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  BC.48 Proceedings of the IConSSE FSM SWCU (2015), pp. BC.48–55

ISBN: 978-602-1047-21-7

  Preparation and characterization of nanosize spinel Ni

  0.9 Fe

  2 Cu

  0.1 O

  4

using pectin as binding agent

_{a b a}

Rodhiansyah Djayasinga and Rudy Situmeang

  

Graduate Student in Department of Chemistry, University of Lampung

_b

Department of Chemistry, University of Lampung

Jln. Prof. Soemantri Brodjonegoro No. 1 Bandar Lampung 35145, Indonesia

  

Abstract

Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial have been prepared using a sol-gel method. Preparation}

of material was carried out by dissolving nitrate salts of iron, cobalt and nickel, in pectin

solution and then the sample was stirred throughly using magnetic stirrer while

adjusting pH to 11. After freeze-drying process, the sample was subjected to calcination

treatment and subsequently characterized using the techniques of X-ray diffraction

(XRD), Debye Scherrer Methods, PSA, and DT-TG analysis. The results of XRD

characterizationand Rietveld calculation indicated that materials consist of four

crystalline phases, such as, CuFe ^{2 O}

^{4 , Cu 0,86 Fe 2,14 O}

^{4 , NiFe 2 O 4 , and NiO. The first three} crystalline phases is superimposed. DT-TGA result showed that spinel Ni _o ^{0.9 Fe 2 Cu 0.1 O 4} formed at 400

  C. Then, PSA determination proved that the grain size of spinel ferrites is

a range of 30–95.2 nm as much as 21%. Crystallite size calculation using Scherrer

equation, proved that the size is 35.42 nm and its size increased as temperature

calcination inclined.

  Keywords : Nanomaterial, BrØnsted–Lowry and Lewis acid sites, spinel ferrites

1. Introduction

  Spinel compounds have attracted great attention due to their many enormous

properties for diverse industrial field applications, such as electronic devices [Waqas et al.,

2012; Roy et al., 2012], magnetic materials [Niyaifar et al., 2014; Qian et al., 2010 ], pigments

[Candeiaa et al., 2004; Imanaka et al., 2015], and catalysis [Daadmehr et al., 2013; Abelo et

al., 2011, Situmeang et al., 2011]. In general, the applications of this spinel compound is

governed by peculiar properties, which in turn depends on the chemical composition and

microstructure [refs]. In general, the structural formula of spinel compound is symbolized as

AB

  2 O 4 for II – III cation systems or A

  2 BO 4 for II-IV, II-III, I-III/IV cation systems (Le et al., 2014;

Hill et al., 1979). Furthermore, the structural formula of spinel compound such as ferrites can

  2+ 3+ 2+ 3+ 1−δ δ δ 2−δ

  4

be written as (M Fe )[M Fe ]O , where parentheses and square brackets denote

cation sites of tetrahedral (A) and octahedral (B) coordination, respectively. δ, which is

determined by the preparation process, represents the so called degree of inversion defined

  

3+

as the fraction of the (A) sites occupied by Fe cations (Corrias et al., 2008; Lazarević et al.,

2012; Sutka et al., 2012).

  Since the choice of preparation method can determine the formation of a peculiar

property of the material, it is crucial to decide which method of preparation will be used.

Based on the literatures, sol-gel method is the better method compared to another method

(Perego & Villa, 1997; Maensiri et al., 2007). This sol-gel method have proved that nano-

materials will be formed (Yehia et al., 2014; Situmeang et al., 2015a,b). The nano-size

SWUP

  BC.49 R. Djayasinga, R. Situmeang

materials are really important and leads to the change of its properties that are needed to

the various current and future specialized applications (Vanaja et al., 2013).

  Spinel ferrites of Ni 1-x Fe

  2 Cu x O 4 (x = 0.1–1) prepared by various method have been

studied by several scientists (Kumar et al., 2012; Murthy et al., 2009; Daadmehr et al., 2013)

and proved that the addition of Cu cation into spinel nickel ferrite will have a significant effect

on the electromagnetic properties and catalytic functions. In this study we would like to

  0.9

  2

  0.1

  4

report the preparation of nano spinel nickel copper ferrite, Ni Fe Cu O prepared using sol-

gel method and pectin as a binding agent. The materials obtained are characterized using

  

XRD to identified the phases formed, PSA to know the particles sizes, Scherrer method to

calculate crystallite sizes, and FTIR to identified both functional groups and bond formations.

