similar regulation for
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formaldehyde. The Mannich reaction temperature has a slight positive effect on
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49 the N content (Fig. S1 (c)), considering the endothermic nature of Mannich
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reaction 31, we choose 90 ℃ for the Mannich reaction. We also use the S content
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55 to evaluate the effect of amount of carbon disulfide on the dithiocarbamate
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57 loading. As shown in Fig. S1 (d), with increasing carbon disulfide dosage the S
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content increases. However, excessive carbon disulfide will evaporate due to its
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6 low boiling point (46℃). Under these optimum reaction conditions: 2.0 g lignin,
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9 2.0 g PEI, 8 mL formaldehyde, and 10 mL CS2, the prepared SFPL contains
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12 46.91 % carbon, 11.97 % nitrogen, 5.92 % hydrogen and 17.93 % sulfur,
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14 determined by element analysis. It can be calculated that the total N content and
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dithiocarbamate groups in SFPL is around 8.5 mmol/g and 2.8 mmol/g,
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19 respectively. This means about 32.9 % amine groups has been converted into
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21 dithiocarbamate groups. Considering the N element comes from PEI, while the S
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element comes from CS2, it can be also calculated that the PEI loading and
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26 carbon disulfide loading in SFPL is about 36.76 % and 21.29%, respectively. It
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28 should be noted that the development of SFPL is a good residual utilization of
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31 lignin and the synthetic route does not produce any waste; the overdosed carbon
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33 disulfide and formaldehyde used in the process can be collected by ice cooled
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35 condensers and reused. Therefore, this method is a simple and environmentally
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38 friendly route for synthesizing surface functional lignin materials.
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40 SEM micrographs show SFPL contains considerable mesopores (Fig. 1 (b)),
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while the original alkaline lignin is in the form of flocks without pores (Fig. 1 (a)).
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45 That is due to the graft of high-branched PEI on lignin and accordingly benefit the
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47 formation of pores and increase of surface area of SFPL. Fifty pores were picked
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50 out from the SEM image, and their form factors were analyzed with ImageJ 1.48v
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52 . As shown in SI Fig. S2, these pores has an average form factor of 0.72 (a
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54 value of 1.0 indicating a perfect circle). The BET surface area and pore diameter
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57 distribution of SFPL were further analyzed by N2 adsorption isotherms. The
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results are shown in Fig 1 (c, d) and tabulated in Table 1. The N2 adsorption
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6 isotherm of SFPL can be classified as type III according to the IUPAC
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8 classification. The increase in the nitrogen adsorption of SFPL at a high relative
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pressure above 0.9 may arise in part from the mesopores and macropores
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13 associated with the interparticulate voids . The BET surface area of SFPL
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15 calculated over a relative pressure (p/p0) range from 0.05 to 0.3 is 22.3 m2/g,
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18 which is 12 times of lignin (SBET=1.8 m2/g). The pore diameter distribution curve
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20 of SFPL (Fig. 1 d) and the average pore size of SFPL (dp=41.3 nm) calculated
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22 using density functional theory (DFT) 34
further suggest the presence of
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25 mesopores and macropores. Besides, SFPL possesses a much larger total pore
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27 volume of 0.23 cm3/g rather than lignin (Vp = 0.01 cm3/g). On the contrary, lignin
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shows a non-porous structure according to the N2 adsorption isotherm and pore
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32 size distribution curve (Fig 1 (c, d)). The increase of the BET surface area and
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34 total pore volume of alkaline lignin confirms that the porous structure is
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37 successfully introduced, which will benefit the adsorption of lead ions from
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39 aqueous solution.
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41 To confirm the -NCSS- group is attached to SFPL during surface treatment of
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44 alkaline lignin we obtained XPS and FT-IR spectra. XPS measurements of lignin
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46 and SFPL show surface treatment introduces nitrogen and sulfur. We observe
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48 three additional peaks having binding energies of 162 eV (S2p), 226 eV (S2s) and
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51 399.5 eV (N1s), which indicates the presence of sulfur and nitrogen , as shown
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53 in Fig. 1(e). FT-IR measurements further confirm the attachment of these two
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elements and also show their bonding configurations, as shown in Fig. 1(f).
