ISRN Nanomaterials

Volume 2012 (2012), Article ID 769528, 7 pages

doi:10.5402/2012/769528

Research Article

Synthesis and Characterization of Nanometric Pure Phase SnO₂ Obtained from Pyrolysis of Diorganotin(IV) Derivatives of Macrocycles

Mala Nath and P. K. Saini

Department of Chemistry, Indian Institute of Technology, Roorkee 247667, India

Received 11 July 2012; Accepted 27 July 2012

Academic Editors: W. Bao and A. Fidalgo

Copyright © 2012 Mala Nath and P. K. Saini. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Thermal decomposition of diorganotin(IV) derivatives of macrocycles of general formula, R₂Sn(L1) and R₂Sn(L2) (where R = n-butyl (1/4), methyl (2/5), and phenyl (3/6); H₂L1 = 5,12-dioxa-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-1,8-diene and H₂L2 = 6,14-dioxa-8,16-dimethyl-1,5,9,13-tetraazacyclotetradeca-1,9-diene), provides a simple route to prepare nanometric SnO₂ particles. X-ray line broadening shows that the particle size varies in the range of 36–57 nm. The particle size of SnO₂ obtained by pyrolysis of 3 and 5 is in the range of 5–20 nm as determined by transmission electron microscope (TEM). The surface morphology of SnO₂ particles was determined by scanning electron microscopy (SEM). Mathematical analysis of thermogravimetric analysis (TGA) data shows that the first step of decomposition of compound 4 follows first-order kinetics. The energy of activation (), preexponential factor (A), entropy of activation (), free energy of activation (), and enthalpy of activation () of the first step of decomposition have also been calculated. Me₂Sn(L2) and Ph₂Sn(L1) are the best precursors among the studied diorganotin(IV) derivatives of macrocycles for the production of nanometric SnO₂.

1. Introduction

In recent years nanometric SnO₂ is of current interest because of its semiconducting, optical, and electronic properties. In addition to these, tin(IV) oxide possesses potential applications such as catalytic supports [1, 2], transparent conducting electrodes [3], and gas sensors [4, 5]. SnO₂ is preferred over other metal oxides in gas sensors because of its high sensitivity and selectivity for different gases (e.g., H₂) in mixture [6]. Nanometric SnO₂ has different properties from bulk crystals; therefore, much attention has been addressed to synthesis and characterization of such materials. To produce nanometric SnO₂, a variety of chemical and physical methods [7–11] have been reported in the literature.

Tetraazamacrocycles and their derivatives have drawn special attention because of their applications in various fields such as analytical, industry, medicinal, and biological [12–16]. A thorough survey of literature reveals that only a few attempts have been made to study the thermal stability of metal complexes of tetraazamacrocycles [17]. However, a considerable attention has been given to the thermal decomposition of organometallic compounds in the last few years because they decompose at low temperature producing metallic oxides/sulfides and metallic particles. A thorough survey of literature reveals that limited studies have been carried out to prepare nanometric SnO₂ by the pyrolysis of single source organotin precursors [18–20]. Further, it is important to mention that there is only a single reference recently reported by us in which some organotin-macrocyclic complexes are used as single source precursors for preparation of nanometric SnO₂ through their pyrolysis route [21]. It is, therefore, worth investigating to explore the best precursors which would produce pure phase, nanosized SnO₂ on thermal decomposition.

In the present study, we report herein a simple route to prepare SnO₂ semiconducting nanoparticles by the thermal decomposition of diorganotin(IV) derivatives of 5,12-dioxa-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-1,8-diene and 6,14-dioxa-8,16-dimethyl-1,5,9,13-tetraazacyclotetradeca-1,9-diene using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques under air atmosphere. The residues (SnO₂) obtained were characterized by infrared (IR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), field emission scanning electron microscopy in combination with energy-dispersive X-ray spectrometry (FESEM-EDX), and transmission electron microscopy with electron diffraction analysis (TEM-ED).

