From Lignin to Three-Dimensional Interconnected Hierarchically

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From Lignin to Three-dimensional Interconnected Hierarchically Porous Carbon with High Surface Area for Fast and Superhigh-Efficiency Adsorption of Sulfamethazine Zhongshuai Chang, Jiangdong Dai, Atian Xie, Jinsong He, Ruilong Zhang, Sujun Tian, Yongsheng Yan, Chunxiang Li, Wei Xu, and Rong Shao Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b02312 • Publication Date (Web): 25 Jul 2017 Downloaded from http://pubs.acs.org on July 30, 2017

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Industrial & Engineering Chemistry Research

From Lignin to Three-dimensional Interconnected Hierarchically Porous Carbon with High Surface Area for Fast and Superhigh-Efficiency Adsorption of Sulfamethazine Zhongshuai Changa,c, Jiangdong Daib, Atian Xieb, Jinsong Heb, Ruilong Zhangc, Sujun Tianb, Yongsheng Yanb, Chunxiang Lib, Wei Xua*, Rong Shaoa* a

School of Marine and Biology Engineering, Yancheng Institute of Technology, Yancheng 224051, P.R. China

b

Institute of Green Chemistry and Chemical Technology, School of Chemistry and Chemical Engineering Jiangsu

University, Zhenjiang 212013, China c

School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013, China

*Corresponding author: Tel: +86-0515-88168011; fax: +86-0515-88298011

E-mail: [email protected] (Rong Shao)

E-mail: [email protected] (Wei Xu)

Abstract A novel three-dimensional lignin-based interconnected hierarchical porous carbon (3DLHPC) with very high specific surface areas (2784 m2 g-1) and large pore volumes (1.382 cm3 g-1) was prepared using sodium lignin sulfonate (SLS) as carbon precursor, via confinement carbonization, etching silica-template and in-situ alkali activation, for fast and super highly efficient removal of sulfamethazine (SMZ) antibiotics from water. By batch adsorption experiments test, 3DLHPC showed a strong adsorption affinity for SMZ with the maximum mono-layer adsorption capacity of 869.6 mg g-1 at 308 K. Owing to this well-defined 3D interconnected hierarchical porous structure, the adsorption equilibrium could reached within 30 min at 298 K. The adsorption

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mechanism might be involved in van der Waals force, π-π EDA interaction, electronic interaction and hydrophobic interaction, as well as hydrogen bonding interaction. Meanwhile, it was demonstrated that 3DLHPC exhibited excellent regeneration ability, showing the potential possibility for antibiotic wastewater treatments. Keywords: Biorenewable resource, 3D interconnected hierarchical porous carbon, Antibiotic removal, Adsorption, Superhigh capacity

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1. Introduction Sulfonamide antibiotics (SAs) have been used to treat infectious diseases for peoples and animals, and to promote growth as a feed additive in livestock industry over the past few decades, because of the low cost and broad-spectrum antimicrobial activity.1,2 Recently, due to the poor metabolization by organism and improper disposal, one of the most used representative sulfonamides, namely sulfamethazine (SMZ), have been detected at high concentrations in water environments (manure, surface and groundwater), soil and sediment.3 The exposure of residual antibiotics have potentially adverse effects onto human and ecological environment. Thus, it is of great significance to explore high-efficient method for the removal of SMZ from water. Up to now, various methods are being used, including biological treatment,4 chlorination,5 advanced oxidation technology,6 electrochemical treatment,7 adsorption,8 and membrane separation method.9 Among them, adsorption has emerged as an advantageous method, such as easy operation, low-cost, high-efficiency, and no risk of highly toxic secondary pollutants. The performance of adsorption was dependent onto the structure-activity between adsorbate and adsorbent under the operating conditions. Many studies reported the adsorption of SMZ onto several adsorbents, e.g. carbonaceous materials,10 zeolites,11 clay and minerals,12 polymer resin,13 and metal organic frameworks (MOFs).14 Amongst, carbonaceous materials have been extensively considered in antibiotic removal, owing to high specific surface area, abundant pore structures, and strong interactions, mainly involving in biochar, activated carbons, template carbons, carbon nanotubes and graphene and their composites. However, these carbonaceous adsorbents still suffered from some limitations generally for a large scale use, such as relatively low adsorption capacity, slow mass transportation, long adsorption equilibrium time, and high price especially for carbon