2. Materials and Methods

2.1 Materials

  Materials used in this work are pectin powder, Ni(NO 3 ) 2 .6H

  2 O (Merck, 99%), Fe(NO 3 ) 3 .9H

  2 O (Merck, 99%), Cu(NO 3 ) 2 .3H

2 O (Merck, 99%), pyridine (C

  5 H

  5 N, J.T Baker), NH

  3 (Merck, 99%), and aquadest.

  2.2 Instrumentations The instruments used for characterization were Fourier Transform Infrared (FTIR)

spectrometer (Shimadzu Prestige-21) for identifying the presence of functional groups, and

  

Differential Temperature and Gravimetry analysis (DT-GA) for elucidating the formation

process . Then, a Philips X-ray diffractometer (XRD) model PW 1710 with Cu-Kα radiation

was used for structural and crystalline phases identification and Particle Size Analyzer (PSA)

for measuring particle size distribution.

  2.3 Preparation of Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial} Stoichiometric amount of Ni (II) nitrate hydrates, Cu (II) nitrate hydrates and Fe (III) nitrate hydrates were dissolve in distilled water, having compositions Ni

  0.9 Fe

  2 Cu

  0.1 O 4 under

magnetic stirring for 1 hour, respectively, followed by mixing each solution to make final

solution weight ratio between nitrates to pectin is 3:2. Adjust the pH=11 in the above solution

o

by addition of ammonia, and heat it at 80 C with continue stirring to form viscous gel. Dried

the gel using freeze dryer for 7 hours to form the precursors’ networks and calcined at 600

o and 800 C for 3 hours. Finally Cu doped Ni - ferrite nanoparticles has prepared.

  2.4 Characterization of Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial} Differential Temperature and Gravimetry Analysis

  Sample of approximately 5–6 mg precursor was placed in Pt-sample compartment and

the instrument was carried out under a flowing nitrogen atmosphere (50 ml/min, SII TG/DTA

o o -1 7300). Then, scan analysis was worked in the range of 25 to 600 C with ramp of 5 C min .

  Particle Size Analysis Particle size distribution of the solid sample is obtained by using the infra-red

scattered through sample particles in ethanol media which was responding to the brownian

movement on Beckman–Coulter Delsa nano. The principle of this analysis is accordance with

Dynamic Light Scattering (DLS) method that is the smaller the particle the faster its moves.

  _{0.9 2}

_0.1

₄ BC.50 Preparation and characterization of nanosize spinel Ni Fe Cu O using pectin as binding agent

The range of particle size could be measured is 0.1 nm to 10 μm. The result of particle size

distribution is both calculated and analysed by using statistical method with mean, median

and modulus parameters (Malvern Instruments, 2012).

  X-ray diffractogram analysis o

  X-ray powder diffraction pattern of the sample was recorded from 2 = 10 to 90 on o

a Philips diffractometer Model PW 1710 using Cu K  radiation at a step 0.02 per second. The

phase identification was performed using search and match method by comparing the x-ray

pattern of the sample to those of the standards in the COD using Phase Identification from

Powder Diffraction program Version-2. The particle size was also determined using Debye–

Scherrer method (Cullity, 1978).

  Acid sites analysis of Ni

  0.9 Fe

  2 Cu

  0.1 O

  4 o After heating at 120

  C, sample was transferred into a crucible and placed in

vaccumized dessicator. Pyridine was transferred into another crucible and placed in the

dessicator to allow the vapour of the pyridine to contact with the sample. After 24 hours,

the sample was taken from dessicator and left on open air for 2 hours to expell the physically

adsorbed pyridine from the sample. Finally, the sample was analyzed using the FTIR

spectroscopy. The analysis was conducted by grinding the sample with KBr of spectroscopy

  −1

grade, and scanned over the wave number in the range of 4000–400 cm (Parry, 1963;

Ryczkowski, 2001).

