Synthesis of Patchouli Biochar Cr2O3 Composite Using Double Acid Oxidators for Paracetamol Adsorption

  10 January 2018

Synthesis of Patchouli Biochar Cr O Composite Using Double

  2

  3 Acid Oxidators for Paracetamol Adsorption _{1 1 2 1} Tutik Setianingsih , Masruri , Bambang Ismuyanto ₂ Department of Chemistry, Brawijaya University, Jl. Veteran 169, Malang, Indonesia _*

Department of Chemical Engineering, Brawijaya University, Jl. Veteran 169 Malang, Indonesia

Corresponding email: tutiksetia@ub.ac.id

Received 18 September 2017; Revised 14 December 2017; Accepted 5 January 2018

  

ABSTRACT

  Composite built by patchouli biochar and metal oxide, Cr O , is a potential

  2

  3

  material for remediation of contaminated wasterwater. Oxidation of biochar using acid or salt oxidators can improve its surface polar functional groups. This treatment may be able to increase impregnation of metal cation (as salt) before calcination to form its oxide. In this research, 3 types of oxidators were used to oxidize the biochar before impregnation with purpose to study its influence toward physichochemistry and adsorption performance of the composite. Preparation of the composite included 3 steps, namely preparation of biochar by pyrolisis of patchouli biomass using

  o

  ZnCl activator at 450

  C, oxidation of the biochar using 3 different

  2 o

  oxidators (H SO -HNO , H PO -HNO , H O ) at

  60 C,

  2

  4

  3

  3

  4

  3

  2 2 –HNO

  3

  impregnation of the oxidized biochar using CrCl

  3 followed by calcination o

  process to form biochar

  2 O 3 composite at 600

  C. Characterization using

• –Cr X-ray diffraction indicated that the composite contains the Cr

  2 O 3 structure.

  FTIR spectrophotometry characterization indicates the different content of C=O, C

• –O, and –OH on the composite surface. SEM images shows irregular micro ball shapes. EDX characterization indicates the different Cr content in the composite with same sequence with FTIR absorbance of both C

  2 O

  3

• –O and –OH. Adsorption of paracetamol indicates effect of Cr showing the same sequence of both.

  Key word: composite, biochar, Cr O , patchouli biomass, adsorption, _{2 3} INTRODUCTION

  Biochar is one of porous material adsorbents which has potential for adsorption of metal cations such as Pb, Cd, Ni, and Cu [1], Zn [1, 2], anion such as phosphate [3] or arsenic (V) [2], and organic substances such as humic and tannic acid [4], trimethyltin [2], various antibiotics [5]. Combination of biochar using various metal oxides can improve performance of biochar in adsorption [6,7,8].

  Treatment of biochar by oxidation of its surface using acid oxidators has been also reported by some previous researchers. This oxidation is useful to improve surface functional groups of biochar. For example, oxidation using HNO creates functional groups of ,

  3

  2

• –NO

  The journal homepage www.jpacr.ub.ac.id p-ISSN : 2302 – 4690 | e-ISSN : 2541 – 0733

  10 January 2018

  C=O, and COOH [9]. The other researcher reported that oxidation by HNO improves

  3

  carboxylic [10]. Peroxide acid oxidation created C=O, C

• –O, and OH functional groups of biochar [11]. HNO

  3 , H

  2 SO 4 , H

2 O 2 gives the micropore and mesopore sizes [12].

  Some research also reported double acids as the oxidator of carbon materials, including mixture of HNO

  3

  2 SO 4 which creates functional groups of

• –H
• –NO(OH) [9]. Combination HNO

  3

2 O 2 improved the carboxyl on CNT [13].

• –H However, calcination treatment can reduce acidity of biochar surface. Acidity of activated carbon surface increases almost 60 times after oxidation, but decreases again after

  o

  calcination by increasing of temperature and there is no acidity after calcination at 950 C. Decreasing of activated carbon acidity is caused by decreasing of carboxyl and phenolic content [14].

  Functionalization by oxidation reaction can improve adsorption of biochar toward

  2+ 2+

  metal cations, such as Zn [15] or Cu [10] and anion such as Cr[VI] [16]. It indicates that oxidation of biochar can improve impregnation of biochar by metal salts. In our previous research, biochar product has been prepared from patchouli biomass using CoCl

  2 activator and impregnated with CrCl which then calcined to form biochar O composite [6].