2. Experimental Section

The details of synthesis and characterization of these organotin(IV)-macrocyclic complexes are similar to those reported previously [22]. Thermal measurements thermogravimetric (TG), differential thermal analysis (DTA) and derivative thermogravimetric (DTG), infrared (IR), and X-ray diffraction pattern (XRD) of residues were recorded on the same instruments as reported previously [22]. Nanometric SnO₂ was prepared by the thermal decomposition of organotin(IV) precursors in a tube furnace under similar experimental conditions up to the formation temperature of SnO₂ as determined by TG analysis. The surface morphology of SnO₂ particles was studied by using scanning electron microscope (SEM) and FESEM-EDX. The SEM images were recorded on a LEO 435 VP electron microscope and FESEM-EDX on FEI Quanta 200 FEG. The transmission electron photographs of SnO₂ particles obtained from Ph₂Sn(L1) and Me₂Sn(L2) were recorded on a FEI TECNAI 20 G2STWIN, at Institute Instrumentation Center, Indian Institute of Technology Roorkee, Roorkee. To record the SEM and FESEM with EDX analysis, SnO₂ particles were previously agitated ultrasonically for 30 min in dichloromethane to separate out nanoparticles from the algometric form. After agitation, the sample was placed on the glass slit with the help of a capillary, which was made conducting by silver gel and after drying the solvent, the sample was covered with gold thin layer. For TEM studies, the agitated particles under suspension were taken on the carbon grid. After drying the sample the TEM photographs were taken and recorded.

3. Results and Discussion

The structure and stoichiometry of the single source precursors, namely, orgaotin(IV) derivatives of macrocycles of general formula, R₂Sn(L1) and R₂Sn(L2) (where R = n-butyl, methyl, and phenyl; H₂L1 = 5,12-dioxa-7,14-dimethyl-1,4,8,11-tetraazacyclotetra-deca-1,8-diene and H₂L2 = 6,14-dioxa-8,16-dimethyl-1,5,9,13-tetraazacyclotetradeca-1,9-diene) were established by the various physicochemical and spectral studies as reported in our previous communication [22], and are again represented in Figures 1(a) and 1(b).

(a)

(b)

Figure 1: Structure of organotin(IV) macrocycles [22].

The TG and DTA curves of these compounds are presented in Figures 2 and 3, respectively, and the XRD patterns of the residues obtained are presented in Figure 4. As reported [22] earlier all of these complexes, except n-Bu₂Sn(L2), decomposed in two or three steps in the temperature range 100–1000°C yielding SnO₂ in the temperature range 252–600°C, which was confirmed by the XRD analysis and by the presence of ν(Sn–O) at 620 ± 5 cm⁻¹.

(a)

(b)

Figure 2: TGA plots of n-Bu₂Sn(L1) ( ), Me₂Sn(L1) ( ), Ph₂Sn(L1) ( ), n-Bu₂Sn(L2) ( ), Me₂Sn(L2) ( ), and Ph₂Sn(L2) ( ).

(a)

(b)

Figure 3: DTA plots of n-Bu₂Sn(L1) ( ), Me₂Sn(L1) ( ), Ph₂Sn(L1) ( ), n-Bu₂Sn(L2) ( ), Me₂Sn(L2) ( ), and Ph₂Sn(L2) ( ).

(a)

(b)

Figure 4: X-ray diffraction of SnO₂ obtained from pyrolysis of (a) n-Bu₂Sn(L1) ( ), Me₂Sn(L1) ( ), Ph₂Sn(L1) ( ); (b) n-Bu₂Sn(L2) ( ), Me₂Sn(L2) ( ), Ph₂Sn(L2) ( ).

The crystallite average size calculated by Scherrer equation [19, 23] (1) is in the range of 36−57 nm (Table 1).

where = 1.5418  is the wavelength of the incident beam, is the full width at half maximum in radians of the highest intensity line, and is the Bragge’s angle.

Table 1: Comparison of average size of the SnO₂ particles obtained by XRD, SEM, and TEM.

SnO₂ particles obtained from precursors
Particlessize by XRD (nm)
Particles size by SEM (nm)
Particles size by TEM (nm)

n-Bu₂Sn (L1)
41.68
50–200
—

Me₂Sn (L1)
57.26
50–145
—

Ph₂Sn (L1)
37.26
20–120
5–20

n-Bu₂Sn (L2)
41.69
50–180
—

Me₂Sn (L2)
35.81
20–100
5–15

Ph₂Sn (L2)
41.69
20–150
—

The SEM image of the residue (SnO₂) obtained by thermal decomposition of n-Bu₂Sn(L1) at 500–525°C is shown in Figure 5. The residues obtained by the pyrolysis of diorganotin(IV) derivatives of macrocycles were agitated ultrasonically for 30 min. In all the cases the SEM images of the residues (SnO₂) showed uniform grain size with almost spherical shape. The grain size measured by SEM is in the range of 20–200 nm in diameter. FESEM image with EDX analysis of the residue obtained by pyrolysis of Me₂Sn(L2) is represented in Figure 6. These images depict the formation of almost spherical particles in all of the cases. EDX analyses of these particles in SEM micrographs at various locations marked with the sign “+” show them to consist of Sn and O with SnO₂ composition.

Figure 5: SEM image of SnO₂ particles obtained by pyrolysis of n-Bu₂Sn(L1).

(a)  

(b)

Figure 6: FESEM image with EDX of SnO₂ particles obtained by pyrolysis of Me₂Sn(L2).