  3. Results and Discussion

  3.1 Differential Temperature and Gravimetry Analysis The precursor of Ni

  0.9 Fe

  2 Cu

  0.1 O 4 nanomaterial prepared were characterized using

thermal analysis techniques such as differential temperature and thermal gravimetric

analysis (DT-TGA). Thermal gravimetric analysis was used to measure the losses of weight as

a function of temperature. The TGA results for the 4.8 h aged precursor containing

[Cu]/[Ni]=1/9 molar ratio is shown in Figure 1 .

  There is a gradual weight loss upon heating to about 200°C; above this temperature o there is a crucial weight loss until 400

  C. During the first period of the weight loss, the o

exothermic process is occured at 173.7 C and the energy of 3.123 Vs/mg. The first weight

loss with temperatures range of 100–200°C and is due to the removal of absorbed water in

pectin networks. The second period of weight losses with temperatures at around 200–

400°C, are considered to be due to the decomposition of pectin, and nitrate precursors, so

that the decomposition at these high temperature regions produce water, carbon dioxides

o and nitrogen oxides simultaneously. Above 400

  C, there was no weight loss and the formation of Ni

  0.9 Fe

  2 Cu

  0.1 O 4 nanomaterial was started.

  3.2 X-ray diffractogram analysis The prepared sample was characterized by Philips PW-1710 X-ray diffractometer using

Cu-K radiation (λ =1.5406 Ǻ) source. The X-ray diffraction pattern of the prepared sample is

   shown in Figure 2.

  The diffraction pattern of Ni

  0.9 Fe

  2 Cu

  0.1 O 4 together with some standards related to the

predicted phases of the sample was presented in Figure 2(a). With the aid of search and

match method, using Phase Identification from Powder Diffraction program Version2, it was

  SWUP R. Djayasinga, R. Situmeang ^BC.51 found that the major phase is spinel NiFe

  

2 O

4 (COD-96-230-0290), CuFe

  Figure 1. DT-TGA curve for Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial precursor with Cu/Ni = 1/9} molar ratio.

  0.1 O

  

2

Cu

  0.9 Fe

  Moreover, the crystallite size of Ni

  (b) Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial after calcining 600 and 800 o} C.

  

(a) (b)

Figure 2. (a) Difractogram of Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial after calcining at 600 o} C and

  2 O 4 (JCPDF no. 10-0325) were more pronounced by their intensities as indicated on Figure 2(b) above.

  2 O 4 (COD-96-901- 2439) and Ni

  2 O

4 (JCPDF no. 34-0425) and NiFe

  2 O 4 crystalline phases are superimpossed. By increasing the calcination temperature, the formation of both CoFe

  2 O 4 and CuFe

  4 (COD-96-230-0296) as a minor phase. In general, it can be implied that both NiFe

  2 O

  1.7 O 4 (COD-96-100-6117). Additional phase identified is spinel NiFe

  1.43 Fe

  4 nanomaterial was calculated from the most prominent peak (211) of XRD using the Scherrer formula (Cullity, 1978): ^{T e m p C e l 6 0 0 .0 5 0 0 .0 4 0 0 .0 3 0 0 .0 2 0 0 .0 10 0 .0 D T A u V /m g 6 .0 0 0 4 .0 0 0 2 .0 0 0 0 .0 0 0 -2 .0 0 0 -4 .0 0 0 -6 .0 0 0 T G % 0 .0 0 -10 .0 0 -2 0 .0 0 -3 0 .0 0 -4 0 .0 0 -5 0 .0 0 -6 0 .0 0 -7 0 .0 0 -8 0 .0 0 D T G u g /m in 7 0 0 .0 6 0 0 .0 5 0 0 .0 4 0 0 .0 3 0 0 .0 2 0 0 .0 10 0 .0 0 .0 5 .3 3 % 3 4 .7 2 % 3 0 .2 5 % 1 7 3 .7 Cel 3 .1 2 3 u V/ m g 1 7 2 .3 Cel 2 6 3 .0 u g / m in - 9 7 8 u V.s/ m g 600 o C 800 o C}

  _{0.9 2}

_0.1

₄ BC.52 Preparation and characterization of nanosize spinel Ni Fe Cu O using pectin as binding agent

  λ = , cos

where D is the crystallite size (nm), λ =1.5406 Ǻ or 0.15406 nm is the wavelength of incident

X-ray, θβis the diffraction angle at the prominent peak and β is the broadening of diffraction

  π

line measured at half maximum intensity, (in radian), and k is a constant with

range of 0.9–1.0 (in this calculation, k = 0.94).  is the Bragg’s angle in degree unit. The

calculation results are compiled in Table 1.

