Ordered Mesoporous Carbonaceous Materials with Tunable Surface

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Ordered Mesoporous Carbonaceous Materials with Tunable Surface Property for Enrichment of Hexachlorobenzene Jianwei Fan, Xianqiang Ran, Yuan Ren, Chun Wang, Jianping Yang, Wei Teng, Liyin Zou, Yu Sun, Bin Lu, Yonghui Deng, and Dongyuan Zhao Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b02258 • Publication Date (Web): 06 Sep 2016 Downloaded from http://pubs.acs.org on September 7, 2016

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Ordered Mesoporous Carbonaceous Materials with Tunable

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Surface Property for Enrichment of Hexachlorobenzene

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Jianwei Fan,† Xianqiang Ran,† Yuan Ren,‡ Chun Wang,‡ Jianping Yang,†,‡ Wei Teng,†

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Liyin Zou,§ Yu Sun,§ Bin Lu,†,* Yonghui Deng‡,ψ *, Dongyuan Zhao‡

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†

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Environmental Science and Engineering, Tongji University, Shanghai 200092, P.R.

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China

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‡

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Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,

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iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan

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University, Shanghai 200433, China

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§

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Company Limited, Shanghai, 200092, P.R. China

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ψ

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Information Technology, Chinese Academy of Sciences, Shanghai 200050, China

State Key Laboratory of Pollution Control and Resource Reuse, College of

Department of Chemistry, State Key Laboratory of Molecular Engineering of

Shanghai Tongji Clearon Environmental-Protection Equipment Engineering

State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and

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Corresponding author: [email protected], [email protected]

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1

ACS Paragon Plus Environment

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Abstract

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A gradient pyrolysis approach has been adopted for synthesis of ordered mesoporous

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carbonaceous materials with different surface and textural properties for removal of hexachlorobenzene. The resultant ordered mesoporous carbonaceous materials possess high surface areas (364 ~ 888 m2/g), large pore volumes (0.23 ~ 0.47 cm3/g),

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uniform pore sizes (2.6 ~ 3.8 nm), and tunable hydrophobic properties. They show high-efficiency removal performances for hexachlorobenzene with high adsorption capacity of 594.2-992.1 µg/g. An enhanced removal rate (> 99 %) can be obtained with the increasing of pyrolysis temperature (900 °C), due to strong hydrophobic-hydrophobic interaction between the carbon framework and hexachlorobenzene molecules. Furthermore, the adsorption behaviors follow the Langmuir equation and obey the pseudo-first-order kinetic model.

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Keywords: Mesoporous materials, Hexachlorobenzene, Water treatment

Carbonization

temperature,

2


Adsorption,

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1. Introduction

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Hexachlorobenzene (HCB) is one kind of typical persistent organic pollutants

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(POPs). It was considered as a commonly efficient fungicide which was once widely

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used in the last century and still could be frequently found in soil, sediment, water, air,

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and also in biota nowadays [1-4].The presence of HCB in environment do great harm

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to human beings and ecosystem [5, 6], causing dermatitis, severe numb in

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cardiovascular and nervous system, and even cancer [7-9].Therefore, it is urgent to

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develop efficient and economical methods for removal of HCB.

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Up to now, various techniques such as chemical enhanced washing, electrokinetic

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(EK) remediation, reductive/oxidation dechlorination, thermal decomposition and

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radiolytic reduction have been adopted for the treatment of HCB in soil and sediment

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[10-20]. However, there are few reports on the removal of HCB in water. In fact, HCB

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accumulated in soil and sediment mainly comes from the surface water, for this

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reason the treatment of HCB in aquatic environment maybe relatively crucial and

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should deserve more attentions [21, 22]. While chemical properties of HCB, such as

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hydrophobic property, bring a great challenge to researchers. Therefore, it is still very

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difficult to find an effective approach for the removal of HCB in water.