The size of SnO₂ particles obtained by pyrolysis of Ph₂Sn(L1) and Me₂Sn(L2) measured by TEM is in the range of 5–20 nm (Figures 7 and 8). There are many particles and holes about 5–20 nm size. Many connected grains form a random net work, in which various nanosized holes appear (Figure 8). Such structure is named as nanosponge [1]. This microstructure leads to a very high rate of interface and surface. There are a large number of nanometric grains in Figure 7, which have well-ordered lattices. The electron diffraction pattern of selected area (inset in Figures 7 and 8) appeared to be typical polycrystalline diffraction rings. According to the diameters of the rings, the spacings are 0.34, 0.026, 0.024 nm and 0.33, 0.026, 0.024 nm for SnO₂ particles obtained by pyrolysis of Ph₂Sn(L1) and Me₂Sn(L2), respectively. They are in accordance with the spacing of [110], [101], and [200] of tetragonal phase SnO₂. This indicates that the grains are nanocrystalline tetragonal SnO₂ [5]. On the basis of the above studies, Me₂Sn(L2) and Ph₂Sn(L1) are the best precursors among the studied diorganotin(IV) derivatives of macrocycles for the production of nanometric SnO₂.

(a)

(b)

Figure 7: TEM images of SnO₂ particles obtained by pyrolysis of Ph₂Sn(L1) with electron diffraction pattern.

(a)

(b)

Figure 8: TEM images of SnO₂ particles obtained by pyrolysis of Me₂Sn(L2) with electron diffraction pattern.

TG curves of n-Bu₂Sn(L2) show that the first step of the complex exhibits a characteristic, well-defined, and nonoverlapping pattern. Two different methods were used to evaluate kinetic data from the TG traces. The following kinetic data are applicable only for the first step of decomposition of the complexes, as the other steps are very slow and do not follow the first-order kinetics; therefore, kinetic parameters for those steps have not been evaluated. The order of decomposition of the n-Bu₂Sn(L2) complex is obtained by using Horowitz and Metzger equation [24]. The value of Cs is 0.391. Therefore, the calculated order shows that the decomposition follows first-order kinetics. The values of energy of activation () and preexponential factor (A) have been calculated using two different methods, namely, Horowitz and Metzger [24] and Coats and Redfern [25] methods. Following equations were employed to calculate the entropy of activation (2), the enthalpy of activation (3), and free energy of activation (4):

where and are the Planck’s and Boltzmann constants, respectively.

Kinetic parameters are given in Table 2. The negative values of indicate that the decomposition reaction is slow. The plot of Horowitz and Metzger method of n-Bu₂Sn(L2) (4) is presented in Figure 9(a), whereas that of Coats and Redfern method is presented in Figure 9(b).

Table 2: Kinetic data of thermal decomposition of n-Bu₂Sn (L2).

Complex
Parameters

From Horowitz and Metzger method

From Coats and Redfern method

n-Bu₂Sn (L2)
(kJ mol⁻¹)
272.20
312.67

A (s⁻¹)
9.01 × 10²³
7.2 × 10²⁴

(J K⁻¹ mol⁻¹)
−672.31
−655.00

(kJ mol⁻¹)
644.70
680.13

(kJ mol⁻¹)
267.53
312.67

(a)

(b)

Figure 9: For n-Bu₂Sn(L2) (a) a plot of [−log(log(/)] versus () () (Horowitz and Metzger method); and (b) a plot of [−log{(ln(/)/}] versus (1/) 10⁻³ K (Coats and Redfern method).

4. Conclusions

The residues obtained from thermal decomposition of R₂Sn(L1) and R₂Sn(L2) are SnO₂ as confirmed previously [22] by XRD analysis and infrared spectral studies. The crystal average size of SnO₂ calculated by Scherrer equation is in the range of 36–57 nm, whereas the size measured by SEM and TEM is in the range of ~20–200 nm and ~5–20 nm, respectively, in diameter. Me₂Sn(L2) and Ph₂Sn(L1) are the best precursors among the studied diorganotin(IV) derivatives of macrocycles for the production of nanosized tetragonal SnO₂. The kinetic parameters of the first-step decomposition of n-Bu₂Sn(L2) indicate that its decomposition is slow.

Acknowledgments

The authors are thankful to the Head, Institute Instrumentation Centre, Indian Institute of Technology Roorkee, Roorkee, India, for providing facilities to carry out thermal studies, X-ray diffraction analysis and to record SEM, FESEM-EDX, and TEM-ED images. Mr. P. K. Saini is thankful to the Council of Scientific and Industrial Research, New Delhi, India, for awarding Senior Research Fellowship.

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