  

Table 1. Crystallite size calculation using Scherrer equation.

Ni ^{0.9 Fe 2 Cu 0.1 O 4 FWHM Size of Crystallite (D)} hkl

  2 (deg) θ

  Calcined at (nm) degree ( )/ radian _o

  β 600 C _o 35.18 211 0.6984 0.012183

  12.48 800 C 35.36 211 0.4571 0.007974

  19.08

  0.9

  2

  0.1

  4 As shown in Table 1, the crystallite sizes of Ni Fe Cu O samples are in the range of

10–20 nm, demonstrating the efficacy of the proposed method to produce nano-size spinel

Ni

  0.9 Fe

  2 Cu

  0.1 O 4 . In relation with the calcination variation, it was found that the higher the calcination temperature the bigger the crystallite size.

  3.3 Particle Size Analysis Figure 3 shows the particle size distribution of the Ni

  0.9 Fe

  2 Cu

  0.1 O 4 sample obtained at

o

one angle of incidence of the laser beam (65 ) by the particle size analyzer (PSA). It implies

that the sample has a variety of particle sizes in both nano and micro scales with maximum

intensity at certain sizes shown in Table 2. The average particle sizes of the sample estimated

from PSA is also displayed in Table 2.

  Figure 3. Particle size distribution of Ni ^{0.9 Fe 2 Cu 0.1 O 4 nanomaterial sample.}

  The existence of micro scale can be concluded that the majority of particles tend to

agglomerate, may be due to the lack of both pre-treatment on preparation of PSA sample

and variation of incident angle of the laser beam. The values of the crystallite sizes calculated

from the XRD patterns is actually all observed in the particle size distribution detected by the

PSA. In other words, the particle size distribution detected by the PSA represents a grain size

and enhances the calculated crystallite sizes from the XRD patterns.

  SWUP

  BC.53 R. Djayasinga, R. Situmeang

  Table 2. Particle size distribution and the average particle sizes of Ni ^{0.9 Fe 2 Cu 0.1 O 4 sample} estimated by PSA.

  Ni ^{0.9 Fe 2 Cu 0.1 O 4} Average particle size Particle Size Percentage of Particle calcined at

  Calculated from PSA data _o (nm) sizes (%) 600 C (nm)

  Group 1

  27.8

  20.8

  32.4 Group 2 417.7 79.2 530.7

  3.4 Acid sites analysis of Ni ^{0.9 Fe 2 Cu 0.1 O 4} Fourier transform infrared spectroscopy was applied to identify the functional groups

present in the sample, primarily to identify the existence of Lewis and BrØnsted–Lowry acid

sites. The acid sites identification is of particular importance since the acidity is

acknowledged as very important characteristic which determine the performance of a

material as a catalyst (Parry, 1963; Tanabe, 1970; Ryczkowski, 2001). The FTIR spectra of

Ni

  0.9 Fe

  2 Cu

  0.1 O 4 sample investigated is shown in Figure 4.

  0.9 Fe ^{2 Cu 0.1 O 4 after exposed to pyridine vapour: a. calcined} Figure 4. FTIR Spectrum of Ni _{o o} at 600 C and b. calcined at 800 C.

  As shown in Figure 4, In general, the peaks appeared at the wavelength range of 3500–

• 1

  

3000 cm are assigned to O-H stretching vibration, and the absorption bands located at

• 1 -1

  

630–580 cm and at 480–420 cm are assigned to strong and weak strecthing vibrations of

M-O modes, respectively (Parry, 1963; Ryczkowski, 2001; Yurdakoç et al., 1999). The

presence of M-O modes is supported by the vibration band located at the wavelength of 570–

• 1

  

560 cm . The existence of BrØnsted – Lowry and Lewis sites is displayed by the absorption

• 1 -1

  

bands located at 1475–1420 cm and 1620–1510 cm , respectively (Yurdakoç et al., 1999;

Boucheffa et al., 2008).