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Ordered mesoporous carbonaceous materials are emerged as the promising

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candidates for pollutants adsorption and removal, because of their stable,

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environmentally friendly properties, the ideal space for the fast accumulation of

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organic pollutants, tunable ordered mesopore sizes ranging from 1.5 to 10 nm [23, 24],

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and the remarkable properties such as high surface areas and large pore volumes 3


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[25-27]. Especially, ordered mesoporous carbons are considered as ideal adsorbents in

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treating environmental issues [28] due to the fast mass transfer in their mesochannels.

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In addition, mesoporous carbons display the excellent adsorption ability for organic

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pollutants, such as reactive dyes (Remazol Red, methylthionine chloride and

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rhodamine B), alcohol biofuel, chloroacetic acid, aminoacids, toluene, lysozyme and

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naphthalene from aqueous solutions [29-33]. However, there are rare reports

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concerning removal of persistent organic pollutants (POPs) using ordered mesoporous

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carbons as the adsorbents. Furthermore, there is a lack of systematic research about

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the effect of different surface properties of mesoporous carbon on their adsorption

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capacities.

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Herein, we detailedly investigate the removal of HCB from aqueous solutions using

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ordered mesoporous carbonaceous materials calcinated at different temperatures (350,

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600 and 900 °C) as adsorbents, which denoted as OMC-350, OMC-600, and

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OMC-900, respectively. All these materials have ordered two-dimensional (2-D)

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hexagonal mesostructure, open mesopore channels, and hydrophobic properties.

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While the hydrophobic property of ordered mesoporous carbonaceous materials

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endow the superior HCB adsorption efficiency (> 99 %). The sorption capacity and

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kinetics were studied using the batch method. The results can provide necessary

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information for a better understanding of the POPs adsorption and separation

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involving mesoporous carbonaceous materials.

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2. Materials and methods

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2.1. Chemicals

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Triblock

copolymer

poly(ethylene

oxide)-block-poly(propylene

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oxide)-block-poly(ethylene oxide) copolymer, Pluronic F127 (EO106PO70EO106, Mw =

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12,600) was purchased from Aldrich. Hexachlorobenzene (HCB) (100 mg/mL) was

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purchased from J&K Chemical Ltd. Pure water was deionized with a Milli-Q water

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purification system (Millipore). Phenol, n-hexane, formaldehyde and ethanol were

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purchased from Sinopharm Chemical Reagent Co., Ltd.

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2.2 . Preparation of ordered mesoporous materials

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The carbon precursor, phenolic resin ethanolic solution (20 wt. %), was prepared

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referring to the method of Meng et al [34]. The ordered mesoporous materials were

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prepared by organic-organic self-assembly approach with phenolic resin as carbon

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source and triblock copolymer Pluronic F127 as the structure-directing agent. The

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synthesis procedure for ordered mesoporous materials was as follows. First, 1.0 g of

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triblock copolymer Pluronic F127 was dissolved in 20.0 g of ethanol with stirring for

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3 h to obtain a clear solution. Then, 5.0 g of phenolic resins ethanolic solution was

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added with stirring for 3 h. After that, the mixture was poured into dishes to evaporate

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ethanol completely at 25 °C for 8 h, and heated at 100 °C for 24 h to obtain the

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as-made samples. Then, it was carbonized at different temperature (350, 600 or

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900 °C) for 3 h under N2 to obtain the samples denoted as OMC-350, OMC-600, and 5


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OMC-900, respectively. The heating rate was 1 °C/min below 600 °C and 5 °C/min

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above 600 °C.

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2.3 . Characterization

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Small-angle X-ray scattering (SAXS) patterns were collected on a Nanostar U

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small-angle X-ray scattering system using Cu Kα radiation at 40 kV and 35 mA. The

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d-spacing values and unit cell parameters (a0) were calculated by the formula

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d = 2π / q and a0 = 2d10 ( 3)−1 , respectively. Transmission electron microscopy

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(TEM) experiments were carried out using a JEOL 2011 microscope operated at 200

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kV. The ground samples for TEM measurements were suspended in ethanol and

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supported on a carbon-coated copper grid. The N2 adsorption-desorption at 77 K was

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performed on a Micromeritics Tristar 3000 analyzer. Before the measurements, all

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samples were degassed at 180 °C in vacuum for more than 6 h. The pore size

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distributions were derived by using the Barrett-Joyner-Halenda (BJH) model. The

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total pore volume (Vp) was estimated from the adsorbed amount at p/p0 of 0.995. The

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specific surface areas were calculated by the Brunauer-Emmett-Teller (BET) method.