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Compared with lignin, SFPL has additional FT-IR absorption peaks at 1120 and
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6 960 cm-1, which can be assigned to the stretching vibrations of the C=S and C-S
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8 bonds within the -NCSS- functional group, respectively 36
. Moreover, the peak
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associated with C-N stretching vibrations has shifted to 1450 cm-1 for SFPL,
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13 which is due to the neighboring double C=S . The band at 1380 cm-1 is due to
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15 the C-O stretching. We thus conclude that the surface treatment transfers the -
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18 NCSS- group to SFPL.
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20 3.2. Effect of pH on Pb(II) adsorption by SFPL
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22 We measured the lead adsorption by SFPL at different pH values ranging from
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25 2 to 6 with an initial lead ion concentration of 20 mg/L at 25±0.5 ℃, the dosage of
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28 SFPL was 0.01 g/50 mL, and for a contacting time of 180 min. As shown in Fig.
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31 2(a), the uptake of lead ions is strongly affected by the solution‘s pH. At pH 2 the
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33 adsorption efficiency is low, ~50%, and increases to ~99% for pH 5. At low pH,
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35 an excess proton in the aqueous solution could compete with heavy metal ions
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38 for the available active sites. At the same time, the functional groups
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40 (amine/imine and dithiocarbamate groups on SFPL) are protonated, i.e., the
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sorbents surface carried more positive charges at lower pH values . With
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45 increasing the initial pH value from 2 to 5, amine/imine and dithiocarbamate
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47 groups can be gradually deprotonated; and hence the lead ions adsorption
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50 efficiency is greatly enhanced. Moreover, lead hydroxide precipitation will occur
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52 as pH > 6 . Therefore, in order to eliminate the effect of precipitation of metal
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54 hydroxides, further adsorption of lead ions was conducted at pH values of 5.
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57 3.3. Effect of SFPL dosage on Pb(II) adsorption
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We also measured the adsorption of lead ions as a function of SFPL dosage at
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6 pH 5 for an initial concentration of 20 mg/L under 25±0.5 ℃ for a contact time of
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9 180 min. As shown in Fig. 2(b) left, the removal of lead increases sharply from 57%
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12 to 99 % with the adsorbent loading increases from 0.005 g/50 mL to 0.01 g/50
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14 mL (corresponding liquid to solid ratio from 10000:1 to 5000:1), which can be
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attributed to the increasing the number of active adsorption sites . While the
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19 dosage continuously increases to 0.05 g/50 mL, the lead removal efficiency
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21 increases slightly. In parallel the absorption amount decreases from 120 mg/g
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down to 20 mg/g with increasing SFPL dosage, as shown in Fig. 2(b) right. This
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26 is due to the decrease of the ratio of adsorbate to adsorbent. As the initial lead
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28 ion content is constant, the adsorbed amount of lead ions per unit mass
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31 decreases with increasing SFPL dosage. Therefore, the optimal adsorbent
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33 dosage for the investigation of adsorption is selected as 0.01 g/50 mL for the
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35 following experiments.
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38 3.4. Effect of contact time on Pb(II) adsorption by SFPL
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40 To determine the absorption kinetics, we measured the amount of lead ions
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adsorbed by SFPL at a lead ion concentration of 20 mg/L, pH=5 with a SFPL
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45 dosage of 0.01 g/50 mL under 25±0.5 ℃. There is a sharp increase of lead
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48 adsorption in the first 15 min and followed by a slow adsorption process, as
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51 shown in Fig. 3(a). In fact, 91% lead are adsorbed at the beginning 20 min. After
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53 30 min of exposure saturation is achieved and almost 99% lead ions are
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removed by the SFPL (Fig. 3(a) right). The adsorption rate is faster than other
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lead-adsorbing materials including carbon nanotubes and activated carbon (as
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6 listed in Table 2). The fast adsorption of lead ions by SFPL is much contributed
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8 by the porous structure and a large number of functional groups of SFPL for
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interacting with lead ions.
