Agar and egg shell derived calcium carbonate and calcium hydroxide nanoparticles: Synthesis, characterization and applications

Chemical Physics Letters 732 (2019) 136662

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Research paper

Agar and egg shell derived calcium carbonate and calcium hydroxide nanoparticles: Synthesis, characterization and applications

T

Shanza Rauf Khana, Saba Jamila, Hummayun Rashida, Shahid Alib, Safyan A. Khanb, ⁎ Muhammad Ramzan Saeed Ashraf Janjuac, a

Laboratory of Super Light Materials and Nanotechnology, Department of Chemistry, University of Agriculture, Faisalabad 38000, Pakistan Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia c Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia b

H I GH L IG H T S

and calcined egg shell are used as precursors for synthesis of calcium carbonate particles via solvothermal approach. • Agar product is calcined at 700 and 900 °C to study its effect on composition and morphology of particles. • Prepared refinements are performed on XRD data and structural models are constructed. • Reitveld the prepared products are found to be a good catalyst for degradation of Congo red dye. • All • All the prepared products have significantly increased the calorific value of Diesel fuel.

A R T I C LE I N FO

A B S T R A C T

Keywords: Egg shell Agar Calcium carbonate Additive Catalysis

Precursors calcined egg shell and agar are used to synthesize calcium carbonate particles by solvothermal method using ethylene glycol/water solvent system. The synthesized products are calcined at 700 and 900 °C for 5 h. Calcination temperature has significantly influence the morphology and composition of particles. Calcium carbonate particles are converted into calcium hydroxide particles after calcining at 900 °C for 5 h. Reitveld refinement is performed on XRD data of all products and their structural models are constructed. Data analysis shown that crystal system of all products is same, but the atomic coordinates have changed after calcination treatment. Scanning and transmission electron microscopic techniques are used for analysis of surface and internal morphology of products. Prepared products are used as catalyst for degradation of Congo red in aqueous medium. Prepared products are also used as fuel additive. Results indicate that the products possess significant potential to be used as catalyst and fuel additive. The product is comprised of oval shaped particles. The size of these oval shaped nanoparticles lies in the range of 80–120 nm.

1. Introduction Egg shell waste is a richest source of calcium and used for synthesis of different materials like talcite, apatite and calcium compounds and composites [1–7]. Calcium compounds like calcium hydroxide and calcium carbonate (CaCO3) are synthesized from egg shell. Egg shell waste is a natural source of calcium carbonate. CaCO3 nanoparticles are largely used in food packaging, feed additive, pharmaceutics, bone grafting, coating pigment, and polymer fillers [8–10]. CaCO3 particles are used in different applications in recent era. Ueno et al have used CaCO3 nanoparticles for controlled release of drug Betamethasone phosphate [11]. Shan et al have synthesized glucose biosensor by

⁎

immobilizing enzyme glucose oxidase on CaCO3 nanoparticles [12]. Barhoum et al have used CaCO3 nanoparticles along with anion and cationic surfactants to coat paper [13]. They concluded that CaCO3 nanoparticles coating made paper more bright, opaque and white as compared to commercial ground CaCO3. The synthesis of inorganic materials with controlled morphology, size and structure is center of attention of scientists due to their vast application range [14–21]. This task cannot be accomplished without understanding of parameters that control the nucleation and growth of particles. Solvothermal, microemulsion, coprecipitation and radiation assisted methods are used for synthesis of CaCO3 nanoparticles [22–25]. Mei Li and Stephen Mann have reported synthesis of CaCO3 nanoparticles by reverse

Corresponding author. E-mail addresses: [email protected], [email protected], [email protected] (M.R.S.A. Janjua).

https://doi.org/10.1016/j.cplett.2019.136662 Received 6 July 2019; Received in revised form 5 August 2019; Accepted 6 August 2019 Available online 07 August 2019 0009-2614/ © 2019 Elsevier B.V. All rights reserved.

