Bioresource Technology 102 (2011) 19471950

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

High surface area porous carbons prepared from hydrochars by phosphoric acid activation
Lili Wang, Yupeng Guo, Bo Zou, Chunguang Rong, Xiaoyu Ma, Yuning Qu, Ying Li, Zichen Wang
College of Chemistry, Jilin University, No. 2699, Qianjin Street, Changchun 130012, China

a r t i c l e

i n f o

a b s t r a c t
In the present work, a new route for preparation of high-performance porous carbons under mild conditions was reported. The high surface area (2700 m2/g) and large pore volume (1.98 cm3/g) porous carbons were prepared from hydrochars by conventional phosphoric acid activation method. The hydrochars described here can be obtained from sulfuric acid hydrolysis of rice husk via dehydration, polymerization and carbonization. A specic capacitance of 130 F g1 was achieved by using the porous carbon, indicating that the porous carbon prepared by this route has good electrochemical performance. Furthermore, the localized graphitic nature of the porous carbon was proved by X-ray diffraction pattern. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 15 July 2010 Received in revised form 25 August 2010 Accepted 26 August 2010 Available online 31 August 2010 Keywords: Rice husk Hydrochars Phosphoric acid Porous carbon

1. Introduction Activated carbons, with their high porosity and large adsorption capacity, have been extensively used in various elds, such as industrial purication, chemical recovery operations, catalyst supports and electrode materials for batteries and electrochemical capacitors (Guo and Rockstraw, 2006). Wood, coal, petroleum have been used as carbon precursors (Amaya et al., 2007; Karagoz et al., 2008; Mussatto et al., 2010). As is well-known, fossil fuels are nite, and lignocellulosic agricultural wastes are investigated as precursors vastly due to their renewability and huge amount. For example, the annual output of rice husk (RH) worldwide and China is about 80 and 40 million tons respectively (Zhang et al., 2010). Chemical activation is a well-known method to obtain high-performance porous carbons. The most commonly used chemical activation agents are KOH, NaOH, H3PO4 and ZnCl2 (Kubota et al., 2009; Demiral and Gunduzoglu, 2010; Martin-Gullon et al., 2004). Alkali hydroxides are usually used to prepare high surface area and large pore volume porous carbons. In our previous studies (Guo et al., 2003, 2002), good performance porous carbons (3300 m2/g, 1.88 cm3/g) were prepared from RH by alkali hydroxide activation, but it was not economical and the activation agents could not be recovered easily in industry (Guo et al., 2002). From both economic and environmental perspectives, phosphoric acid is the preferred activation agent because the activation conditions are milder compared to alkali hydroxide, and it could be recovered in industry

(Guastalli et al., 2009). However, the surface area of porous carbons prepared from coal, wood and lignocellulosic materials by phosphoric acid activation is not large enough (<2000 m2/g). In this sense, there is great interest in using new precursors to prepare high-performance porous carbons by phosphoric acid activation. In this work, a carbon-rich solid product denoted as hydrochars was selected as a new carbon precursor, which was prepared from sulfuric acid hydrolysis solution of RH via dehydration and carbonization. Sulfuric acid is the suitable reagent for the high yield extraction of sugars from cellulosic based biomass, and it also performs well in carbonization of sugars (Harmer et al., 2009). The formation of the hydrochars containing large quantities of oxygen functional groups through the hydrothermal carbonization of sugars is the consequence of dehydration, polymerization and aromatization reactions (Wang et al., 2001). Combined with the characteristics of phosphoric acid activation, it is possible to prepare high surface area porous carbon using hydrochars as precursor. Thus, the main objective of this work was to study the preparation of high-performed porous carbons from hydrochars by H3PO4 activation, and investigate the effects of activation conditions. Moreover, the electronic property of the product was also tested.

2. Methods 2.1. Materials

Corresponding author. Tel./fax: +86 431 85155358.