  3

  2

  3

• –Cr In this research, biochar was prepared using ZnCl activator by consideration that

  2

  based on our previous research, ZnCl

  2 gave highest porosity of biochar after CoCl 2 activator

  [6]. The biochar was oxidized using 2 different acids with purpose to study their effect on the compos ite’s surface functional groups and its performance in adsorption of paracetamol, as contaminant model.

  EXPERIMENT Chemicals and instrumentation

  This research used some chemicals, including nitric acid (Merck), sulfuric acid 96% (Merck), peroxide acid (Merck), phosphoric acid (Merck), chromium chloride hexahydrate (Merck), zinc chloride anhydrate (Merck), paracetamol (pharmacy), distilled water.

  Some instrumentations were used in this research for characterization of the products, including FTIR spectrophotometer (Shimadzu FTIR QP89500) by using KBr pellet, X-ray diffractometer (PANalytical type XPert PRO), SEM (FEI type Inspect S50), EDX (EDAX, AMETEK). UV-Vis spectrophotometer (Shimadzu) is used for analysis of paracetamol.

  Procedure reaction Preparation of biochar using ZnCl activator

2 A mixture was prepared by mixing patchouli biomass (60 g), ZnCl

  2 (180 g) and o o

  distilled water (360 mL). The mixture was evaporated at 100

  C, then pyrolized it to 450 C for 0.5 h in a closed porcelain cup. Due to the size of the cup, the ZnCl impregnated biomass was divided into 3 parts. The calcined composite product was washed using HCl solution (1 M)

  o and distilled water to remove the activator. The product was dried at 130 C for 6 hrs.

  Oxidation of biochar surface

  This procedure was conducted using the concentrated acids. The biochar (5 g) was mixed with acid mixture (100 mL) at volume ratio of 1:1, including H

  2 SO

  4 3 , H

  3 PO

  4

• –HNO –

  o

  HNO

  3 , and H

2 O

  2 3 and then heated to 60 C for 0.5 h.

• –HNO

  10 January 2018 Impregnation of the oxidized biochar

  The oxidized biochar was mixed with CrCl solution (0.9 M) and shaked at 175 rpm for

  3 o

  24 hrs. After decantation process, the impregnated biochar then was calcinated to 600 C for 1 h to produce biochar

2 O 3 composite.

• –Cr

  Adsorption test

  The paracetamol solution (100 ppm, 25mL) was mixed with each 0.05 g of the composites and shaked at 175 rpm for 24 h. The mixtures were filtered and the filtrate was analyzed using UV

• –Vis spectrophotometry at maximum wavelength (243 nm). Standart curve of paracetamol was prepared based on measurement of a series of paracetamol solution of 10 –50 ppm.

RESULT AND DISCUSSION

  Characterization of the composites using FTIR spectrophotometry. FTIR spectrophotometry has been used to identify surface functional groups of the composites which may change due to oxidation treatment. FTIR spectra of the composites are reported in Figure 1 to Figure 2. Figure 1 shows different pattern of spectra, especially correspond to

• 1

  ,

• –OH, C=O, aromatic C=C and C–O at 3400, 1720, (1620 and 1560), and 1240 cm respectively. Those peaks are fit with interpretation given in previous researches, i.e. the band
• 1
• 1

  at 1700 cm is related to C=O vibration, 1000 -1300 cm indicates the stretching of C

• –O
• 1

  bond, 3200 is OH stretching band, and 1590 is correspond to oxonium due to

• –3500 cm breakdown of aromatic carbon after oxidation [16].

  Figure 1. FTIR spectra of composites prepared using 3 different oxidator mixture

  (HPHN=H

  3 PO 3 ; HS

2 SO

  4 3 ; HO

  2 O

  2 3 )

• –HNO –HN=H –HNO –HN=H –HNO

  10 January 2018

  Figure 2. FTIR spectra of composites prepared using 3 different double oxidators (HP

  3 PO

  4 3 ; HS

  2 SO

  

4

3 ; HO

  2 O

  2 3 )

• –HN=H –HNO –HN=H –HNO –HN=H –HNO FTIR absorbance was calculated and reported in Figure 3. The absorbance of
• –OH and C PO < H O < H SO . On the

  3

  4

  

3

  2

  2

  3

  2

  4

  3

• –O bands increases in sequence of H –HNO –HNO –HNO other side, the C=O band also increases by using oxidators in sequence of H O <

  2 2 –HNO

  3

• 1

  H

  2 SO

  4 3 < H

  3 PO

  4 3 . The presence of OH (at about 3250 cm ), C=O, and C

• –HNO –HNO
• –O groups indicates that the composites contain carboxyl group. Moro
• –OH functional group can includes hydroxyl or hydrate.