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13 We use pseudo-first-order and pseudo-second-order models, as well as
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intraparticle diffusion model to analyze the kinetic experimental data by these
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18 linear equations:
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21 Pseudo-first-order: log − = log .
(1)
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23

24 Pseudo-second-order: = + (2)
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26

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Intraparticle diffusion: = + (3)
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30 where k1 (1/min) is the pseudo-first-order rate constant, and k2 (g/ (mgmin)) is
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32 the pseudo-second-order kinetic rate constant, kint (mg/g min1/2) is the constant
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35 related to diffusion coefficient, θ is the intercept, Qe and Qt are the amounts of the
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37 metal ions adsorbed (mg/g) at equilibrium and at contact time t (min),
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39 respectively. Lines obtained of the plots with linear regression coefficients (R2)
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42 indicate the applicability of the pseudo-first-order and the pseudo-second-order
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44 models for fitting the adsorption process (Fig. 3 (b)). The correlation coefficients
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of the pseudo-first-order and pseudo-second-order equations for the adsorption
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49 of Pb(II) ions are given in Table 3. Comparison of the correlation coefficients of
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51 the two equations for Pb(II) adsorption indicates the pseudo-second-model (R2 =
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0.9985) is better to describe the adsorption behavior over the whole range of
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56 adsorption. The pseudo-second-model assumes that the rate-limiting step of
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adsorption is a chemisorption between metal ions and the binding sites of
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6 adsorbents . Therefore, we can infer that the adsorption of Pb(II) on SFPL is
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8 mainly controlled by the chemical interaction between SFPL and lead ions.
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According to HSAB theory , lead is a Lewis soft acid, which can react with
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13 Lewis soft bases by covalent bonds, for example, the amine/imine and
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15 dithiocarbamate groups.
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18 The kinetic results are also analyzed by using the intraparticle diffusion model. If
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20 the so-called Weber-Morris plot of Qt versus t1/2 is a straight line, and such a
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22 plot passes through the origin, then the adsorption process is controlled by intra-
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25 particle diffusion only. However, if the data exhibit multi-linear plots, then two or
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27 more steps influence the sorption process 50. As shown in Fig. 3 (C), the plots are
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correlated by three straight lines – the first straight portion depicting the external
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32 resistance to mass transfer surrounding the particles which involves the
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34 movement of lead ions from the bulk solution to the solid phase; and the second
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37 linear portion representing the intraparticle diffusion of lead ions into the
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39 mesopores and macropores; the third linear portion representing the equilibrium
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41 adsorption where the adsorption slows down due to low adsorbate contents in
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44 bulk solution. Since the plot does not pass through the origin (θ=40.8),
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46 intraparticle diffusion is not the only rate-limiting step . These findings suggest
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48 that the adsorption process of lead ions on SFPL involves complex mechanisms,
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51 including intraparticle diffusion and chemisorption process.
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53 3.5. Effect of initial lead concentration on Pb(II) adsorption by SFPL
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To obtain the adsorption capacity of SFPL for lead ions we measured
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adsorption isotherms in a range of initial lead concentrations at pH 5, with a
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6 dosage of SFPL 0.01 g/50 mL under 25±0.5 ℃ for a contact time of 180 min. The
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9 alkaline lignin was used as a reference. The adsorption capacity increases with
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12 the increasing of the initial lead concentration, as shown in Fig. 4(a). This
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14 increase in loading capacity of SFPL is due to the higher the lead concentration,
15
16
the more active adsorption sites of SFPL are involved, and thus leads to a larger
17
18
19 adsorption amount. The saturated adsorption capacity of Pb(II) on SFPL is 188
20
21 mg/g, which is 13-fold higher than on lignin (14.3 mg/g). SFPL also shows a
22
23
24
much higher adsorption capacity for lead ions rather than other lead-adsorbing
25
26 materials, including carbon nanotubes (2 times), activated carbon (7 times) and
27
28 silica gels (2 times), as tabulated in Table 2. The high adsorption capacity of
29
30
31 SFPL for lead is due to its porous structure and the surface-attached
32
33 dithiocarbamate and amine/imine groups.
