Eggshell

Available online at www.sciencedirect.com

ScienceDirect Materials Today: Proceedings 19 (2019) 1340–1345

www.materialstoday.com/proceedings

ICCSE 2018

Excellent Performance Integrated Both Adsorption and Photocatalytic Reaction Toward Degradation of Congo Red by CuO/Eggshell Nurul Fahmi Khairol, Norzahir Sapawe*, Mohamed Danish Universiti Kuala Lumpur Branch Campus Malaysian Institute of Chemical and Bioengineering Technology (UniKL MICET), Lot 1988 Vendor City, Taboh Naning, 78000 Alor Gajah, Melaka, Malaysia

Abstract Performance in photocatalytic activity of copper oxide supported eggshell (1wt% CuO/ES) catalyst was tested by Congo red decolorization. A simple electrochemical was used in catalysts synthesis. Briefly, the decolorization of Congo red through adsorption under 1 h dark condition 37%, 15%, and 13% respectively for 1wt% CuO/ES, CuO, and ES. After 4 h illuminated under visible, 1wt% CuO/ES, CuO, and ES decolorize 80%, 82%, and 37% of Congo red respectively referring to photocatalytic activity. The functional group and correlation of copper semiconductor with support material eggshell were analyse using Fourier transform infrared spectroscopy (FTIR). © 2019 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and Engineering: Advance and New Materials, ICCSE 2018. Keywords: CuO/ES; Electrochemical; Photocatalytic; Decolorization; Congo Red

1. Introduction Natural dyes are abundant in natural resources such animals, insects, bacteria, fungi, minerals, and various parts of plants including roots, bark, leaves, flowers, and fruit [1]. The industries of textile, paper, cosmetic, food, pharmaceutical and leather are synonym with utilization of dyes in production process [2]. Nowadays, the synthetic dyes totally dominated in market due extensive and variety of these dyes as well easy to produce with good fastness * Corresponding author. Tel.: +6013-5757795 E-mail address: [email protected] 2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and Engineering: Advance and New Materials, ICCSE 2018.

N.F. Khairol et al. / Materials Today: Proceedings 19 (2019) 1340–1345

1341

feature [3]. In cons, synthetic dyes become main contribution for environmental pollution besides excessive use has led serious health hazards and disturbances in eco-balance of nature [4-6]. Recently, the advance oxidation process has attracted researches in treatment of organic pollutant especially dyes. Photocatalytic reactions occur when the semiconductor particle absorbs a photon of light that more energetic compared to bandgap of the semiconductor [7]. Then, electron from the valence bond is promoted to the conduction band leaving a hole behind produce a hole–electron pair and lead to the oxidation and reduction processes of adsorbed substrates [8]. In aqueous solution, the adsorbed water or hydroxide ions oxidize by holes at the valence band while molecular oxygen reduces by electron in the conduction band on the semiconductor superoxide anion forming hydroxyl radical and superoxide radical respectively [9]. The organic pollutant like dyes attack by hydroxyl radicals have strong oxidizing power and decompose as carbon dioxide and water [10-18]. Not only a narrow band gap (1.2eV), copper oxide (CuO) has features which ease of fabrication with high chemical, thermal stability and adjustable electronic properties [19]. In addition, CuO become significant semiconductor which widely utilized in other technology such as gas sensors, solar cells, high-TC superconductors, heterogeneous catalysis, lithium-ion electrode materials, and field emissions [20]. Thus, CuO can be potential catalyst for photodegradation of organic compound. Previous study reported the uses of support material for examples HY zeolite [21], clinoptilolite zeolite [22,23], graphene oxide [24], palygorskite [25], and X zeolite [26,27] enhanced the photocatalytic activity of CuO. The porous nature of eggshell draw interest to apply as support material. Each eggshell was determined consist of approximately between 7000 to 17000 pores [28]. Moreover, the major compound eggshell is 94% of calcium carbonate and the rest are magnesium carbonate (1%), calcium phosphate (1%) and organic matter (4%) [29]. The aim of this study to evaluate the performance copper oxide supported eggshell (CuO/ES) catalyst for photocatalytic degradation of Congo red (CR). The catalyst synthesized via a simple electrochemical method and undergo characterization. This research may contribute in wastewater treatment technology as well provide new knowledge such as the correlation between semiconductor and support material. 2. Experimental Procedures 2.1. Materials and method The chicken eggshell (ES) were collected from the nearest farm, stall, and restaurant as solid waste at Melaka. The chemicals that will be used are N,N-dimethylformamide (DMF), naphthalene, and tetraethylammonium bromide solution was purchased from Merck, Fluka, and QReCTM respectively. Zinc (Zn) and copper (Cu) plate cell were acquired from Nilaco Metal, Japan (>99.9% purity). All the reagents were in analytical grade and were used as received. The pH solution by adjustment using 0.1 M HCl and NaOH solution were prepared by using deionised water. 2.2. Catalyst preparation The collected eggshell (ES) were washed with water to remove any impurities adhering to the surface before was oven-dried at 80 °C for 24 h. After that, the ES were crush into pieces. The powder of CES was form after the pieces have been blended and sieved to a consistent size of 355–600 μm. Lastly, the resultant ES powder was kept into the plastic bottle. In a normal one-compartment cell, it is consists of a Pt plate (2 × 2 cm2) as cathode while a Cu plate (2 × 2 cm2) as anode where a dimethyl formamide (DMF) solution containing 0.1 M tetraethylammonium perchlorate (TEAP) has been electrolyzed in the presence of mediator which is naphthalene (6 mmol) and was carried out using 480 mA/cm2 of constant current density under open atmosphere at 273 K [21,30-35]. The resultant mixture from the electrolysis formed a white powder of CuO after it was undergoing impregnated, dried in an oven overnight at 378 K as well as calcined at 823 K within 3 h. Finally, the catalyst is ready to be subjected for characterization and photocatalytic testing.