  After impregnation with CrCl and calcination, the bands were reduced which indicate

  3

  that the degradation reaction occured. However, all composite spectra show sharp bands

• 1

  between 500 and 600 cm . These bands are connected correspond to Cr

  2 O 3 as

• –O of Cr interpreted in previous research [17].

  Figure 3. FTIR absorbance of C=O, C

• –O, and O–H functional groups of biochar after oxidation treatment using 3 different double oxidizing agents (HP

  3 PO

  4 3 ;

• –HN=H –HNO HS SO ; HO O )

  2

  4

  3

  2

  2

  3

• –HN=H –HNO –HN=H –HNO

  10 January 2018 Characterization of the composites using X-ray diffraction

  In this research, the active biochar was modified with Cr(III) oxide by adsorption of salt, i.e. CrCl

  3 , in the first step, then was continued by calcination of biochar

  3

• –CrCl composite to form biochar

  2 O 3 composite. Some previous researchs have called this way

• –Cr of modification by term of impregnation [18,19,20].

  X-ray diffraction method was conducted to identify crystal structure of the impregnant (Cr O ) in the composite. The X-ray diffractogram is presented in Figure 4 and the

  2

  3

  interpretation data are listed in Table 1. Figure 4 shows some peaks which indicated that the composite crystalline materials. By comparing the diffractogram data of Cr

  2 O 3 in previous

  researchs [17, 21, 22], the composite indicates that it also contains Cr

  2 O 3 structure. By

  characterization the synthesis Cr

2 O 3 using X-ray diffraction method, another previous research gave more specific term of structure, i.e O [23].

  α–Cr

  2

  3 104 110 116 024

  Figure 4. X-ray diffractogram of biochar O composite which was prepared using

• –Cr

  2

  3 H

2 SO

  4

  3

• –HNO Tabel 1. X-ray diffractogram data of sample and Cr O as comparison

  2

  3 Sample Cr

  2 O 3 [17,21,22]

  d (Å)

  I R (%) hkl 2ϴ d (Ǻ)

  33.67 2.66 100.00 2.66 104

  36.28

  2.47

  91.24 2.47 110

  50.30

  1.82

  37.07 1.81 024

  54.90

  1.67

  86.77 1.67 116

  65.21

  1.43

  30.21 1.43 214

  Characterization of morphology by SEM

  Morphology of the composites were characterized using SEM. The SEM images of all composites in Figure 5 shows micro ball shape. The smallest microball shape was obtained by using H

3 PO

  4 3 . There are some holes among microball particles shown by SEM

• –HNO images. However, both composites synthesized by using H SO and H O

  2

  4

  3

  2

  2

  3

• –HNO –HNO

  10 January 2018

  oxidators show more holes than using H PO . This may be connected to stronger

  3

  

4

  3

• –HNO oxidizing ability of the former than the later.

HS-HN HO-HN HP-HN

  

Figure 5. SEM images of the composites prepared using 3 different double oxidizing agents

  (HP PO ; HS SO ; HO O )

• –HN=H

  3 4 –HNO 3 –HN=H

  

2

4 –HNO 3 –HN=H

  2 2 –HNO

  3 Characterization of composition by EDX

  EDX characterization is reported in Figure 6 and 7. It indicates that content of Cr in the composite is increasing by sequence of HP

• –HN < HO–HN < HS–HN. This sequence is relatively fit with sequence of absorbance of C –O and O–H groups in Figure 3. Those functional groups contain Lewis base oxygen atom, which are rich of lone pairs, hence they have better affinity to Lewis acid Cr(III) CrCl 3 impregnation process.

  On the other side, the content of O on the surface of biochar is increasing by sequence of HS

• –HN < HO–HN < HP–HN. This sequence is relatively fit with the total C=O, C–O, and OH groups in Figure 3.

  10 January 2018 (a) (b) (c)

  

Figure 6. EDX spectra, content table, and SEM images where the content of the composites

  3 PO

  4 3 ; HS

• –HN=H –HNO HN=H
• – prepared using 3 different double oxidizing agents: (HP

2 SO

  4 3 ; HO

  2 O

  2 3 )

• –HNO –HN=H –HNO

  10 January 2018

Figure 7. Content of Cr and O in composites prepared using 3 different double oxidizing

  agents (HP

3 PO

  4 3 ; HS

  2 SO

  4 3 ; HO

  2 O

  2 3 )

• –HN=H –HNO –HN=H –HNO –HN=H –HNO

  Adsorption test

  Adsorption test was performed using paracetamol adsorbate. The adsorption data was presented in Figure 8. The adsorption values show that there is an increasing of adsorption value in sequence of HP

• –HN < HO–HN < HS–HN. This sequence is fit with the sequence of Cr content in Figure 7. It indicates that Lewis acid of Cr(III) in Cr

  2 O 3 influence the

  adsorption. The other side, the order of adsorption is fit with order of both C-O and

• –OH content in Figure 3. Hence, it indicates that –COOH group also gives effect on adsorption.