34
35 We use the Langmuir isotherm model to fit our experimental data, which is
36
37
38 based on the assumption that the adsorption occurs on monolayer sorption onto
39
52
40 a surface with a finite number of homogeneous sites . It can be given by the
41
42
43
following linear equation:
44

45 = + " (4)
! ! #
46
47
48 where Qm is the maximum adsorption capacity (mg/g), Ce is the final equilibrium
49
50 lead concentration, and b is the Langmuir constant (L/mg). The adsorption
51
52
53 capacity is in good agreement with the Langmuir adsorption model (R2=0.9975),
54
55 as shown in Fig. 4(b) and Table 4. The adsorption capacity (Qm=200 mg/g) is in
56
57 accordance with the experimental saturation amount (Qe=188 mg/g), which
58
59
60 14
1
2
3
indicates the homogeneous properties of the SFPL surface and the adsorption
4
5 52
6 belongs to a monolayer adsorption . Freundlich isotherm model is also used to
7
8 analysis the adsorption data. The Freundlich model assumes a heterogeneous
9
10
11
adsorbing surface and active sites, is given by the following linear expression 53:
12

13 log = log$% + log& (5)
14
15
16 where KF is a constant relating the adsorption capacity (L/g), and n is an
17
18 empirical parameter related to the adsorption intensity. Compared with the
19
20
21 Langmuir model, the low correlated coefficient (R2 =0.9582) of the Freundlich
22
23 model indicates that it is in poor agreement with the experimental data, as shown
24
25 in Table 4 and Fig. 4(b).
26
27
28 3.6. Effect of temperature on Pb(II) adsorption by SFPL
29
30 To investigate the effect of temperature on the adsorption process, different
31
32
33 temperatures 25, 40 and 55 ℃ are chosen to obtain adsorption amount of Pb(II)
34
35
36 by SFPL at C0=40 mg/L, SFPL dosage=0.01 g/50 mL, pH=5, t=180 min. The
37
38 standard Gibbs free energy change (∆Go), standard enthalpy change (∆Ho) and
39
40
41 standard entropy change (∆So) are determined by using Eqs. (6), (7) 54:
42
43 ∆G o = -RT lnkd (6)
44
45
46
∆H o ∆S o
47 lnk d = - + (7)
48 RT R
49
50 where kd is the distribution coefficient, R is the gas constant (J/mol K).
51
52
53 The effect of temperature on the adsorption of Pb(II) by SFPL is given in Fig. 5
54
55
(a). With increasing temperature from 25 to 40 and 55 ℃, the adsorption amount
56
57
58
59
60 15
1
2
3
of Pb(II) by SFPL increases from 143 to 156 and 169 mg/g, respectively. The
4
5
6 probable reason is that the diffusion rate of the sorbate within the pores
7
8 increases and the solution viscosity decreases as the temperature increases,
9
10
11
thereby causing an increase in the frequency of collisions between the SFPL and
12
55
13 lead ions , and thus enhancing the adsorption amount. From the plots of the
14
15 distribution coefficient kd versus temperatures in Fig. 5 (b). It can be found that kd
16
17
18 increases with increasing temperature, a certification of endothermic adsorption
19
12
20 in nature . According to Eq. (7), the values of ∆Ho and ∆So can be calculated
21
22 respectively from the slope and intercept of lnkd versus 1/T plots. The calculated
23
24
25 values of thermodynamic parameters are presented in Table 5. The overall Gibbs
26
27
free energy changes during the adsorption process at 25, 40 and 55 ℃ are
28
29
30
31 negative, indicating the spontaneous adsorption process of Pb(II) by SFPL. The
32
33 increase in absolute value of ∆Go as temperature rising indicates that the
34
35 adsorption process becomes more favorable at higher temperature 56
. The
36
37
38 positive value of the enthalpy change (∆Ho=21.9 kJ/mol) indicates that the
39
57
40 adsorption is endothermic in nature . The positive value of entropy change
41
42
(∆So=94.4 J/K mol) suggests the randomness at the solid-solution interface
43
44
45 increases during the adsorption of Pb(II) on SFPL 58.