Chemical Physics Letters 732 (2019) 136662

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(a)

(b)

(104)

JCPDS # 05-0586 Calcite (CaCO3)

Intensity

Intensity

JCPDS # 05-0586 Calcite (CaCO3)

(024)

(012)

(018) (116)

(110) (202) (113)

(10 10)

(104)

(202) (012)

(018)

(024)

(110)

(10 10)

(113)

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(006)

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2-theta (degree)

(c)

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JCPDS # 04-0733 Portlandite (Ca(OH)2)

(011)

Intensity

(001)

(100)

(102)

(110) (111)

(002)

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20

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40

50

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2-theta (degree) Fig. 1. XRD pattern of products synthesized by solvothermal method: (a) XRD pattern of product before calcination (Sample A), (b) XRD pattern of product after calcination at 700 °C for 5 h (Sample B), and (c) XRD pattern of product after calcination at 900 °C for 5 h (Sample C). Experimental pattern is represented by black line (—) while Rietveld refined pattern is represented by blue line (—). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

calcined egg shell and agar as starting materials. The influence of calcination temperature on morphology, composition and size of particles is reported. The composition of the all the products are analyzed by Xray diffractometry. The morphology of the products is analyzed by scanning electron microscopy and transmission electron microscopy. Synthesized products are used as catalyst for degradation of Congo Red dye in aqueous medium. Moreover synthesized products are also used as fuel additive.

microemulsion method [26]. Shirsath et al have synthesized CaCO3 nanoparticles using ultrasonic irradiation method [27]. CaCO3 particles are synthesized in this work through solvothermal method using agar. Previously agar is used as capping agent to control the morphology of nanoparticles. Jong-Whan Rhim and Paulraj Kanmani have synthesized gold nanoparticles of size range 2–20 nm using agar as reducing and stabilizing agents [28]. Shukla et al have synthesized silver nanoparticles using agar as a stabilizing agent [29]. Agar is first time used as reactant for synthesis of carbonate nanoparticles in this work. Despite diverse application range of CaCO3 nanoparticles, it does not previously used as fuel additive. Iron oxide, manganese oxide, tin oxide, cobalt oxide and cerium oxide nanoparticles are used as fuel additive in literature [30–36]. Energy demands are at peak due to rapid urbanization and population explosion. Therefore attention is diverted to get maximum benefit from available resources. Nanoparticles are found to be an efficient additive as it significantly increased the calorific value of fuel. It also reduces the chances of accidental fires, spillage and choking by modulation the cloud point, flash point, viscosity and gravity of fuel. In this work CaCO3 and Ca(OH)2 particles are synthesized using

2. Experimental 2.1. Materials Agar, sodium dodecyl sulfate and ethylene glycol were purchased from Sigma-Aldrich USA. De-ionized water was used throughout the experimental work.

2

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Fig. 2. The structure of trigonal lattice (hexagonal axes) of CaCO3 (sample B) synthesized by solvothermal method followed by calcination at 700 °C temperature for 5 h. (a) Position of calcium, carbon and oxygen species in lattice. (b) The bonding of oxygen with carbon in lattice. (c–d) Diffraction plane of atoms [1 1 0] and [1 0 4] in unit cell.

2.2. Procedure

3. Results and discussion

Chicken egg shells were collected, and their membrane was removed. Then its surface was cleaned and ground to fine powder. The obtained powder was calcined at 900 °C for 48 h in an electric furnace. 3 g calcined powder and 3 g agar-agar were dissolved in 60 mL ethylene glycol. 6 g sodium dodecylsulfate was added into it. Then 10 mL distilled water was added into reaction mixture and sonicated for 20 min at room temperature. Then the prepared mixture was poured into a Teflon vessel and placed in a solvothermal autoclave reactor. The autoclave was heated at 190 °C for 20 h. The obtained product was washed with water and ethanol and dried in an oven at 60 °C for 24 h. The obtained product is termed as Sample A. Sample A was calcined in electric furnace at 700 °C for 5 h to obtain product B. Sample A was also calcined at 900 °C for 5 h to obtain product C.