1342

N.F. Khairol et al. / Materials Today: Proceedings 19 (2019) 1340–1345

The 1wt% CuO/ES was generated by adding ES (15 g) to the electrolysis previously and then, followed the similar procedure which give a grey powder catalyst as final product. Based on the Faraday’s Law of electrolysis, the weight percent and the time that are necessary for CuO deposited onto ES to be accomplished through electrolysis were calculated [21,30-35]. The electrolysis was run to synthesize 1 wt% CuO precursor of CuO/ES with duration 959 s approximately. 𝑡=

𝑧×𝑛

(1)

where t = total time for the constant current applied (s); F = 96,486 C mol−1, which is the Faraday constant; I = the electric current applied; z = the valency number of ions of substances (electrons transferred per ion); and n = the number of moles of Zn (no of moles, liberated n = m/M). 2.3. Characterization The functional groups of catalysts were identified using a Perkin Elmer Spectrum RX 1 Fourier-transform infrared (FT-IR) Spectrometer using the KBr method with a scan range of 400–4000 cm−1. 2.4. Photocatalytic testing The photocatalytic activity of the prepared catalyst was tested for the decolorization of Congo red (CR) solution. An amount of 1 g L-1 catalyst was dispersed in 100 mL of 10 mg L-1 CR aqueous solution. The adsorptiondesorption equilibrium was achieved under dark conditions after 1 hr, and the mixture was irradiated by visible light from fluorescent lamp at room temperature for 4 h with constant stirring with a cooler. The distance between the light and the reaction vessel about 15 cm. At the specific time intervals, 2.5 mL of the sample solution was withdrawn and centrifuged prior measurement of the CR concentration by a UV-vis spectrophotometer (Lambda EZ 210) using the characteristic adsorption band of the CR which is 498 nm. The CR decolorization percentage was calculated as follow, 𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝐶𝑅 𝑑𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛 % =

× 100

(2)

where C0 represents the initial concentration (mg L-1) and Ct denotes a variable concentration (mg L-1). 3. Results and Discussion 3.1. Characterization 3.1.1. Vibrational spectroscopy The functional group contain within catalysts was determined through FT-IR spectroscopy, as shown in Figure 1. Overall, the wide band at 3427 cm-1 indicate to the moisture of water molecules absorbed on the surface of catalysts. In addition, the vibration distortion of O-H group on CuO catalyst also evaluated as peak emerged at 1547 cm-1. The Cu-O vibration exhibited by weak band at 529 cm-1 for CuO catalyst but this band did not appear for 1wt% CuO/ES may due to very small amount Cu-O species. Peaks was produced at 2516 cm-1 for ES and 1wt% CuO/ES catalysts point to the hydride vibration [36]. Further, carbonate minerals within eggshell matrix was display by strong peak at around 1420 cm-1 [37,38] while two peaks resulted at 876 cm-1 and 712 cm-1 correspond to the inplane deformation and out-plane deformation modes of calcium carbonate respectively [37-39]. The interaction between semiconductor and support presented by 2516 cm-1, 1420 cm-1, 876 cm-1 and 712 cm-1 where the strength of these peaks decrease CuO was introduced to the ES.

1343

Intensity (a.u.)

N.F. Khairol et al. / Materials Today: Proceedings 19 (2019) 1340–1345

CuO ES 1 wt% CuO/ES

4000

3400

2800 2200 1600 Wavenumber (cm-1)

1000

400

Fig. 1 FT-IR spectra of catalysts 3.2. Photocatalytic testing The photocatalytic activity of copper oxide supported eggshell (1wt% CuO/ES) catalyts was evaluated on decolorization of Congo red (CR) and compared with the bared CuO and ES catalysts; and results are shown in Figure 2. The experiment was conducted under dark condition within 1 hr before exposed to the visible light and adsorption-desorption equilibrium was achieved. The adsorption and photocatalytic activity by ES which are 13% and 38% respectively does not give significant impact toward decolorization of CR. The 1wt% CuO/ES catalyst give 80 % CR decolorization after 4 hrs irradiated under visible that close to bared CuO catalyst with 82% CR decolorization. Even with small amount of semiconductor used, the photocatalytic activity of 1wt% CuO/ES catalyst reach same level as bared CuO where fully depend on semiconductor. Not only reduce the amount of semiconductor required, the present of support material ES improve the photocatalytic activity due to the structural features and correlation with materials [34]. The effective decolorization may cause by proper distribution of the CuO nanoparticles on the surface of the ES which increase surface exposure toward light [34].

1344

N.F. Khairol et al. / Materials Today: Proceedings 19 (2019) 1340–1345

Decolorization percentage (%)

100

Photocatalytic

Dark

80

60

40

1wt% CuO/ES

20

CuO ES

0 -60

0

60 120 Time (min)

180

240

Fig. 2 Catalysts performance for CR [pH =5, C0 = 10 mg L-1, W = 1 g L-1] 4. Conclusion To be conclude, present eggshell (ES) with mesoporous structure as support for catalyst enhanced the photocatalytic activity also minimize copper (Cu) semiconductor usage. A simple electrochemical method generates nanosized of Cu and distribute Cu properly onto the ES contribute in copper oxide supported eggshell (1wt% CuO/ES) catalyst performance. The interception of Cu species in eggshell structure was identify parallel with decreasing of peak intensity of hydride, carbonate minerals, and calcium carbonate vibration. Acknowledgements The authors are grateful for the financial support by the Short Term Research Grant (STRG) from Universiti Kuala Lumpur (Grant No. 17004 & 17029) and Majlis Amanah Rakyat (MARA) Malaysia, the awards of Pinjaman Pengajian Tinggi Perak (Nurul Fahmi Khairol), and also the Universiti Kuala Lumpur Branch Campus Malaysian Institute of Chemical and Bioengineering Technology for their support. References [1] [2] [3] [4] [5] [6] [7] [8]