46
47 3.7. Comparison adsorption of heavy metals by SFPL
48
49
50 Solutions containing Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) (each of 100 mg/L,
51
52 pH=5) were prepared. To 50 mL each of the above-prepared solution, 0.1 g
53
54 SFPL was added and stirred for 180 min, respectively. After that, the adsorption
55
56
57 amount of these metals by SFPL was calculated. The adsorption results are
58
59
60 16
1
2
3
presented in Fig. 6. It is found that the Qe of Cd(II) and Pb(II) are much higher
4
5
6 than the other metals with the ordering of Cd(II)>Pb(II)>Zn(II)>Cu(II)>Ni(II),
7
8 indicating that the SFPL exhibits obvious adsorption selectivity to Cd(II) and
9
10
11
Pb(II). Both of the functional group’s characteristics and the metal ion properties
12
13 should be taken into consideration to account for the adsorption selectivity.
14
15 48
According to HSAB theory , as Lewis soft acids, cadmium and lead ion has
16
17
18 precedence, over zinc, copper and nickel ions which can be regarded as middle-
19
20 soft acids, in the interaction with the amine/imine and dithiocarbamate groups of
21
22 SFPL which belong Lewis soft bases 59
. Thus, SFPL show stronger covalent
23
24
25 affinity to Cd(II) and Pb(II), versus weaker interaction to Cu(II), Zn(II) and Ni(II).
26
27 3.8. Adsorption mechanism of Pb(II) by SFPL
28
29
30
The fast adsorption rate and high adsorption capacity of Pb(II) onto SFPL can
31
32 be clarified as follows. First, as it is well known, PEI carries large amounts of
33
34 amine and imine functional groups. After esterified with carbon disulfide, the
35
36
37 SFPL has plenty of additional functional groups, i.e. dithiocarbamate groups. The
38
39 sulfur and nitrogen coexisting functional groups are expected to have strong
40
41 20, 60
affinity to Pb(II) ions from aqueous solutions . It is reasonable that these
42
43
44 functional groups can provide sufficient active adsorbing sites to form strong
45
46 complexes with Pb(II) on SFPL surfaces and thereby enhance the adsorption
47
48 capacity of Pb(II). Second, the graft of high-branched PEI on lignin increases the
49
50
51 specific surface area and total pore volume of SFPL, and increases the
52
53 interaction areas between the sorbent and the adsorbate, and accordingly
54
55
56
effectively enhance the adsorption rate and capacity of Pb(II) ions. Besides, there
57
58
59
60 17
1
2
3
are abundant ether and phenolic units on lignin chains, which could also form
4
5 14, 61
6 complexes with Pb(II) in the aqueous solution . The synergistic effect of
7
8 these functional groups, large surface area and lots of mesopores certainly plays
9
10
11
a key role in the adsorption.
12
13 Given alkali lignin is the main organic ingredient residing in black liquor from
14
15 pulp & paper industry which has not yet been converted into high-value products
16
17
18 on a large-scale and today it is mainly used for energy recovery at the pulp mills,
19
20 the preparation of SFPL from alkaline lignin for lead removal from aqueous
21
22 solution provides great advantages of wide availability, high value-added, fast
23
24
25 and efficient adsorption, and environmentally friendliness compared to other
26
27 sorbents, such as carbon nanotube and active carbon. Lignin structure is much
28
29 62
30
dependent on the sources and delignification processes , the active hydrogen
31
32 near Ph-OH may be occupied by methoxy group, which makes it is hard to take
33
34 place Mannich reaction. Thankfully, demethoxylation can be accomplished by
35
36 63 64 65 66
37 enzyme , fungi , thermal treatment , and hydrotreating . Thus, suitable
38
39 pretreatments (e.g. demethoxylation, degradation, etc.) for different lignins are
40
41 essential to achieve the reproduction of surface functional porous lignin with
42
43
44 similar properties and yields.