E-mail address: wangzc@jlu.edu.cn (Z. Wang). 0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2010.08.100

Rice husk was obtained from a rice mill nearby Changchun city. RH was washed thoroughly with distilled water and then dried at

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L. Wang et al. / Bioresource Technology 102 (2011) 19471950

110 C overnight, and porphyrized to 60 mesh before employment. The elemental analysis of RH was 37.05 wt.% C, 8.80 wt.% H, 11.06 wt.% N and 40.44 wt.% O. The main constituent of RH was 18.2 wt.% hemicellulose, 35.2 wt.% cellulose, 24.5 wt.% lignin and 18.8 wt.% silicon dioxide, which was almost consistent with our previous work (Zhang et al., 2010). 2.2. Reagents Sulfuric acid and phosphoric acid used in the synthetic procedures of this work were purchased from Beijing Chemicals Co. Ltd., which was of analytical grade. Distilled water was applied for all synthesis and treatment processes. 2.3. Preparation of hydrochars In this work, RH was hydrolyzed with 72% (wt.%) sulfuric acid, the ratio of RH mass (g) to 72% H2SO4 solution volume (ml) was 1:10. Water was then added to the hydrolysis solution to produce the solution with different acid concentrations of 42%, 52%, 62% and 72%, respectively. After ltrating process, the ltrate was carbonized at 95 C for 6 h to prepare hydrochars. The solid products were collected and washed to neutral with distilled water and then dried at 120 C overnight to prepare porous carbon. Sulfuric acid used for hydrolysis could be condensed for recycle. These processes were consistent with our previous work (Wang et al., 2010). 2.4. Preparation of porous carbon The hydrochars prepared under different sulfuric acid concentrations were impregnated with 85% phosphoric acid. The impregnation ratio (the weight ratio of hydrochars to phosphoric acid) was varied from 1:1 to 1:6. Then the samples were heated up to the activation temperature (300700 C) for 0.5 h to 2 h under N2 atmosphere. Finally, the product was washed to neutral and dried in an oven at 120 C overnight to obtain the nal product. 2.5. Analysis Characterization of porous carbons was carried out by nitrogen adsorptiondesorption isotherms measured at 77 K using an ASAP 2010 Micromeritics instrument. Prior to gas adsorption measurement, the carbon was degassed at 300 C under vacuum for 3 h. The BET surface area was calculated from N2 adsorption isotherms by using the BrunauerEmmettTeller (BET) equation. The total pore volumes were estimated at a relative pressure of 0.995. The structure and the composition of samples were analyzed by X-ray powder diffraction (XRD) (SHIMADZU XRD-6000 diffractometer employing Ni-ltered Cu Ka radiation, at a scanning rate of 6/ min with 2h ranging from 5 to 60). The elemental analysis of the hydrochars was carried out on PerkinElmer 2400 C, H, N, O analyzer. The electrochemical tests were performed using a Parstat 2273 electrochemical workstation. 3. Results and discussion 3.1. Effects of activation conditions on porous carbons Factors, such as the impregnation ratio, activation temperature, activation time and sulfuric acid concentration could affect the characteristic of porous carbons. Therefore, those factors were investigated, respectively. All the experimental data were repeated for three times and the relative standard deviation was less than 5%.