3.1. X-ray diffraction analysis XRD diffraction patterns of all the products are given in Fig. 1. The XRD pattern of product before calcination is given as Fig. 1a while the XRD pattern of products calcined at 700 °C and 900 °C are given as Fig. 1b and c respectively. The diffraction peaks of both patterns (Sample A and B) are positioned at similar 2-theta values. Fig. 1a possess diffraction peaks at 2-theta values 23.0°, 29.4°, 35.9°, 39.4°, 43.1°, 47.1°, 47.4°, 48.5°, 57.4° and 58.0° which correspond to miller indices (0 1 2), (1 0 4), (1 1 0), (1 1 3), (2 0 2), (0 2 4), (0 1 8), (1 1 6), (1 2 2) and (10 10) respectively. This set of values is characteristic to calcite (CaCO3) (JCDPS No. 05-0586). Then the product was calcined and its XRD pattern was measured (Fig. 1b). The sharpness of peaks increases after calcination but their 2-theta values and corresponding miller indices remain almost same. This shows that composition of products does not change after heating treatment at 700 °C for 5 h. It means chemical composition of sample A and B are same. But the morphology of both products is different from each other (as shown in SEM images). This also shows that CaCO3 is stable at 700 °C temperature. Rietveld refinements are also performed on XRD pattern of samples and refined parameters are used to construct the structural model of lattices of sample A and B. The refined parameters are listed in Table S1. The values of scale factor, profile factor (Rp), weighted profile factor (Rwp), expected weighted profile factor (Rexp), Durbin–Watson statistic (DW-stat), Chi square (χ2) and goodness of fit (Rwp/Rexp) of sample A and B are given in this Table S1. Small chi square and goodness of fit values indicate that good refinements have performed. The refined atomic coordinates and lattice parameters are also given in Table S1. The structural model is constructed on Software Vesta by using these values. CaCO3 is consists of trigonal unit cell. 50 atoms are present per unit cell constituted by 16 calcium, 12 carbon and 22 oxygen atoms. Out of 16 calcium atoms, 8 are present at corners, 4 are present in middle of edges and 4 are present within unit cell in [1 1 0] plane. All

2.3. Characterization Rigaku D/max Ultima III X-ray powder diffractometer equipped with Cu-Kα radiation source (wavelength 0.15406 nm) was used for XRD analysis of product in 10−80° 2θ range with 0.02° scanning step. This diffractometer operates at 0.130 A current and 40 kV voltage. JEOL JSM-6480A scanning electron microscope and PHILIPS CM 200 FEG, 160 kV Transmission electron microscope were used to analyze the morphology of product. Synthesized nanoparticles are used as additive to check the efficiency of commercial diesel obtained from PSO limited. APEX-JCX309 Closed Cup Flash Point Tester, Apex Lab Equipment Company is used for determination of flash point of fuel samples. Gravity meter DA-640, Kyoto Electronics Manufacturing Corporation Limited, is used for measurement of specific gravity of fuel samples. APEX-JCX406 Oxygen Bomb Calorimeter operating at standard GB/T 213 is used for determination of calorific value of fuel samples. American Society for Testing and Materials (ASTM) standard procedures are used for determination of cloud point and pour point [37]. 3

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chemical composition is remained same after calcination treatment, but it has completely changed the particles size and morphology. The elongated structures are transformed into bean like particles having depression at one side (Fig. 4d–e). Their boundaries are distinct and without irregularity. The surface of these particles also seems to be smooth. The length and width of these particles lie in 4.0–4.5 μm and 1.5–2.5 μm ranges respectively. These particles are randomly arranged with each other and formed ball like structure (Fig. 4d). Although the particles are joined with each other at one or more points, but small pores can be seen on the surface of these structures. Particles have developed a loosely packed structure. Few particles are also attached around a single particle and developed into another type of aggregate (Fig. 4f). The depression at the surface of bean like particles is clearly shown in Fig. 4g. The product is also calcined at 900 °C for 5 h to obtain the product C. The SEM images of this product are given as Fig. 4h–i. The chemical composition and morphology of product has completely changed by this calcination treatment. CaCO3 particles are converted into calcium hydroxide particles (as confirmed from XRD analysis given as Fig. 1c). The bean shaped particles are broken down into tiny and irregular shaped particles. The size distribution of the particles is wide because small and large particles are observed in these images. Due to influence of high temperature, these tiny particles are also grown into aggregates and their boundaries are fused. The TEM images of the product B and C are given as Fig. 5 and Fig. 6 respectively. TEM images of Fig. 5 show that shape of particles is bean like with a depression on one side only. No contrast is seen in these images which show that the particles are not hollow from inside. Fig. 5a shows the overview of the product. It seems that the product is consists of aggregates. The closer analysis of the product is given in Fig. 5b and c. Fig. 5b shows that depression is present at the surface. While Fig. 5c shows that boundaries of product are not irregular. The aggregate of the particles is visible in Fig. 5c. Four to five particles are attached around a single particle at center. The length and width of big size particles measured from TEM images lie in 350–450 nm and 200–300 nm ranges respectively. Few small particles are also observed with similar morphology. The length and width of these particles lies in 200–300 and 150–250 nm range respectively. The TEM images of product C are given as Fig. 6. These images are scanned at magnification 15,000× and 25,000×. These images clearly show that Ca(OH)2 nanoparticles are present in the form of aggregates in product C. The boundaries of the particles are fused with each other. The particles are arranged one above the other and developed aggregated structures.