45
46 4. Conclusions
47
48
49 We have reported a surface functionalized porous lignin (SFPL) synthesized by
50
51 a two-step process, and it has been successfully incorporated with
52
53
54
dithiocarbamate functional groups (2.8 mmol/g). The material has a high BET
55
56 surface area (22.3 m2/g) with a large number of mesopores (41.3 nm). Compared
57
58
59
60 18
1
2
3
to other lead-adsorbing materials, the SFPL has a high lead adsorption capacity
4
5
6 (Qe=188 mg/g) with a fast adsorption rate (t=30 min). The adsorption kinetics of
7
8 lead by SFPL can be well described by the pseudo-second-order model that
9
10
11
indicates the chemical interaction of lead ions and SFPL. The adsorption
12
13 isotherm fits well by the Langmuir model. According to the values of
14
15 thermodynamic parameters, i.e. ∆Ho and ∆Go, the adsorption of lead by SFPL is
16
17
18 an endothermic and spontaneous process. The effectiveness of SFPL is due to
19
20 its high porosity, the high affinity of lead ions to dithiocarbamate and amine/imine
21
22 groups, and its large surface area. Moreover, since lignin is a renewable biomass
23
24
25 obtained as a by-product from pulp & paper industry, the manufacture of SFPL
26
27 from lignin is both cost-effective and environmentally friendly. The SFPL exhibits
28
29
30
great potential for treating wastewater containing toxic heavy metal ions.
31
32
33
34
35 Supporting Information
36
37 Figures indicating the influences of the synthetic parameters on the N content
38
39
40 and S contents of SFPL, the form factor distribution of SFPL determined by
41
42 ImageJ 1.48v. This material is available free of charge via the Internet at
43
44
http://pubs.acs.org.
45
46
47
48
49
50 Acknowledgements
51
52 We acknowledge the support from the National Natural Science Foundation of
53
54
55 China (Nos. 21264002, 21464002).
56
57
58
59
60 19
1
2
3
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4
5 61. Mohan, D.; Pittman, C. U.; Steele, P. H., Single, Binary and Multi-Component Adsorption of
6
7 Copper and Cadmium from Aqueous Solutions on Kraft Lignin - a Biosorbent. J. Colloid Interf. Sci 2006,
8
9 297, 489-504.
10
11 62. Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M., The Catalytic Valorization
12
13 of Lignin for the Production of Renewable Chemicals. Chem. Rev. 2010, 110, 3552-3599.
14
15 63. Lopretti, M.; Cabella, D.; Morais, J.; Rodrigues, A., Demethoxylation of Lignin-Model
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17 Compounds with Enzyme Extracts from Gloeophilum Trabeum. Process. Biochem. 1998, 33, 657-661.
18
19 64. Niemenmaa, O.; Uusi-Rauva, A.; Hatakka, A., Demethoxylation of O(14)Ch(3) -Labelled Lignin
20
21 Model Compounds by the Brown-Rot Fungi Gloeophyllum Trabeum and Poria (Postia) Placenta.
22
23 Biodegradation. 2008, 19, 555-565.
24
25 65. Asmadi, M.; Kawamoto, H.; Saka, S., Thermal Reactions of Guaiacol and Syringol as Lignin
26
27 Model Aromatic Nuclei. J. Anal. Appl. Pyrol. 2011, 92, 88-98.
28
29 66. Deutsch, K. L.; Shanks, B. H., Hydrodeoxygenation of Lignin Model Compounds over a Copper
30
31 Chromite Catalyst. Appl. Catal. A-gen. 2012, 447, 144-150.
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1
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4 Figure captions
5
6
7 Scheme 1. Two-step synthesis process of SFPL from lignin, PEI and carbon
8
9 disulfide. (a) Mannich reaction, (b) Esterification. The lignin is colored green, the
10
11 dithiocarbamate is red, and PEI is blue.
12
13
14 Fig. 1 (a): SEM image of lignin, (b): SEM image of SFPL, (c): Nitrogen adsorption
15
16 isotherms of lignin and SFPL, (d): pore diameter distributions of lignin and SFPL,
17
18
(e): XPS spectra and (f): FTIR spectra of lignin and SFPL.