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nanotubes and graphene. The above studies about carbonaceous materials focused on the preparation of one- or two- dimensional structured carbons. Therefore, to explore novel, cheap and high-performance carbonaceous materials was urgent for the removal of SMZ antibiotic. One way to achieve this object is to develop new three dimensional hierarchically porous carbons (3D HPCs) with very high surface areas and large pore volumes, possessing the different types of interconnected pores, in which macropores can minimize diffusion distances and microand mesopores provide larger accessible surface areas and smaller transport resistance. 3D HPCs has drawn much attention of researchers and exhibited good application prospect in the super-capacitor, lithium battery, catalysis, and separation. Up to now, there was no report about the preparation of 3D HPCs for the removal of antibiotics including SMZ. In order to obtain low-cost 3D HPCs, the cheap and renewable carbon precursor and effective preparation route should be adapted. Sodium lignin sulfonate (SLS), as a non-toxic, biorenewable and low-cost resource, can be easily obtained from in the paper mill wastewater15,16 and possessed a high content of phenolic group and good water-solubility, which has been one of very ideal candidates.17 For example, activated mesoporous carbon was synthesized using SLS as precursor, with a high specific surface area of 1148 m2/g and a pore volume of 1.0 cm3/g.18 In our previous research, we reported the preparation of HPCs via the combination of halloysite nanotubes-template and in-situ KOH activation using SLS as carbon precursor, with the high specific surface area of 2320 m2 g-1 and large pore volume of 1.342 cm3 g-1, showing the very large adsorption of two antibiotics, tetracycline and chloramphenicol.19 Thus, the object of this work was to prepare a novel 3D HPCs with very high surface areas and large pore volumes, by using SLS as carbon precursor, via confinement carbonization, etching

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silica template and subsequent in-situ alkali activation, which was expected to have fast adsorption speed and large adsorption capacity of SMZ antibiotic from water. This obtained 3DHPC was characterized by XRD, SEM, TEM, XPS, Raman and N2 adsorption-desorption analysis. Various effect factors, such as pH values, contact temperatures and time, initial concentration and ion strength, was investigated to evaluate the behavior of adsorption equilibrium and kinetics in detail. What’s more, the reusability of this 3DHPC was also studied by adsorption and SEM images. 2. Experimental 2.1 Materials Sulfamethazine (SMZ, AR, 99%), tetraethoxysilane (TEOS, AR, 98%), hydrofluoric acid (HF, AR, ≥40%), sodium lignin sulfonate (SLS, AR) and NH3·H2O (AR, 25-28%) were purchased from Aladdin Industrial Corporation (Shanghai, China). Absolute ethanol (AR, 99.7%), KOH (AR, 96%) and HCl (AR, 36%~38%) were obtained from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). All other reagents were used without any purification. 2.2 Instruments The carbonization and activation processes were carried out in a tube furnace (SK-GO6123K, Tianjin, China). Elemental analysis was conducted by using an element analyzer (FLASH1112A, CE, Italy). The micro-texture and morphology were analyzed by transmission electron microscopy (TEM; JEOL IEM-200CX, Japan) and scanning electron microscopy (SEM; JSM-7001F, JEOL, Japan). X-ray diffraction (XRD) analysis was taken on an X-ray diffractometer (Bruker D8 Advance, Bruker AXS, Germany) using Cu Ka radiation (λ=1.5406 Å, 40 kV, 40 mA), with the 2θ value from 10 to 70° at a scan rate of 7° min-1 for phase identification. Raman spectra were analyzed by using a Laser Raman spectrometer (DXR, Thermo Fisher, USA) with a 532 nm

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wavelength incident laser light and 10 mW power. The N2 adsorption-desorption isotherms were measured by using a BELSORP instrument (BEL, Japan) at 77 K. X-ray photo-electron spectroscopy (XPS) analysis was conducted in a Kratos Axis Ultra DLD spectrometer with X-ray excitation provided by a monochromatic Al Kα source. 2.3 Preparation of silica nanospheres 25 mL of deionized water, 70 mL of ethanol and 2.0 mL of NH3·H2O were added to a beaker with vigorous stirring for 15 min, and then 6.0 mL of TEOS was added dropwisely. The mixture were stirred at 298 K for 2.0 h. The white product was separated by centrifugation at 9000 r min-1 and washed with deionized water and ethanol for several times. Finally, silica nanospheres (SNs) were dried at 60 oC for next use. 2.4 Preparation of 3D lignin-based hierarchical porous carbon (3DLHPC) 1.5 g of silica were mixed with 30 wt% of SLS aqueous solution under ultrasonic dispersion. The mixture were treated under the vacuum to remove the bubbles and centrifugated for dense packing at 3000 r min-1 for several hours. The upper SLS liquid was removed and dried at 60 oC under the vacuum. The mixture were carbonized at 500 oC for 2.0 h with a heating ramp rate of 5 o