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13

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spectrometer. The

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and the contact time was 1 ms. Adamantane was used as a reference for 13C chemical

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shift. Infrared Spectrum scanned from 4000 ~ 400 cm-1 was detected at ambient

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temperature on a Nicolet Fourier transform infrared spectrometer.

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2.4. Adsorption experiments

C NMR spectrum was recorded at room temperature on a Bruker MSL-300 13

C resonance frequency was 75 MHz. Their cycle time was 2 s,

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Experiments

were

carried

out

to

investigate

adsorption

behaviors

of

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hexachlorobenzene using the ground samples in batch mode. The absorbate solution

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was prepared by diluting HCB standard solution (100 mg/mL in methanol) to a series

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of certain concentrations. All adsorption studies were conducted as follows: a fixed

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mass of adsorbent was added into a conical flask with 50 mL of HCB solution with

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various initial concentrations. Each flask was sealed, and stirred in a rotary shaker at

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150 rpm under different constant temperatures (± 0.5 °C) for 24 h. After that, the

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mixture was taken out and filtered using a membrane filter for further analysis. All the

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experiments were carried out with repeated trials.

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In order to screen out the optimal adsorbent with maximum adsorption ability, three

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kinds of ordered mesoporous materials (10 mg) calcined at 350, 600, and 900 °C and

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commercial active carbon (surface area of ~1900 m2/g, pore size of 0.99), indicating that the diffusion including

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liquid film and intra-particle diffusion are the rate-controlling steps for the HCB

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adsorption on OMC-900 material. The coefficient of determination (R2 = 0.996) for

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pseudo-first-order model is higher than that for Lagergren-second-order model (R2 =

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0.994), suggesting that the kinetic process can be better explained by

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pseudo-first-order model. Additionally, the value of qe (933.30 µg/g) calculated using

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the pseudo-first-order model is closer to the experimental data (962.31 µg/g).

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4. Conclusions

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In summary, ordered mesoporous carbonaceous materials with different surface

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properties have been successfully synthesized by organic-organic self-assembly

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method with phenolic resin as carbon source, triblock copolymer Pluronic F127 as

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structure-directing agent at different pyrolysis temperature. The obtained OMC-350,

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OMC-600 and OMC-900 have ordered hexagonal mesostructures, uniform pore size

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distribution, high surface area for adsorption removal of HCB. OMC-900 material

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show the highest adsorption capacity (992.09 µg/g), which is higher than that of 17


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commercial active carbon at 25 °C (809.05 µg/g). Theoretical fitted results based on

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thermodynamics data indicate that the adsorption of HCB is physical adsorption with

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an exothermic process. Meanwhile, these equilibrium data fit well with the Sip’s

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isotherm model and demonstrate a heterogeneous adsorption. The adsorption of HCB

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by OMC-900 can be well explained by a pseudo-first-order kinetic model. This new

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kind of ordered mesoporous carbon (OMC-900) with high surface area and

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hydrophobic characteristic is supposed to be applied in the adsorption of hydrophobic

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pollutants from water.

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5. Acknowledgments

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This work was supported by the National Natural Science Foundation of China

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(21377096, 51372041, 51422202), the State Key Laboratory of Pollution Control and

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Resource Reuse Foundation (NO. PCRRK16009), the Shanghai Committee of

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Science and Technology (14ZR1400600), the “Shu Guang” Project (13SG02) of

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Shanghai Municipal Education Commission, Shanghai Municipal Science and

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Technology Commission (13140902401, 14JC1400700), and National Youth

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Top-notch Talent Support Program in China.