  In the samples investigated, the presence of O-H functional group is indicated by the

• 1

  

absorption band, resulted from stretching vibration, located at 3450.62 cm . The existence

of Lewis acid sites in the sample is displayed by the adsorption bands located at 1637.78 cm

• 1

  

which indicate that the pyridine was bound to the surface of the sample by coordination

bond (Parry, 1963), while the existence of BrØnsted–Lowry acid sites is presented by the

  _{0.9 2}

_0.1

₄ BC.54 Preparation and characterization of nanosize spinel Ni Fe Cu O using pectin as binding agent

• 1

  

absorption bands located at 1384.28 cm . By comparing the intensities of the absorption

bands associated with Lewis and BrØnsted–Lowry acid sites, it can be concluded that the acid

characteristic of the sample is dominated by Lewis acid. In the fingerprint region of the

spectra, the absorption band representing strecthing vibration of Fe-O and bending vibration

• 1

  

of Ni-O and Cu-O was detected at 586.62, 450 and 430 cm (Ryczkowski, 2001 ; Situmeang

b

et al., 2015 ), suggesting the existences of Fe-O-Ni and Fe-O-Cu bond which confirms the

  0.9

  2

  0.1

  4 formation of Ni Fe Cu O structure as expected.

4. Conclusion and remarks

  This current study demonstrated the potential of pectin solution as a binding agent for

preparation of nano-size materials using sol gel method. The XRD results revealed that the

• – crystallite size of the Ni

0.9 Fe

2 Cu

  0.1 O 4 sample prepared is in the range of 12 to 20 nm. The

samples were found to exhibit Lewis and BrØnsted Lowry acid characteristics, with Lewis

• – acid as the dominant site, as revealed by the FTIR analyses. The agglomeration of Ni

  0.9 Fe

  2 Cu

0.1 O 4 particles reflected by a microsize distribution in PSA is characterized by the existence of particles with varied sizes and shapes.

  Acknowledgment The authors wish to thank and appreciate the Health Ministry, Republic of Indonesia

for research funding provided through Center for Standard and Certification, Health

  Polytechnics Program, Bandar Lampung.

  References Boucheffa, Y., Benaliouche, F., Ayrault, P., Mignard, S., & Magnoux, P. (2008). NH ^{3 -TPD and FTIR} Spectroscopy of pyridine adsorption studies for characterization of Ag- and Cu- exchanged X- zeolites. Microporous and Macroporous Material, 113(1–3), 80–88.

Candeiaa, R.A., Bernardi, M.I.B., Longoc, E., Santos, I.M.G., & Souzaa, A.G. (2004). Synthesis and

_{2 4} characterization of spinel pigment CaFe O obtained by the polymeric precursor method. Mater.

  Lett., 58, 569–572.

  Cullity, B.D. (1978). Elements of X-ray diffraction (2nd Ed.). Addison–Wesley, London. Corrias, A., Carta, D., Loche, D., Mountjoy, G., & Navarra, G. (2008). NiFe ^{2 O 4 nanoparticles dispersed}

in an aerogel silica matrix: An X-ray absorption study. J. Phys. Chem. C, 112, 15623–15630.

  

Daadmehr, V., Akbarnejad, R. H., Rezakhani, A. T., Tehrani, F. S., Aghakhani, F., & Gholipour, S. (2013).

  Catalytic activity of the spinel ferrite nanocrystals on the growth of carbon nanotubes. J.

  Supercond. Nov. Magn., 26(2), 429–435.

  

Hill, R.J., Craig, J.R., & Gibbs, G.V. (1979). Systematics of the spinel structure type. Phys. Chem.

  Minerals, 4(4), 317–339.

  

Imanaka, N., Wendusu, Yoshida, T., & Masui, T. (2015). Novel environmentally friendly inorganic

red pigments based on calcium bismuth oxides. J. Adv. Ceram., 4(1), 39–45.

Kumar, G.R., Kumar, K.V., & Venudhar, Y.C. (2012). Synthesis, structural and magnetic properties of

copper substituted nickel ferrites by Sol–Gel method. Mater. Scie. Appl., 3(2), 87–91.