C min-1 under nitrogen atmosphere. The silica template was etched by dilute hydrofluoric acid

and the 3D lignin-based porous carbon (called 3DLC) was obtained. Furthermore, The 3DLC was uniformly mixed with KOH at a mass ratio of 1:4, and reacted at 850 oC for 2.0 h with a heating ramp rate of 5 oC min-1. The black product was washed with dilute HCl and hot deionized water to remove inorganic impurities. Finally, 3DLHPC were obtained after vacuum drying. The fabrication process for 3DLHPC were shown in Figure 1.

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Figure 1 Schematic illustration of the fabrication process for 3DLHPC

2.5 Batch adsorption experiments In order to investigate adsorption isotherms, 2.0 mg of 3DLHPC were added into 10 mL of SMZ solution with the initial concentrations of 50, 80, 120, 160, 200, 250 and 300 mg L-1 at temperature of 298, 308 and 318 K for 12 h to reach equilibrium, respectively. Supernatant were obtained through a 0.45 mm membrane filter and the determined by an UV-vis spectrophotometer (UV2450, Shimadzu, Japan) at a fixed wavelength of 262 nm. The free concentration of SMZ was calculated by the formula as follow:

Qe =

(C0 − Ce )V M

(1)

Qe (mg g -1) is the equilibrium adsorption capacity. Co and Ce (mg L-1) is in the initial and equilibrium SMZ concentration, respectively. V (mL) is the solution volume and M (mg) is a mass of carbon adsorbent. The adsorption kinetics were performed at different time intervals, including 1, 3, 5, 10, 20, 30, 60, 90 and 120 min, with the initial concentration of 50, 80, 120 mg L-1 at 298 K, respectively. The adsorption amount of Qt (mg g-1) was calculated by the following equation:

Qt =

(Co − Ct )V M

(2)

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herein, Ct (mg L-1) is the SMZ concentrations at any time (t). Furthermore, the solution pH was adjusted at 3.0-9.0 by using NH3·H2O or HCl. The ionic species were adjusted by adding the different metal salt, such as NaCl, KCl, CaCl2, CoCl2·6H2O, NiCl2·6H2O. To research the effect of the real water environment on adsorption of SMZ, humic acids were used to simulate the real water environment. 2.0 mg of 3DLHPC were mixed with 10 mL of SMZ solution (Co=160 mg L-1) with the humic acid concentration of 10, 25, 50 and 100 mg L-1, respectively. 3. Results and discussion 3.1 Characterization SEM images of 3DLC and 3DLHPC were shown in Figure 2. Soluble SLS was filled into the template voids and sintered to form hard carbon texture via confinement carbonization. After the etch of SiO2 template, 3DLC presented a three-dimensional continuous cellular-like structure with an average macro-porous diameter of about 200 nm, which was consistent with the size of SNs. After in-situ alkali-activation, 3DLHPC still maintained a three-dimensional continuous macroporous structure and carbon framework became thinner. Further, pore structure of 3DLC and 3DLHPC were analyzed by TEM, as observed in Figure 3, which was consistent with the results of SEM. Both 3DLC and 3DLHPC showed a three-dimensional continuous cellular-like structure. Importantly, 3DLC was smooth and compact (Figure 3a, b) , while 3DLHPC exhibited a relatively rough surface with a large number of small size nanopores (Figure 3c, d), which were produced by the crucial alkali activation reaction.

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Figure 2 SEM image of 3DLC (a and b) and 3DLHPC (c and d)

Figure 3 TEM image of 3DLC (a and b) and 3DLHPC (c and d)

The N2 adsorption-desorption isotherm of 3DLHPC was shown in Figure 4a. The N2 adsorption isotherms of 3DLHPC followed typical types-I and IV according to the IUPAC classification.20 The steep peak appeared at a low relative pressure area, indicating the presence of