carbon atoms are present within unit cell. Each carbon atom is coordinated with 3 oxygen atoms and formed carbonate. The distance between carbon and oxygen atoms is 1.28269 Å. Diffraction plane [1 1 0] is shown in Fig. 2c. This plane is formed by calcium atoms. Diffraction plane [1 0 4] is shown in Fig. 2d which is constituted by carbon and oxygen atoms. Diffraction peak of highest intensity is appeared due to this plane of atoms because its four planes are present in one unit cell (Fig. 1b). XRD pattern is also measured after calcination at 900 °C for 5 h. Diffraction peaks are obtained at 2-theta values 18.1°, 28.7°, 34.1°, 36.6°, 47.1°, 50.8°, 54.3°, 56.2° and 59.4° which are indexed to (0 0 1), (1 0 0), (0 1 1), (0 0 2), (1 0 2), (1 1 0), (1 1 1), (0 0 3) and (2 0 0) respectively. This set of miller indices indicate that product is calcium hydroxide Ca(OH)2 (JCPDS No. 04-0733). No diffraction peak of CaCO3 is present in XRD pattern of Sample C which shows that CaCO3 has completely converted into Ca(OH)2 at 900 °C through Eqs. (1) and (2).

CaCO3

900 °C,5 h

→

CaO + CO2

CaO + H2 O→ Ca(OH)2

(1) (2)

Rietveld refinement is also performed on this XRD pattern. The refinement parameters are given in Table S1. Values of chi square and goodness of fit are 8.02 and 2.8 respectively. Refined lattice parameters and atomic coordinates are also given in Table S1. The structure of unit cell of Sample C is constructed using the parameters given Table S1. Trigonal unit cell is shown in Fig. 3a. Calcium atoms are present at corners of unit cell. No calcium atom is present in middle of edges as in lattice of Sample B. Unit cell length along z-axis of Sample C is more than double of the same dimension of Sample B. In Sample C, all calcium atoms are exposed as compared to that of Sample B. Oxygen and hydrogen atoms are present within unit cell. 8 calcium, 2 oxygen and 2 hydrogen atoms constitute one unit cell of Sample C. Diffraction peaks of miller indices [0 0 1] and [0 1 1] show highest intensity in Fig. 2c which are indicated in structural model given in Fig. 3b. These planes are constituted by calcium atoms. 3.2. Scanning and transmission electron microscopic analyses In order to analyze the morphology and size of particles, all the products are characterized by SEM. The SEM images of the product before calcination are given as Fig. 4a–c. It is cleared from Fig. 4a–c that the product is comprised of oval shaped particles. The size of these oval shaped particles lies in the range of 80–120 nm. The boundaries of these particles seem to be fused together. These particles have arranged to form of elongated structures with irregular boundaries. These elongated structures are compactly arranged one above the other and formed layers. This layer-by-layer assembly is clearly shown in Fig. 4b–c. The width of these elongated structures lies in 80–120 nm range and their length lies in 550–700 nm range. This product is calcined at 700 °C for 5 h and product B is fabricated. Although the

3.3. Preparation scheme Egg shells are chiefly (~94%) are composed of CaCO3. Upon calcination at 900 °C for 48 h, it is converted into calcium oxide (CaO) (Eq. (3)). When CaO and agar are heated in autoclave at 190 °C for 20 h then CaCO3 particles are formed (Eq. (4)). Temperature 190 °C is chosen for