Mongkholrattanasit R, Saiwan C, Rungruangkitkrai N, Punrattanasin N, Sriharuksa K, Klaichoi C, Nakpathom M. Eco-dyeing of silk fabric with Garcinia Dulcis (Roxb.) Kurz bark as a source of natural dye by using the padding technique. J Nat Fibers 2016; 13: 65–76. Sanjeeda I, Taiyaba AN. Natural dyes: their sources and eco-friendly use as textile materials. J Environ Rese & Dev 2014;8 :683‒688. Patil PD, Rao CR, Wasif AI, Anekar SV, Nagla JR. Cashew-nut husk natural dye extraction using Taguchi optimization: green chemistry approach. J Sci Ind Res 2015; 74: 512–517. Khan AA, Iqbal N, Adeel S, Azeem M, Batool F, Bhatti IA. Extraction of natural dye from red calico leaves: gamma ray assisted improvements in colour strength and fastness properties. Dyes Pigments 2014; 103: 50-54. Ehishan NS, Sapawe N. Performance studies removal of chromium (Cr6+) and lead (Pb2+) by oil palm frond (OPF) adsorbent in aqueous solution. Mater Today: Proc 2018; 5(10): 21897-21904. Fazry AHZ, Sapawe N, Aziz AIFA, Zainudin MZH, Hafiz MHH, Idris MAF, Hanafi MF, Fozi MFM. Microwave induced HNO2 and H3PO4 activation of oil palm frond (OPF) for removal of malachite green. Mater Today: Proc 2018; 5(10): 22143-22147 Gouvêa CAK, Wypych F, Moraes SG, Durán N, Nagata N, Peralta-Zamora P. Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution. Chemosphere 2000; 40: 433-440. Sauer T, Neto GC, José HJ, Moreira RFPM. Kinetics of photocatalytic degradation of reactive dyes in a TiO2 slurry reactor. J Photoch Photobio A 2002; 149: 147–154.

N.F. Khairol et al. / Materials Today: Proceedings 19 (2019) 1340–1345 [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]