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a large number of micropores.21 Furthermore, the hysteresis phenomenon was emerged in the relative pressure range of 0.2 to 1.0, due to the existence of mesopores and macropores. The pore size distribution and cumulative pore volume curve of 3DLHPC were analyzed by the DFT method. As can be seen in Figure 3b, for 3DLHPC, the majority of pores had less than 2.0 nm diameter, and some pores with the diameter size between 2.0 and 4.0 nm. Thus, 3DLHPC had 3D hierarchical porous structure, which was demonstrated by the SEM, TEM and BET test. Also, 3DLHPC exhibited a large pore volume, which was favor for the fast mass transfer of antibiotic. It is clear that 3DLHPC possessed a high specific surface area of 2784 m2 g-1 and large pore volume of 1.382 cm3 g-1. The pore parameters of 3DLHPC were list in Table S1. According to the t-plot method, high specific surface area and pore volume of micropores of this porous carbon were 2618 m2 g-1 and 1.188 cm3 g-1, respectively, with a high microporosity, mainly owing to highly efficient KOH activation reaction.

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Figure 4 N2 adsorption-desorption isotherms (a), pore size distribution and cumulative pore volume curve (b) of 3DLHPC

The crystal structure of 3DLHPC were analyzed by XRD and the result was shown in Figure 5a. As can be seen, a broad diffraction peak at 2θ = 23.7 ° and a weak peak at 2θ = 42.9 °,22 which was corresponded to carbon structure that has layered ordered stack (002) and ordered hexagonal carbon structure (100), respectively, indicating the presence of a few graphite structure in carbon framework. Raman spectra of 3DLC and 3DLHPC were presented in Figure 5b. There are two prominent peaks at 1350 (D band) and 1580 cm-1 (G band), which were correspond to the graphitic lattice vibration mode and disorder in the graphitic structure, respectively.23 Typically, ratio value of ID/IG was used to assess the degree of graphite.24 The ID/IG ratio of 3DLHPC was larger than 3DLC, which indicated the disorder degree were increased through KOH activation. This is may 11



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due to the produced gases in the activation process, such as steam potassium, hydrogen and carbon dioxide, were intercalated into carbon layer lead to spacing expanding and dislocation.

Figure 5 XRD pattern of 3DLHPC (a) and Raman spectra of 3DLC and 3DLHPC (b)

XPS analysis of 3DLC and 3DLHPC were given in Figure 6. The C1s spectra of both 3DLC and 3DLHPC could be resolved into four main peaks at 284.5, 285.1, 286.8 and 288.1 eV,25-28 which were associated with sp2 C-C, C=C, C-O and C=O, respectively. In the O1s spectrum, the three peaks at 530.3, 531.7 and 532.6 eV,29,30 corresponding to sp2 C=O, H-O, C-O-C, respectively. From Figure 6b, d, we can found that the type of chemical bonds before and after activation have not changed, while the proportion changed some extent. The percentages of functional groups were recorded in Table S2 in detail, showing that surface of 3DLHPC contained many oxygen-containing functional groups, which were beneficial to bind SMZ molecules.

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Figure 6 High-resolution XPS spectra of 3DLC (a and b) and 3DLHPC (c and d)

3.4 Effect of solution pH Figure 7 showed effect of solution pH on SMZ adsorption by 3DLHPC. It can be seen that adsorption capacity was maximum (640 mg g-1) at pH 3 and decreased slowly from pH 3.0 to 7.0. When pH increased above 7.0, adsorption decreased significantly. The pH-dependent adsorption depended on changes of chemical structure of SMZ and surface property of 3DLHPC at different pH values. On the one hand, SMZ has two pKa value of 2.2 and 7.4. The SMZ dominant species became cat-ionic (SMZ+) at pH < pKa1 (2.2), anionic (SMZ-) at pH > pKa2 (7.4) and neutral (SMZ0) at the range of pH 2.2-7.4. With the increase of pH, the amount of neutral molecules gradually increased, leading to the reduction of electrostatic attraction. As pH increased to 8 and 9, the anionic species was dominant in solution and the adsorption reached a minimum value because of increasing electrostatic repulsion of SMZ and 3DLHPC surface.31,32 On the other hand, the increased pH resulted in the deprotonation, which could reduce the π-withdrawing ability and hydrophobicity of SMZ, therefore suppressing π-π electron-donor-acceptor (EDA) interaction and

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hydrophobic interaction between SMZ and surface π-donor graphite structure of 3DLHPC. The SMZ solution which were used in adsorption experiment did not adjust the pH value.