Fig. 3. (a) The structural model of trigonal lattice (hexagonal axes) of Ca(OH)2 (Sample C) obtained after calcination of Sample A at 900 °C for 5 h. (b) Diffraction planes [0 0 1] and [0 1 1] producing highest intensity diffraction peaks in XRD analysis. 4

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Fig. 4. SEM images of synthesized products. (a–c) SEM images of Sample A (CaCO3) before calcination: (a) overall view of product and (b–c) arrangement of nanoparticles in the form of layers. (d–f) SEM images of Sample B (CaCO3) obtained after calcination of Sample A at 700 °C for 5 h in the presence of air: (d) aggregate of oval shaped microstructures obtained via Ostwald’s ripening of nanoparticles, (e) randomly oriented microstructures, (f) bear like arrangement of microstructures and (g) magnified view of surface of these microstructures. (h–i) SEM images of Sample C (Ca(OH)2) obtained after calcination of Sample A at 900 °C for 5 h in the presence of air.

maximum at 495 nm wavelength in aqueous medium, so this wavelength is chosen to monitor the concentration of dye in reaction mixture. Catalytic degradation of dye is studied by UV–visible spectrophotometry in the presence of excess of H2O2, so it obeys pseudo first order kinetics [39,35,40]. The catalytic degradation of CR dye is monitored at different intervals of time. The UV–Visible spectra of catalytic degradation of dye is shown as Fig. 9. It is observed from this figure that absorbance at 495 nm wavelength is continuously decreasing with time. Value of absorbance is indicator of concentration of dye, according to Beer-Lambert’s law. It means catalyst is playing its role and degrade the dye molecules into non-toxic components. Absorbance at different time intervals is noted and plot of Fig. 10 is plotted using the Eq. (5).

heating reaction mixture in autoclave because solvent ethylene glycol/ water is used. Ethylene glycol is boiled around 190 °C. CaCO3 particles (product A) are calcined under two different temperatures: 700 °C and 900 °C. The composition of the product is remained same after heating at 700 °C, but the morphology of particles has changed as shown in Fig. 7. After calcination at 900 °C, CaCO3 is decomposed into CaO which is converted into Ca(OH)2 due to moisture (Eqs. (1) and (2)).

CaCO3

900 °C,48 h

→

CaO + Agar

(3)

CaO + CO2 190 °C,20 h

→

Ethylene glycol/water

CaCO3

(4)

3.4. Catalytic application

A ln ⎛ t ⎞ = −k app × t A ⎝ o⎠ ⎜

Degradation of CR dye is selected to study the catalytic activity of synthesized products A, B and C. It is a water-soluble dye and mostly used to color the apparels in the industry. Therefore, concentration of dye in the waste water is increasing day-by-day. CR dye is constituted by aromatic rings which make it difficult to eliminate from water. It also contains chromophore secondary diazo group (eN]Ne) and auxochrome sulfonate group (eSO3H) that are associated with benzene ring as shown in the Fig. 8. Dye shows blue color in acidic medium and red brown color in basic medium [38]. CR dye molecules absorb

⎟

(5)

In this Eq. (5), absorbance at 0 min and at any time are denoted by A0 and At respectively. Apparent rate constant is denoted by kapp and time is indicated by t. Eq. (5) is a pseudo first order kinetic equation. Variable ln(At/A0) is plotted as a function of time according to Eq. (5) in Fig. 10. The plot of ln(At/Ao) versus time in the presence of catalyst A, B and C is given in Fig. 10a. At the start of reaction, significant change in the value of ln(At/Ao) is observed as its value is decreasing with time. 5

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Fig. 5. TEM images of Sample B (CaCO3). (a–b) TEM image of overall view of the aggregate of microstructures. (c) TEM image of bear like assembly formed by arrangement of oval like microstructures.