3.1.1. Effects of different hydrochars on porous carbon The elemental analysis of hydrochars prepared under different H2SO4 concentrations is displayed in Table 1. Meanwhile, the specic surface area (SBET) and pore volume (VTotal) of the porous carbons prepared from different hydrochars at 500 C for 1 h with the impregnation ratio of 1:4 were investigated. From the results of elemental analysis, we could see that the content of elements was almost same for different hydrochars, but the specic surface area and pore volume of the porous carbons prepared from different hydrochars were obviously different. The results indicated that the specic surface area and the pore volume of porous carbon decreased with the increase of sulfuric acid concentration and reached the maximum value (2530 m2/g, 1.98 cm3/g) when the hydrochars prepared under 42% acid concentration. The reason was with the increase of acid concentration, the growth rate of hydrochars might be much accelerated, resulting in the aggregation of tiny carbon nanoparticles, so phosphoric acid cannot penetrate into the interior of the particles. Therefore, the specic surface area and pore volume of porous carbon were not large enough. 3.1.2. Effects of impregnation ration on porous carbon The BET surface areas and pore volumes of the samples (hydrochars prepared under 42% H2SO4) prepared at 500 C for 1 h with different impregnation ratios are displayed in Fig. 1a. The results indicated that BET surface area of porous carbons reached a maximum value of 2700 m2/g at impregnation ratio of 1:2.5. Whereas, the pore volume reached the maximum value when the impregnation ratio of hydrochars to phosphoric acid was 1:4, this is because with the increase of impregnation ratio, the ratio of mesoporous was increased, resulting in the large pore volume and decreased surface area, which would be further proved by N2 adsorption isotherms. 3.1.3. Effects of activation temperature and time on porous carbon The specic surface areas and pore volumes of the samples (hydrochars prepared under 42% H2SO4) prepared at different activation temperature for 1 h with impregnation ratios of 1:2.5 are displayed in Fig. 1b. The results indicated that BET surface area of porous carbons reached a maximum value of 2700 m2/g at 500 C. Whereas, the pore volume reached the maximum value when the activation temperature between 500 and 600 C. The similar effect of activation time on porous prepared at 500 C with impregnation ratios of 1:2.5 carbon is shown in Fig. 1c. The results indicated that the optimal activation time was 1 h. With the increase of the activation temperature and time, the surface area and pore volume decreased, this was because the excessive temperature and time leaded to the collapse of pores, so the surface area and pore volume became smaller. 3.2. N2 adsorption isotherms of porous carbons Fig. 2 shows the N2 adsorption isotherms of the porous carbons prepared under different impregnation ratios at 500 C for 1 h. According to the BDDT (BrunauerDemingDemingTeller) classication (Ania et al., 2009; Kubota et al., 2009), the isotherms in this

Table 1 The elemental analysis of hydrochars prepared under different H2SO4 concentrations: (a)-42%, (b)-52%, (c)-62% and (d)-72%. Hydrochars (a) (b) (c) (d) C (%) 64.12 63.56 64.25 61.81 H (%) 4.453 4.524 4.422 4.234 N (%) 0.376 0.453 0.316 0.340 O (%) 31.05 31.46 31.01 33.61

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2800 2.5

1949

a
2600

1400
Amount of adsorbed N2 (cm /g)

Adsorption Desorption

1200 1000 800 600 400 200 0

1:1.5 1:2 1:4 1:6

BET surface area (m /g)

2.0

2400 1.5 2200 1.0 2000

SBET VTotal
1 2 3 4 5 6

0.5

Pore volume (cm /g)

0.0

0.2

0.4

0.6

Relative pressure, P/P

0.8

1.0

Impregnation ratio , g/g

3000 2.5

Fig. 2. N2 adsorption isotherms of porous carbons prepared under different impregnation ratios.

b
2500

SBET VTotal
2.0

BET surface area (m /g)

2000

1.5

(activation temperature and time were 500 C and 1 h, impregnation ration of 1:4) obviously shown that the porous carbon has well-developed pore structure, which enable the porous carbon to have large surface area and pore volume. 3.3. XRD of hydrochaars and porous carbon For the hydrochars prepared under 42% acid concentrations and the different porous carbons (activation temperature and time were 500 C and 1 h, different impregnation rations), X-ray diffraction patterns (Fig. 3ae) show two peaks at about 20 and 44. The pattern shows a broad diffraction peak in a 2h range of 1030. Our wide-angle XRD pattern matches well with that previously reported (Wang et al., 2009; Ruland and Smarsly, 2002) for non-graphitic carbon. While localized graphitization is manifested by the diffraction peak at 44, which assigned to the plane (1 0 0). It was impossible to completely graphitize in such low-temperature system, so the macroscopy of the samples show amorphous structure. 3.4. Electrochemical tests As for the electronic property of the porous carbon, we have detected the specic capacitance (C) of the products (The porous carbon prepared under different impregnation ratios when the activation temperature, time and sulfuric acid concentration were 500 C, 1 h and 42%, respectively) based on the method shown in