19
20
21 Fig. 2 (a): Dependence of the adsorption efficiency on pH (c0 =20 mg/L, SFPL
22
23 dosage =0.01 g/50 mL, 25±0.5 oC, t=180 min), and (b): SFPL dosage (c0 =20
24
25
26
mg/L, pH=5, 25±0.5 oC, t=180 min).
27
28 Fig. 3 (a): Adsorption kinetics of lead on SFPL (c0 =20 mg/L, SFPL dosage =0.01
29
30 g/50 mL, pH=5, 25±0.5 oC). (b): Fitting results by the pseudo-first-order model
31
32
33 and pseudo-second-order model. (c): Plots of lead adsorption on SFPL according
34
35 to the intraparticle diffusion mode.
36
37 Fig. 4 (a): Adsorption isotherms of lead on SFPL (SFPL dosage =0.01 g/50 mL,
38
39
40 pH=5, 25±0.5 oC, t=180 min) with lignin as a reference. (b): Fitting results by the
41
42 Langmuir isotherm model and Freundlich isotherm model.
43
44
Fig. 5. (a) Effect of temperature on the adsorption of Pb(II) by SFPL (c0 =40 mg/L,
45
46
47 SFPL dosage =0.01 g/50 mL, pH=5, t=180 min); (b) Plot of lnkd against 1/T for
48
49 the adsorption of Pb(II) by SFPL.
50
51
52
Fig. 6 Comparison adsorption of Pb(II) and other heavy metals by SFPL.
53
54
55
56
57
58
59
60 26
1
2
3
Table 1. Textural properties of lignin and SFPL.
4
5
6 SBET (m2/g) Vp (cm3/g) dp (nm)
7
8 Lignin 1.8 0.01 25.3
9
10
11 SFPL 22.3 0.23 41.3
12
13
14
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60 27
1
2
3
Table 2. Comparison of Pb(II) uptake on SFPL and other adsorbents.
4
5
6 Adsorbent Equilibrium time Adsorption references
7 (min) capacity (mg/g)
39
8 Glycerol modified lignin 240 9
9
10 40
Modified soda lignin 60 46
11
12 Amine modified lignin 60 61 20
13
14 12
15
Lignin xanthate 90 62
16 41
17 Carbon nanotube 240 101
18 42
19 Acidified carbon nanotube 360 91
20
43
21 Silica gels 40 83
22
23 44
Activated carbon 105 27
24
25 SFPL 30 188 Present study
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27
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30
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60 28
1
2
3
Table 3. Adsorption kinetics fitting results of lead ions on SFPL by the pseudo-
4
5
6 first-order and pseudo-second-order model, as well as intraparticle diffusion
7
8 model.
9
10
11 pseudo-first-order model pseudo-second-order Intraparticle
12
13 model diffusion model
14
15 Qe k2 R2 Qe k2 (g/ R2 θ kint R2
16 (mg/g) (1/min)) (mg/g) (mg min))
17
18
60.3 0.097 0.9600 102 0.0039 0.9985 40.8 7.3 0.5802
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60 29
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2
3
Table 4. The Langmuir model and Freundlich model fitting parameters for lead
4
5
6 ions adsorption on SFPL.
7
8 Langmuir model Freundlich model
9
10 Experiment Qm (mg/g) b (L/mg) R2 KF n R2
11 Qe (mg/g)
12
13
14 188 200 0.005 0.9975 87.9 5.26 0.9582
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60 30
1
2
3
Table 5. Thermodynamic parameters for the adsorption of Pb(II) by SFPL.