That’s why it shows least catalytic activity. Catalytic activity is a surface related process. So high surface area to volume ratio, high catalytic activity. Value of kapp obtained by using catalyst C is found to be greater than that of catalyst B. The particles of catalyst B is of bigger size than that of catalyst C. Although aggregates are present in product C but high catalytic activity shows that particles still possess good surface activity. The catalytic activity of synthesized catalysts is comparable to other catalysts reported in literature for degradation of CR dye [41–43,35,44,45]. Synthesized catalysts (A, B and C) possess advantage over those catalysts because these are prepared from a waste product, so it has no economic constraints. Moreover, agar a natural compound is used in synthesis of these catalysts. Therefore, a waste product is used

This decrease in its value indicates that the degradation of dye is progressing successfully. After linear decrease, it is also observed that value of ln(At/Ao) do no change with time. This shows that catalysis has completed. Linear region of plots of Fig. 10a is used to calculate value of kapp (Fig. 10b). Slope of this linear region is equal to value of kapp. Its value is found to be 0.010, 0.013 and 0.019 min−1 for catalyst A, B and C respectively. Value of correlation coefficient (R2) is found to be 0.97, 0.91 and 0.97 for catalyst A, B and C respectively. The comparison of kapp values indicates that catalyst A shows least catalytic degradation activity among all catalysts and the catalytic activity of catalyst B and C are comparable to each other. Catalyst A possess elongated structures with fused boundaries, so its available surface for catalysis is very low.

Fig. 6. TEM images of Sample C (Ca(OH)2). (a) TEM image of overall view of the product. (b–d) Nanoparticles are joined with each other. 6

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Fig. 7. Preparation scheme of product A (CaCO3), B (CaCO3) and C (Ca(OH)2).

increases in case of catalyst B. kapp is related to degradation of dye molecules after adsorption on surface of catalyst. Elongated structures of catalyst A are fused with each other so dye molecules do not found enough surface for adsorption. That’s why the dependence of kapp on dosage of catalyst A is smallest among all catalysts. The values of kapp in case of catalyst B and C are comparable to each other. The value of kapp sharply increases with increase in dosage of catalyst B and C because of their small particle size. Particles of catalyst B are not fused and possess smooth surface for adsorption of dye molecules. Similarly particles of catalyst C are very small in size. These parameters favor the adsorption and degradation of dye molecules and kapp value is increased. Histogram of percentage degradation of dye and dosage of catalysts A, B and C is shown as Fig. 11b. It is observed from the plot that percentage degradation of dye is increased with increase in catalyst dosage. The percentage degradation of catalyst C is greater than that of A and B at every dosage. While percentage degradation of catalyst A and B are comparable to each other. This shows that catalyst C has ability to degrade more number of dye molecules in short time if its dosage is increased. While catalyst B has ability to degrade same number of molecules as that of catalyst A but at higher speed. This is due to the morphology and size of particles of catalyst B as compared to that of A. Due to fusion of boundaries, the percentage degradation of catalyst A is lowest among all catalysts.

Fig. 8. Structure of Congo red dye. 1.4 1.2

max

0 min 8 min 16 min 24 min 32 min 40 min 48 min 56 min

495 nm

Absorbance

1.0 0.8 0.6 0.4

3.5. Fuel additive 0.2 0.0 300

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Product A, B and C are used as diesel additive to determine their influence on physiochemical properties of fuel by using ASTM standard methods. The effect of additives on following fuel properties is determined: flash point, fire point, cloud point, pour point, kinematic viscosity, specific gravity and calorific value. Results of pure diesel and modified diesel are also compared. The dependence of calorific value of diesel on the concentration of prepared additive A, B and C is studied and results are plotted as Fig. 12a. It is observed from this figure that calorific value is increased with increase in concentration of additive. The increase in calorific value is observed because particles of additive provide active sites for diesel adsorption and facilitates its oxidation. Calorific value is the maximum heat that generated from fuel excluding heat of vaporization and this heat is used to run engines. It is a property to test the fuel quality. So, obtained results strongly favor the use of nano/micro

750

Wavelength (nm)

Fig. 9. UV–Visible spectra of catalytic degradation of CR dye at various intervals of time (conditions: dye = 20 ppm, [H2O2] = 0.08 M and [catalyst A] = 0.1 mg/mL).

for beneficial purposes through this approach. Activity of all the three synthesized catalysts is studied at 0.10, 0.15, 0.20 and 0.25 mg/mL dosages (Fig. 11a). This figure shows that kapp value is increased with increase in dosage of all catalysts but dependence of kapp value on dosage of all catalysts is not same. kapp value slowly increases in case of catalyst A while kapp value is sharply 7

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(b)

(a) 0.0 A B C

-0.1

A B C

-0.1

-0.2

ln (At / Ao)

-0.2

ln (At/Ao)