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1 2 3 4

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Table 1. Properties of the samples prepared at different pyrolysis temperature. SBET is the BET specific surface area; a0 is the unit-cell parameter; D is the pore diameter; T is the thickness of pore walls; VP is the total pore volume; qe is the adsorption capacity.

pyrolysis temperature

a

SBET

b

a0

c

D

d

T

e

Vp

q e

sample

(°C)

(m2/g)

(nm)

(nm)

(nm)

(cm3/g)

(µg/g)

OMC-350

350

364

10.85

3.82

7.03

0.23

594.18

OMC-600

600

596

10.00

2.65

7.35

0.31

875.78

OMC-900

900

888

9.27

2.61

6.66

0.47

992.09

5

a

6

b

7

c

8

d

9

e

Calculated by the BJH model from sorption data in a relative pressure range from 0.04 to 0.2. Calculated from SAXS results.

Calculated by the BJH model from the adsorption branches of the isotherms. Calculated by the formulas T= a0-D.

Estimated from the adsorbed amount at p/p0 of 0.995.

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Langmuir

1

Table 2. Equilibrium and thermodynamics parameters for the adsorption of hexachlorobenzene

2

(HCB) by ordered mesoporous carbon (OMC-900).

Langmuir T

R2

°C

Feundlich Qm

a

R2

µg/g

L/µg

b

Sips b

kf

c

nf

R2

Qm

d

µg/g

L/µg

ks

e

ms

25

0.98

530.02

2.16

0.94

287.69

0.30

0.96

637.22

0.87

1.05

35

0.97

528.87

0.38

0.93

175.19

0.34

0.98

560.68

0.32

1.11

45

0.94

523.52

0.22

0.92

120.02

0.43

0.95

557.90

0.19

1.18

3

a

b is a Langmuir constant relating to the energy of adsorption for an adsorbent

4

b

kf is a Freundlich constant relating to the adsorption capacity

5

c

nf is an empirical parameter relating to the adsorption intensity

6

d

7

e

ks is a median association constant of Sips model

ms is a heterogeneity factor of Sips model

8 9

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Langmuir

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1 2

3 4 5 6 7 8

Figure 1. Synthetic procedure of ordered carbonaceous materials (a). Small-angle X-ray scattering (SAXS) patterns (b), N2 adsorption-desorption isotherms (c), and the corresponding pore size distribution curves (d) of OMC-350, OMC-600, and OMC-900. The isotherms for OMC-600 and OMC-900 are offset vertically by 115 and 175 cm3/g, respectively.

9 10

24


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Page 25 of 29

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Langmuir

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5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Figure 2. SEM (a-c) and TEM (d-f) images of ordered mesoporous carbonaceous materials: (a, d) OMC-350, (b, e) OMC-600, and (c, f) OMC-900.

25


Langmuir

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1 2 3

4 5 6

Figure 3. The 13C solid-state NMR (a) and the Fourier transform infrared spectra (b) of ordered mesoporous polymer (OMC-350) and ordered mesoporous carbon (OMC-900).

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Langmuir

1 2 3

4 5 6 7 8 9

Figure 4. (a) Removal percentage and adsorption amount of hexachlorobenzene (HCB) on the ordered mesoporous carbonaceous materials at different carbonization temperatures of 350, 600, and 900 °C (OMC-350, OMC-600, and OMC-900) and the commercial active carbon. The initial concentration of HCB is 200 µg/L. (b) the image of adsorption mechanism.

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Langmuir

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1 2

3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Figure 5. Adsorption isotherms of hexachlorobenzene (HCB) by using ordered mesoporous carbon material (OMC-900) as adsorbent in Milli-Q water at 25, 35 and 45 °C with experimental data (dots), Langmuir model curves (full line in (a)) and Freundlich model curves (full line in(b)). Hexachlorobenzene (HCB) adsorption isotherms (c) according to Sips model at 25, 35 and 45 °C. The adsorption capacity (d) of HCB versus contact time on OMC-900 with initial concentration of 200 µg/L in deionized water.

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Langmuir

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TOC graphic

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Ordered Mesoporous Carbonaceous Materials with Tunable Surface

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