  Adsorption of carbon material lasts through 3 steps, including mass transfer of adsorbate molecules onto exterior of the carbon, diffusion of molecules into the pores of carbon, and physical adsorption, i.e through the weak interactive forces [24]. This weak interaction can be hydrogen bond or Van der Waals force [25]. Based on its chemical structure, paracetamol molecule has functional groups of C=O, -OH, and

• –NHR [26]. Thus, it can be predicted that those functional groups of paracetamol can make hydrogen bonds with

  2 O 3 structure is also

• –COOH groups of the composite. The Cr(III) cations is in Cr potential to make Van der Waals force (ion – dipole) with them.

  

Figure 8. Adsorption value of paracetamol by composites prepared using 3 different double

  oxidizing agents (HP

3 PO

  4 3 ; HS

  2 SO

  4 3 ; HO

  2 O

  2 3 )

• –HN=H –HNO –HN=H –HNO –HN=H –HNO
• –HNO

• –HNO
• –HNO
• –O and –OH infrared absorbance in the same sequence of the oxidizing agents.

  [4] Jung, C., Phal, N., Oh, J., Chub, KH., Jang, M., Yoon, Y., J Hazard Mater, 2015, 300, 808

  REFERENCES

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  Ball-Milling, Juan Mauricio Venegas, 2014

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  by Palm Oil Mill Sludge Biochar Prepared by Microwave, Faculty of Engineering

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  ACKNOWLEDGMENT

  [6] Setianingsih, T., Ismuyanto, B., Masruri, Int J Chemtech Res., 2016, l9(12), 610-621. [7] Moosavi, E., Dastgheib, S., and Karimzadeh, R., Energies., 2012, 5, 4233-4250 [8] Han, Z., Sani, B., Mrozik, W., Obst, M. Beckingham, B., Karapanagioti, HK.,

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  40 [10] Kulkarni, S., JCCS, 2015, 5(8), 443-447 [11] Olivier, C.F., An investigation into the degradation of biochar and its interactions

  with plants and soil microbial community, Faculty of AgriSciences, Stellenbosch

  University, 2011 [12] Yakout, S.M., Daifullah, A.H.M., el-reefy, S.A., EEMJ, 2015, 14( 2), 473-480 [13] Ahmed, DS., Haider, AJ., Mohammad, MR., Energy Procedia, 2013, 36, 1111

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  We thank DIKTI for research funding and acknowledge Brawijaya University for supports for this research.

  content is also fit with the sequence of both C

  2010, 11, 927-942.

  3 < H

  10 January 2018 CONCLUSION

  Synthesis and application of composite based on patchouli biomass has been conducted. Based on characterization of the composites it can be concluded that type of oxidizing agents affects the content of Cr

  2 O 3 in the composite, surface functional groups of

  biochar before impregnation, and paracetamol adsorption. Sequence of adsorption value is in line with sequence of Cr

  2 O 3 content in the composite, i.e H

  3 PO

  4

  2 O

  3

  2

  3 <

  H

  2 SO

  4

  3

  . Sequence of Cr

  2 O

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• –94 [15] Atieh, M.A., IJESD, 2011, 2(2), 1-4 [16] Lawrinenko, M., Anion exchange capacity of biochar, Iowa State University, 2014 [17] Farzaneh, F. and Najafi, M., J. Sci. I. R. Iran, 2011, 22(4), 329-333 [18] Abbas, A., Abussaud, B.A., Ihsanullah, Al-Baghli, N.A.H., Khraisheh, M., and Atieh, M.A., J Nanomater., 2016, 2016, 1-10.

  10 January 2018

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  [24] Wu, J., 2004, Modeling Adsorption of Organic Compounds on Activated Carbon A multivariate approach, Université de Neuchâtel, Neuchâtel, Schweiz, 2004. [25] Oscik, J., Cooper, I.L (editor), Adsorption, 1982, John Wiley & Sons Inc., Queensland. [26]

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