0.0

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-0.6 0

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Time (min)

Time (min)

Fig. 10. (a) Plot of ln(At/Ao) versus time of catalytic degradation of CR dye in the presence of catalyst A, B and C. (b) Linear region of plot ln(At/Ao) versus time used to calculate kapp (conditions: dye = 20 ppm, [H2O2] = 0.08 M and [catalyst] = 0.1 mg/mL).

kinematic viscosity of diesel is small in the absence of additive and found to increase with addition of additive. As viscosity is the internal resistance in the layers of fluid and related to the lubrication of fluid. High kinematic viscosity value of fuel provides enough lubrication. Fuels having low viscosity do not show sufficient lubrication and turbulence in their flow in observed. Kinematic viscosity of fuel is also related to the performance of fuel injection in the equipment and efficiency of engine. On the other hand, high viscosity is also a cause behind poor combustion and increase the percentage of unburnt hydrocarbons in smoke emissions. So dosage level of additives is retained between these two fact because it effects the engine performance. In case of all the three additives A, B and C, the increment in viscosity is not very high that decreases the engine efficiency. So these additives can be used to increase the engine performance. Smallest increase in kinematic viscosity of fuel with increase in concentration of additive is observed for additive A. While the kinematic viscosity of fuel in the presence of additive B and C is greater than observed in the presence of additive A. The concentration of additive A, B and C is varied from 0 ppm to 60 ppm to analyze their effects on specific gravity of diesel and results are given in Table 1. Specific gravity of pure and modified diesel is also compared. Table 1 shows that specific gravity of pure and modified

particles as additives to increase the efficiency of fuel. It is also observed from Fig. 12a that increase in calorific value does not follow same trend for all additives A, B and C. In case of additive A, the calorific value of 0 and 10 ppm concentration of additive is almost same. For additive A, calorific value is found to linearly increase when concentration of additive is increased above 10 ppm. Significant increase in calorific value is observed when 10 ppm of additive B and C is used. Although the calorific value is increased when concentration of additive B and C is increased from 10 to 60 ppm but this increment is smaller than observed initially from 0 to 10 ppm. This is due to particle size and morphology of the additives A, B and C. Maximum fuel molecules have adsorbed on tiny particles of additive B and C at their 10 ppm concentration, so significant increase in calorific value is observed. When concentration of additive is increased from 10 to 60 ppm then no such large number of fuel molecules are available for oxidation. Particle size of additive is an important factor in increasing/decreasing the calorific value of fuel. Small particle size favors the oxidation of fuel and produces high energy. Previously iron oxide [36] and cobalt oxide [32] nanoparticles have been reported as fuel additive. Calorific value obtained in case of additive A, B and C are comparable to them. The dependence of kinematic viscosity is also studied as function of concentration of additive A, B and C (Fig. 12b). It is observed that

(b)

0.10

0.08

Sample A Sample B Sample C

60

0.06 -1

kapp (min )

Sample A Sample B Sample C

50

% Degradation

(a)

0.04

40 30 20

0.02

10 0.00 0.00

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0.15

0.20

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0.10

Catalyst dosage (mg/mL)

0.15

0.20

0.25

Catalyst dosage (mg/mL)

Fig. 11. (a) Plot of kapp as a function of catalyst dosage of all the three synthesized catalysts A, B and C. (b) Percentage degradation of dye catalyzed by A, B and C catalysts under various catalyst dosages. 8

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(a) 40

(b)

A B C

2 -1

2.82

-6

30

Calorific value (kJ/g)

A B C

2.85

Kinematic viscosity (10 x m s )

35

25 20 15 10 5 0 0

10

20

30

40

50

2.79

2.76

2.73

2.70

0

60

10

20

30

40

50

60

Concentration of additive (ppm)

Concentration of additive (ppm)

Fig. 12. Plot of (a) calorific value and (b) kinematic viscosity of fuel in the presence of 10, 20, 40 and 60 ppm concentration of additive A, B and C.

difference is observed in their cloud point and pour point. The cloud point is observed to be decreased by 2–3 °C while pour point is found to be decreased by 1–2 °C for all additives. So it is concluded that additives have no remarkable effect on the low temperature characteristics of fuel. Cloud point and pour point are low temperature characteristics. When fuels are chilled at sufficient low temperature, they lose their ability to flow.