Pore volume (cm /g)

1500

1.0

1000

0.5

500 300 400 500 600

o

0.0 700

Temperature ( C)

2700

SBET VTotal

2.0

2600

BET surface area (m /g)

Pore volume (cm /g)

2500 1.5 2400

2300

1.0

2200

2100 0.5 1.0 1.5 2.0

0.5

Time (h)
6000

Fig. 1. Effect of (a) impregnation ratio, (b) activation temperature and (c) activation time on the specic surface area (SBET) and pore volume (VTotal) of the porous carbons.

5000

work were classied into type I (1:1.5 and 1:2) and type IIV (1:4 and 1:6). For the samples with impregnation of 1:1.5 and 1:2, the amount of adsorbed N2 was found to increase rapidly even at relative pressures lower than 0.1, indicating that all porous carbons had well-developed micropores. Further, in the cases of impregnation of 1:4 and 1:6, amount of adsorbed N2 was found to increase even at relative pressures higher than 0.1 and had hysteresis loop at a relative pressure of around 0.5. Therefore, in these porous carbons, the mesoporous were considered to be developed. The amounts of adsorbed N2 were different, indicating that the adsorption property could be tuned by changing the impregnation ratios of phosphoric acid. HRTEM image of the porous carbon prepared

Intensity (a.u.)

4000

3000

2000

e d c b a
10 20 30 40 50

1000

2Theta (deg)
Fig. 3. XRD of hydrochars and porous carbons prepared under different impregnation ratio: (a)-hydrochars, (b)-1:1.5, (c)-1:2, (d)-1:4 and (e)-1:6.

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Table 2 The properties of the porous carbons prepared under different impregnation ratios and the porous carbons reported previously. Sample 1:6 1:4 1:2 1:1.5 CC Z4 SBET (m2/g) 2263 2530 2610 2342 1180 2360 VTotal (cm3/g) 1.94 1.98 1.52 1.22 0.432 1.636 C (F g1) 124 130 89 71 92 96

Acknowledgements This work was supported by Key Project of the National Eleventh Five-Year Research Program of China (2008BAE66B00) and Scientic and Technological Planning Poject of Jilin Province (20075009). References
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reference (Yuan et al., 2005). Furthermore, the comparison on the properties between the porous carbons obtained in this work and reported in previous literature (Ania et al., 2009) is shown in Table 2. CC represents a commercially available activated carbon cloth, and Z4 represents the porous carbon prepared from furfuryl alcohol via various processes as previous literature reported. Table 2 shows the specic capacitance increased with the impregnation ratio increasing, and a specic capacitance of 130 F g1 is achieved, indicating that the porous carbon has good electrochemical performance. The porous carbon may also be a promising material for catalyst, separation and adsorption in chemical and medical industries. Furthermore, as a new kind of carbon precursor, hydrochars can be prepared from sugars such as sucrose, xylose and glucose or the waste solution containing sugars derived from pharmaceutical factory and food factory. The precursors obtained from hydrolysis solution contain large quantities of organic functional groups and pores (Wang et al., 2001; Sevilla and Fuertes, 2009), which allows phosphoric acid to penetrate rapidly into the interior of the particles. Phosphoric acid appears to function both as an acid catalyst to promote bond cleavage reactions and the formation of crosslinks through processes such as cyclization, condensation, and to combine with organic species to form phosphate and polyphosphate bridges that connect and crosslink biopolymer fragments. After removal of the acid, leaves the matrix in an expanded state with an accessible pore structure (Jagtoyen and Derbyshire, 1998).

4. Conclusion This work has shown that the hydrochars could be used as an excellent precursor for preparation of porous carbon with high surface area and pore volume. The pore volume and surface area of the as-prepared porous carbons can be tuned by simply changing the activation conditions. The porous carbon had good electrochemical performance, and the localized graphitic nature of the porous carbon was proved by X-ray diffraction pattern.