Figure 7 Effect of solution pH on adsorption of SMZ by 3DLHPC

3.2 Adsorption isotherm The adsorption isotherm plots and non-linear fitting curves of SMZ adsorption by 3DLHPC were displayed in Figure 8a. It was clear that adsorption capacity increased with the increasing initial concentration, and gradually into equilibrium. Also, the optimum reaction temperature was 308 K, to obtain the largest adsorption amount.Three adsorption isothermal models, namely Langmuir, Freundlich and Temkin equation,33,34 were used to analyze the data to understand adsorption behavior.

Qe =

K L QmCe 1 + K L Ce

RL =

(3)

1 1 + K L Co

(4)

Qe = K F Ce1/ n

(5)

Qe = K T ln(Ce ) + K T ln( f )

(6)

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here Qm ( mg g-1) is maximum monolayer adsorption capacity. KL (L mg-1) and KF (mg g-1) (mg-1)1/n was Langmuir and Freundlich isotherm constant, respectively. RL is separation factor. KT and f are Temkin isotherm constants.

Figure 8 The adsorption isotherm of SMZ onto 3DLHPC (a) and Effect of the initial concentration on the value of RL of the Langmuir isotherm (b)

Adsorption isotherm parameters were listed in Table S3. The correlation coefficients (R2) of Langmuir model were higher than 0.99, which were better than two other adsorption models. Meanwhile, the fitting curves was well matched with the plot from experimental data. It is indicated that Langmuir model could well describe the adsorption isotherm data. The maximum monolayer adsorption capacities of SMZ onto 3DLHPC were 800.0, 869.6 and 735.3 mg g-1 at 298, 308 and 318 K, respectively. Figure 8b presented the RL curves of 3DLHPC at three temperatures. All the RL values were less than 0.1, which indicated that adsorption process was favorable and the optimal property was obtained at 308 K at a higher initial concentration. As compared with those previously reported SMZ adsorbents, the 3DLHPC synthesized in this work showed a far higher adsorption of SMZ from water, mainly due to the higher specific surface area and pore volume, as listed in Table S4.35-42 3.3 Adsorption kinetics

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Adsorption kinetics study was crucial to evaluate performance of adsorbent. Figure 9 showed effect of contact time and initial concentration on adsorption kinetics of SMZ by 3DLHPC. With the reaction time increased, adsorption amount increased significantly in the initial stage within 30 min, and increased slowly to saturation within 60 min. higher initial SMZ concentration was favor for higher adsorption capacity, but needed more time to reach adsorption equilibrium. In order to explore adsorption behavior, two kinds of kinetic models were used to fit adsorption data.43 The linear expression of the pseudo-first-order44 and pseudo-second-order kinetic model45 is written as follow, respectively:

ln(Qe − Qt ) = ln Qe -k1t

(7)

t 1 t = + 2 Qt k2Qe Qe

(8)

Qe and Qt (mg g-1) are adsorption capacity of at equilibrium and time t, respectively. k1 (min-1) and k2 (g mg-1 min-1) is the pseudo-first-order and pseudo-second-order adsorption rate constant, respectively.

Figure 9 Effect of contact time and initial concentration on adsorption kinetics of SMZ by 3DLHPC

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The pseudo-first-order and pseudo-second-order kinetic linear fitting curves of adsorption of SMZ onto 3DLHPC was illustrated in Figure 10, and these kinetic parameters were listed in Table S5. As can be seen, the R2 values of the pseudo-second-order model were higher than 0.999. However, the R2 values of pseudo-first-order model was relatively low. Thus the experiment data were well fitted by the pseudo-second-order kinetic model.

Figure 10 The linear-fitting kinetics curves by the pseudo-first-order (a) and pseudo-second-order (b) rate mode

In order to more clearly understand adsorption process, experimental data were analyzed by the particle diffusion model, which was expressed as follow:46

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Qt = Ki1/2 + C

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(9)

where Ki (mg g-1 min-1/2) and Ci (mg g-1) are the intra-particle diffusion coefficient. According to this model, if fitted Qt vs t1/2 is a straight line through the origin, the particle diffusion is the rate controlling step in the whole adsorption process. Linear fitting curves of SMZ adsorption by particle diffusion model were presented in Figure 11 and parameters was listed in Table S6. The fitted line displayed the three linear stages intercept, which indicated adsorption process were effected by multiple steps. The large intercept C1 at the initial stage indicated fast boundary layer diffusion rate of SMZ from water due to the available binding sites and high specific surface area. The second linear curve was controlled by intra-particle diffusion of SMZ molecules in the micropores and mesopores, showing a low removal rate. Finally, adsorption process approached equilibrium slowly. The fitting curves were not through the origin, indicating the intra-particle diffusion was not the only rate control step, and the process might involve in membrane diffusion.47-49