diesel samples is almost same in case of all additives. The values of flash point and fire point at 0, 10, 20 and 60 ppm concentration of additive A, B and C are also given in Table 1. The flash and fire points of pure diesel are measured to 67 °C and 72 °C respectively. These characteristics of fuel are affected by concentration of additives, but flash point is found to increase with increase in concentration of additive A and B and its value is found to decrease with increase of concentration of additive C. Similar trend is also observed for fire point values in the presence of these additives. Flash point values is greater than fire point values for all the samples. The increase in flash and fire points value with increase in concentration of additive A and B indicates that volatility of fuel is decreased by these additives. It means additive C is increased the volatility of fuel. High flash and fire points indicates that fuel can be safely stored and transported under high temperature and pressure conditions. The chances of accidental fires are also reduced. In the previous literature cerium oxide nanoparticles are reported as fuel additives to increase the efficiency of diesel. Increase in flash point and fire point values is found by increasing the concentration of cerium oxide nanoparticles. Literature study also revealed that high flash point and fire point values are favorable for safer handling of diesel. The cold temperature characteristics cloud and pour points of diesel are also measured in the presence of 10, 20, 40 and 60 ppm concentration of additive A, B and C (Table 1). The cloud and pour points of diesel are found to be almost same for all the additives. No significant

4. Conclusion Calcium carbonate particles are synthesized by using calcined egg shell and agar as precursors. The morphology of product is changed into elongated structures after calcination at 700 °C for 5 h. CaCO3 elongated structures are converted into Ca(OH)2 particles after calcination at 900 °C for 5 h. The catalytic and fuel additive applications of prepared products are studied. Apparent rate constant (kapp) and percentage degradation of Congo red are significantly affected by catalyst dosage. The value of kapp of catalytic degradation of Congo red is found to be highest for Ca(OH)2 particles as compared to other products. This shows that Ca(OH)2 particles are better catalyst than elongated CaCO3 particles. Calorific value obtained in case of Ca(OH)2 particles are comparable to that obtained in case of CaCO3 bean like particles. Comparative analysis indicates that Ca(OH)2 possess better additive properties as compared to CaCO3 particles. In this work a waste product is converted into a good catalyst and additive.

Table 1 Summary of fuel characteristics (fire, flash, cloud and pour points and specific gravity) in the presence of prepared additives A, B and C. Properties

ASTM D6751 Standards

3

Fuel without additive

Specific gravity (g/mm ) at 25 °C

ASTM D1298

8.4

Flash point (°C)

ASTM D93

67.8

Fire point (°C)

ASTM D93

72.2

Cloud point (°C)

ASTM D2500

8.0

Pour point (°C)

ASTM D97

−14.3

Additive

A B C A B C A B C A B C A B C

9

Modified fuel (fuel with additive) 10 ppm

20 ppm

40 ppm

60 ppm

8.5 8.5 8.5 68.1 68.0 67.6 72.8 73.0 71.8 7.0 5.6 5.6 −14.4 −14.4 −14.4

8.5 8.5 8.5 68.1 68.5 67.2 73.0 73.2 71.2 6.8 5.3 5.3 −14.4 −14.4 −14.6

8.5 8.5 8.5 68.5 69.0 67.0 73.2 74.0 69.0 6.7 5.0 5.0 −15.0 −15.0 −14.9

8.5 8.5 8.5 68.2 69.3 66.8 73.5 74.5 68.2 6.6 4.9 4.9 −15.0 −15.2 −15.2

Chemical Physics Letters 732 (2019) 136662

S.R. Khan, et al.

Declaration of Competing Interest [20]

This manuscript has NOT been published previously and is not under consideration for publication in another journal at the time of submission.

[21]

Acknowledgement

[22]

The authors would like to acknowledge the support provided by the University of Agriculture, Faisalabad (UAF), Pakistan. This research work was initiated, designed and completed at UAF with the help of corresponding author. However, the final write up was accomplished at King Fahd University of Petroleum and Minerals (KFUPM), Dhahran, Kingdom Saudi Arabia.

[23]

[24]

[25]

Appendix A. Supplementary material

[26]

Supplementary data to this article can be found online at https:// doi.org/10.1016/j.cplett.2019.136662.

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