4
5 T (1/K) ∆Go (kJ/mol) ∆Ho (kJ/mol) ∆So (J/K mol)
6
7
8 298 -6.2
9
10 313 -7.5 21.9 94.4
11
12 328 -9.1
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60 31
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Scheme 1
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60 32
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Fig. 1
4
5
6
7 (a) (b)
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18
19
20 (c) (d) 0.5
21
Differential pore volume (cm /g)

Adsobed volume (cm /g, STP)
150
3
22 SFPL 0.4 SFPL
125
Lignin Lignin
23
3
100 0.3
24
25 75
0.2
26 50
27 25 0.1
28
0
29 0.0
0.0 0.2 0.4 0.6 0.8 1.0 10 100
30 p /p0 Pore diameter (nm)
31
32
33 (e)1.2x10
34
5
(f) 1450
1380
1120
960
Na1s
N1s
O1s
C1s
S2s
S2p
35 1.0x10
5
Intensity (Counts/s)
36 8.0x10
4
SFPL
Transmission
37 4
SFPL
6.0x10
38
39 4.0x10
4
Lignin Lignin
40 2.0x10
4
41
0.0
42
43 1000 800 600 400 200 0 4000 3500 3000 2500 2000 1500 1000 500
-1
44 Binding Energy (eV) Wavenumber (cm )
45
46
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60 33
1
2
3
Fig. 2
4
5
6
7 (a) 110
8
9 100
10
11 90
12
13 80
14
E (%)
15 70
16
17 60
18
19 50
20
21 40
22 2 3 4 5 6
23 pH
24
25
26
27 (b) 140
28 100
120
29
30 90
31 100
32
Qe (mg/g)
E (%)
33 80 80
34
35 70 60
36
37 40
38 60
39 20
40 50
41 0.00 0.01 0.02 0.03 0.04 0.05
42 Dosage (g/50 mL)
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60 34
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Fig. 3
4
5
6
7 (a) 1.2
120
8
9 100 0.9
10
11 80
0.6
Qt (mg/g)
12
ce/c0
13 60
14 0.3
40
15
16 20 0.0
17
18 0
0 20 40 60 80 100 120
19
t (min)
20
21
22
23
24 (b)
pseudo-first-order model
25 1.5 pseudo-second-order model 4
26
27
1.0
ln(Q e-Qt)
28
t
t /Q
29 2
30 0.5
31
32
0
33 0.0
34
35 0 20 40 60 80 100 120
36 t (min)
37
38
39 (c)100
40
41 80
42
43 60
Qt (mg/g)
44
45 40
46
20
47
48 0
49
50 0 2 4 6 8 10 12
1/2 1/2
51 t (min )
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60 35
1
2
3
Fig. 4
4
5
6
7
8
(a) 200
9
175
10
11 150 SFPL
12
13 125
Qe (mg/g)
14
100
15
16 75
17
18 50
19 Lignin
25
20
21 0
22 0 15 30 45 60 75 90 105
23 Ce (mg/L)
24
25
26
27
28
logce
29
30 (b) 0.5 2.0 1.6 1.2 0.8 0.4
31 2.0
Freundlich model
32
33 0.4
2.1
34
35
ce/Qe
36 0.3
2.2
logQe
37
38 0.2
39 2.3
40
41 0.1 2.4
42
Langmuir model
43
44 0.0 2.5
45 0 15 30 45 60 75 90
46 Ce (mg/L)
47
48
49
50
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53
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59
60 36
1
2
3
Fig. 5.
4
5
6
7 (a) 180
8
9 160
10
11
140
12
Qe (mg/g)
13
14 120
15
16 100
17
18 80
19
20 60
21 25 30 35 40 45 50 55
22 o
T ( C)
23
24
25
26
27
(b)
3.4
28 ln(kd)
29
3.2
Linear Fit of ln(kd)
30
31
32 3.0
33
ln(kd)
34 2.8
35
36 2.6
37
38
2.4
39
40 0.0030 0.0031 0.0032 0.0033 0.0034 0.0035
41
42 1/T (1/K)
43
44
45
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49
50
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55
56
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58
59
60 37
1
2
3 Fig. 6.
4
5
6
7
200
8
9 175
10
11 150
12
Qe (mg/g)
13 125
14
15 100
16 75
17
18 50
19
20 25
21 Pb Cu Cd Ni Zn
22 Heavy metal
23
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60 38
1
2
3
1.2
4 120
5 100 0.9
6 80
7 0.6
Qt (mg/g)
ce/c0
60
8 0.3
40
9
10 20 0.0
11 0
0 20 40 60 80 100 120
12 t (min)
13
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Differential pore volume (cm /g)

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