Figure 11 The curve of Intra-particle diffusion equation

3.5 Effect of coexisted ions

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The effect of ions species on adsorption of SMZ onto 3DLHPC was shown in Figure 12. It can be seen that the effect of monovalent and divalent metal ions on adsorption was little, indicating electrostatic interaction was not the main adsorption mechanism. Among, transition metal ions had a certain effect on adsorption capacity, because Co2+ and Ni2+ ions could be adsorbed onto the inner and outer surface and weaken the electrostatic interaction and van der Waals forces between SMZ molecules and 3DLHPC surface.50

Figure 12 Effect of ion species on the adsorption of SMZ by 3DLHPC

3.6 Effect of soluble humic acid Figure 13 showed effect of added soluble humic acid on SMZ adsorption. It was obvious that SMZ adsorption onto 3DLHPC greatly decreased with the increase of humic acid concentration. This phenomenon was caused by the competition adsorption of humic acid toward binding sites surface located on surface of 3DLHPC through π-π EDA and van der Waals forces. A portion of active sites were occupied by humic acid molecules, leading to a significant decline of SMZ adsorption.51,52 Importantly, we first found that there was a good linear correlation between SMZ adsorption capacity and the addition concentration of humic acid.

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Figure 13 Effect of concentration of humic acid on adsorption

3.7 Adsorption mechanism analysis Many factors could affect adsorption mechanism, including the property of absorbent, mass-transfer process in solution and surface chemistry. The strong adsorption of 3DLHPC toward SMZ was mainly due to high specific surface area and pore volume. The van der Waals forces exist widely between molecules and molecules. The strong van der Waals force could happen easily between SMZ and surface of 3DLHPC and has a certain effect on adsorption.53 What’s more, SMZ has a planar benzene ring with the strong electron withdrawing ability, as π-electron-acceptors, which can interact with the polarized graphite surface of 3DLHPC via π-π EDA interaction .54 From the investigation of pH effect, electronic interaction and hydrophobic interaction was partly for SMZ adsorption. Besides, hydrogen bonding interaction might be formed between sulfamide, amine and pyrimidine of SMZ and the O-containing groups on surface of 3DLHPC. 3.8 Regeneration performance of 3DLHPC Regeneration ability is an important parameter of the adsorbent. SEM images of regenerated 3DLHPC were shown in Figure 14. It was clear that the morphology of 3DLHPC had almost no

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changed after repeated use and still maintained three-dimensional interconnected macroporous structure. Also, recycled adsorption results of 3DLHPC were shown in Figure 15. It can be observed that 3DLHPC still kept a high adsorption of SMZ after 10 cycles, suggesting good regeneration property. Thus, 3DLHPC possessed a good reusability and excellent structural stability.

Figure 14 SEM image of regenerated 3DLHPC after recycles

Figure 15 Regeneration property of 3DLHPC

4. Conclusions In summary, we successfully provided an effective approach for the conversion of industrial SLS to a novel 3DHPC with three-dimensional continuous macro-porous and meso/micro-porous

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structure, by using the combination of template-assisted, confinement carbonization and in-situ chemical activation method. 3DLHPC showed very high specific surface area of 2784 m2 g-1 and huge total pore volume of 1.382 cm3 g-1, resulting in a superhigh adsorption capacity of SMZ (869.6 mg g-1) at 308 K and fast adsorption rate. The possible mechanism of strong absorption was due to van der Waals force, π-π EDA interaction, electronic interaction, hydrophobic interaction, and hydrogen bonding interaction. The excellent reusability of 3DLHPC provided a potential as advanced adsorbents for the large scale application in antibiotic wastewater treatment. This universal synthetic strategy can be also extended to the fabrication of multifunctional hierarchical porous carbon materials derived from other biorenewable biomass, including chitosan, starch, cellulose, sodium alginate and so on, for wide applications, e.g. electrochemical, energy, medicine, catalysis and environment. Acknowledgments This work was financially supported by the National Natural Science Foundation of China (Nos. U1407123 21576111, U1510126, 51608226 and 21676127), Natural Science Foundation of Jiangsu Province (BK20140534, BK20140580, BK20160501, and BK20151350), Research Fund for the Doctoral Program of Higher Education of China (20133227110022 and 20133227110010) and Jiangsu Planned Projects for Postdoctoral Research Funds (1501067C).

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From Lignin to Three-Dimensional Interconnected Hierarchically

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