1345

Behnajady MA, Modirshahla N, Hamzavi R. Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst. J Hazard Mater 2006; 133: 226–232. Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972; 238: 37–38. Sapawe N, Hanafi MF. Facile one-pot electrosynthesis of high photoreactive hexacoordinated Si with Zr and Zn catalyst. RSC Adv 2015; 5: 75141-75144. Sapawe N. Effective solar-based iron oxide supported HY zeolite catalyst for the decolorization of organic and simulated dyes. N J Chem 2015; 39: 6377-6387. Sapawe N. Hybridization of zirconia, zinc and iron supported on HY zeolite as a solar-based catalyst for the rapid decolorization of various dyes. N J Chem 2015; 39: 4526-4533. Zamri MSFA, Sapawe N. Performance studies of electrobiosynthesis of titanium dioxide nanoparticles (TiO2) for phenol degradation. Mater Today: Proc 2018; 5(10): 21797-21801. Khairol NF, Sapawe N. Electrosynthesis of ZnO nanoparticles deposited onto egg shell for degradation of Congo red. Mater Today: Proc 2018; 5(10): 21936-21939. Hanafi MF, Sapawe N. Remarkable degradation of methyl orange by tetragonal zirconia catalyst. Mater Today: Proc 2018; 5(10): 2184921852. Hanafi MF, Sapawe N, Rahim MZA, Rahman NN, Rahman AHA, Ahmad AA. Performance of EGZrO2-EGFe2O3/HY as photocatalyst and its efficacy in decolorization of dye-contaminants. Mal J Anal Sci 2016; 20(5): 1052-1058. Sapawe N, Jalil AA, Triwahyono S. Photodecolorization of methylene blue over EGZrO2/EGZnO/EGFe2O3/HY photocatalyst: Effect of radical scavenger. Mal J Fund Appl Sci 2013; 9: 67-73. Rao MP, Wu JJ, Asiri AM, Anandan S, Photocatalytic degradation of tartrazine dye using CuO straw-sheaf-like nanostructures, Water Sci Technol 2017; 75: 1421-1430. Mageshwari K, Sathyamoorthy R, Park J. Photocatalytic activity of hierarchical CuO microspheres synthesized by facile reflux condensation method. Powder Technol 2015; 275: 150-156. Jalil AA, Satar MAH, Triwahyono S, Setiabudi HD, Kamarudin NHN, Jaafar NF, Sapawe N, Ahamad R. Tailoring the current density to enhance photocatalytic activity of CuO/HY for decolorization of malachite green. J Electroanal Chem 2013; 701:50–58. Nezamzadeh-Ejhieh A, Amiri M. CuO supported clinoptilolite towards solar photocatalytic degradation of p-aminophenol. Powder Technol 2013; 235: 279–288. Nezamzadeh-Ejhieh A, Zabihi-Mobarakeh H. Heterogeneous photodecolorization of mixture of methylene blue and bromophenol blue using CuO-nano-clinoptilolite. J Ind Eng Chem 2014; 20: 1421–1431. Choi J, Oh H, Han S-W, Ahn S, Noh J, Park JB. Preparation and characterization of graphene oxide supported Cu, Cu2O, and CuO nanocomposites and their high photocatalytic activity for organic dye molecule, Curr Appl Phys 2017; 17: 137–145. Huo CL, Yang HM. Preparation and enhanced photocatalytic activity of Pd–CuO/palygorskite nanocomposites. Appl Clay Sci 2013; 74: 87–94. Nezamzadeh-Ejhieh A, Salimi Z. Solar photocatalytic degradation of o-phenylenediamine by heterogeneous CuO/X zeolite catalyst. Desalination 2011; 280: 281–287. Nezamzadeh-Ejhieh A, Karimi-Shamsabadi M. Comparison of photocatalytic efficiency of supported CuO onto micro and nano particles of zeolite X in photodecolorization of methylene blue and methyl orange aqueous mixture. Appl Catal A 2014; 477: 83–92. Mittal A, Teotia M, Soni RK, Mittal J, Applications of egg shell and egg shell membrane as adsorbents: A review. J Mol Liq 2016; 223: 376–387. Ngadi N, Wan NSWJ. Removal of etyhl orange dye using waste eggshell. Jurnal Teknologi: Sciences & Engineering 2013; 64:101-107. Sapawe N, Jalil AA, Triwahyono S, Sah RARN, Jusoh NWC, Hairom NHH, Efendi. Electrochemical strategy for grown ZnO nanoparticles deposited onto HY zeolite with enhanced photodecolorization of methylene blue: Effect of the formation of Si–O–Zn bonds. Appl Catal A: Gen 2013; 456: 144–158. Sapawe N, Jalil AA, Triwahyono S. One-pot electro-synthesis of ZrO2–ZnO/HY nanocomposite for photocatalytic decolorization of various dye-contaminants. Chem Eng J 2013; 225: 254–265. Sapawe N, Jaafar NF, Hairom NHH, Satar MAH, Ariffin MN, Triwahyono S, Jalil AA. A facile preparation of nanosized ZnO and its use in photocatalytic decolorization of methyl orange. Mal J Fund Appl Sci 2011; 7: 19-23. Sapawe N, Jalil1 AA, Triwahyono S. Photodecomposition of methylene blue over EGZrO2/HY in aqueous alkaline solution. Mal J Fund Appl Sci 2011; 7: 137-139. Sapawe N, Jalil AA, Triwahyono S, Adam SH, Jaafar NF, Satar MAH. Isomorphous sub substitution of Zr in the framework of aluminosilicate HY by an electrochemical method: Evaluation by methylene blue decolorization. Appl Catal B: Environ 2012; 125: 311-323. Jusoh NWC, Jalil AA, Triwahyono S, Setiabudi HD, Sapawe N, Satar MAH, Karim AH, Kamarudin NHN, Jusoh R, Jaafar NF, Salamun N, Efendi J. Sequential desilication–isomorphous substitution route to prepare mesostructured silica nanoparticles loaded with ZnO and their photocatalytic activity. Appl Catal A: Gen 2013; 468:276–287. Muhammad IM, El-Nafaty UA, Abdulsalam S, Makarfi YI. Removal of oil from oil produced water using eggshell. Civ Environ. Res 2012; 2: 52-64. Zulfikar MA, Novita E, Hertadi R, Djajanti SD. Removal of humic acid from peat water using untreated powdered eggshell as a low cost adsorbent. Int J Environ Sci Technol 2013; 10: 1357–1366. Tsai WT, Yang JM, Lai CW, Cheng YH, Lin CC, Yeh CW. Characterization and adsorption properties of eggshells and eggshell membrane. Bioresour Technol 2006; 97: 488–493. Eletta OAA, Ajayi OA, Ogunleye OO, Akpan IC. Adsorption of cyanide from aqueous solution using calcinated eggshells: Equilibrium and optimisation studies. J Environ Chem Eng 2016; 4: 1367-1375.