Le, M.-V., Dao, H.-A., Ken-Hirota, Masaki-Kato, Phuo, Huynh-Ky, H. (2014). Preparation and

_{2 4 rd} characterization of spinel co-doped MnAl O obtained by Sol–Gel method. Proceedings of the 3

  World Conference on Applied Sciences, Engineering & Technology, Nepal, 709–715.

  

Maensiri, S., Masingboon, C., Bonochom, B., & Seraphin S. (2007). A simple route to synthesize nickel

_{2 4} ferrite (NiFe O ) nanoparticles using egg white. Script. Mat., 56, 797–800.

  SWUP R. Djayasinga, R. Situmeang ^BC.55

Murthy, Y.L.N., Viswanath, I.V.K., Rao, T.K., & Singh, R. (2009). Synthesis and characterization of nickel

copper ferrite. Int.J. ChemTech Res., 1(4), 1308–1311.

Niyaifar, M., Nazari, S., & Mohammadpour, H. (2014). Magnetic and structural studies of Mg 1-

_{x Zn x Fe 2 O 4 . Proceedings of AES-ATEMA 18 th} Int. Conf., Canada, 203–212.

Parry, E.P. (1963). An Infrared study of pyridine adsorbed on acidic solids characterization of surface

acidity. J. Catal., 2(5), 371–379. Perego, C., & Villa, P. (1997). Catalyst preparation methods. Catal. Today, 34, 281–305.

Qian, F.Z., Jiang, J.S., Jiang, D.M., Wang, C.M., & Zhang, W.G. (2010). Improved multiferroic properties

and a novel magnetic behavior of Bi ^{0.8 La 0.2 Fe 1-x Co x O 3 nanoparticles, J. Magn. Magn. Mater,} 322(20), 3127–3130.

Malvern Instruments (2012). A basic guide to particle characterization. Malvern Instrument Limited,

UK. Retreived from http://www.atascientific.com.au/publications/wp-content/uploads/2012/

07/MRK1806-01-basic-guide-to-particle-characterisation.pdf.

  

Roy, A., Gupta, R., & Garg, A. (2012). Multiferroic memories. Adv. Condens. Matter Phys., 2012, 1–12.

Ryczkowski, J. (2001). IR spectroscopy in catalysis. Catalysis Today, 68, 263–381.

Situmeang, R., Wibowo, S., Simanjuntak, W., Supryanto, R., Amalia, R., Septanto, M., Manurung, P., &

Sembiring, S. (2015a). Characteristics of nanosize spinel Ni ^x Fe ^3-x O ⁴ prepared by Sol–Gel method using egg white as emulsifying agent. J. Indones. Chem., 15(2), 116–122.

  

Situmeang, R., Manurung, P., Sulistiyo, S. T., Hadi, S., Simanjuntak, W., & Sembiring, S. (2015b). Sol–

Gel method for preparation of nanosize NiFe 2-x Co x O ^{4 using egg white. Asian J. Chem., 27(3), 1138–} 1142.

  

Sutka, A., Borisova, A., Kleperis, J., Mezinskis, G., Jakovlevs, D., & Juhnevica, I. (2012). Effect of nickel

addition on colour of nanometer spinel zinc ferrite pigments. J. Austral. Ceram. Soc., 48(2), 150– 155. Tanabe, K. (1970). Solid acids and bases: their catalytic properties. Kodansha, Tokyo.

Vanaja, M., Gnanajobitha, G., Paulkumar, K., Rajeshkumar, S., Malarkodi, C., & Annadurai, G. (2013).

  Phytosynthesis of silver nanoparticles by Cissus quadrangularis: influence of physicochemical factors. J. Nanostruct. Chem., 3(17), 1–8.

Waqas , H., Qureshi, A.H., Subhan, K., & Shahzad, M. (2012). Nanograin Mn–Zn ferrite smart cores to

miniaturize electronic devices. Ceram. Internat., 38(2), 1235–1240. Yehia, M., Labib, Sh., & Ismail, S.M. (2014). Structural and magnetic properties of nano-NiFe ^{2 O 4} prepared using green nanotechnology. Physica B, 446, 49–54.

Yurdakoç, M., Akçay, M., Tonbul, Y., & Yurdakoç, K. (1999). Acidity of silica-alumina catalysts by amine

titration using Hammett indicators and FT-IR study of pyridine adsorption. Turk. J. Chem., 23,

  319–327.