J Sol-Gel Sci Technol DOI 10.1007/s10971-017-4317-z ORIGINAL PAPER: SOL-GEL AND HYBRID MATERIALS WITH SURFACE MODIFICATION FOR APPLICATIONS Synthesis and characterization of a binary system La2O3–SiO2 prepared by combustion method 1 1 1 1 W. Nowicki ● Z. S. Piskuła ● P. Kuźma ● P. Kirszensztejn Received: 4 October 2016 / Accepted: 17 January 2017 © The Author(s) 2017; This article is published with open access at Springerlink.com Abstract La2O3–SiO2 powders were prepared by the Graphical Abstract La2O3–SiO2 binary oxide system sol–gel and combustion method without addition of strong was prepared by the sol–gel method without addition of polar solvents to the initial system. Changes in the crys- strong polar solvents (e.g., water, alcohol). The present talline La2O3 structure and modification of surface binary study is to propose a method for the synthesis of oxides system were described as a function of concentration La2O3–SiO2 samples with the use of three components of the second component, that is silicon dioxide. A series of (tetraethoxysilane, acetic acid, lanthanum acetate). samples of La to Si molar ratios of 1:0.0, 1:0.1, 1:0.2, 1:0.3, and 1:0.4 were characterised by X-ray powder diffraction, Thermogravimetric analysis, fourier transform infrared spectrum and low temperature nitrogen adsorption mea- surements. According to the results, even a large quantity of silicon oxide component in the binary oxides system led to relatively small increase in defects in hexagonal lanthanum oxides obtained in a non-aqueous medium. Keywords Non-aqueous sol–gel ● Binary supports ● ● La2O3/SiO2 Texture 1 Introduction Lanthanum oxide has a lot of attractive properties that permitted its wide applications, e.g., as catalysts [1, 2], Electronic supplementary material The online version of this article support for metal [3, 4], dielectric material [5, 6] and optical (doi:10.1007/s10971-017-4317-z) contains supplementary material, fi which is available to authorized users. lters [7]. In our previous work [8, 9], we have studied the amorphous nature of SiO2–La2O3 system even for the lar- * W. Nowicki gest quantity of lanthanum oxide (1:1 Si/La), which prefers [email protected] crystalline forms. We have presented the influence of a 1 fi – Faculty of Chemistry, Adam Mickiewicz University, Umultowska speci c type of anhydrous sol gel synthesis on the pro- 89b, 61-614 Poznań, Poland ducts, besides we have determined such parameters such as J Sol-Gel Sci Technol thermal stability and textural analysis [10]. The study pre- LaSi0.2, LaSi0.3 and LaSi0.4 respectively. The La2O3/SiO2 sented in this paper was undertaken for two reasons. The system was prepared on the basis of a modified procedure first aim was to study the structural changes in the crys- described in details in the previous paper [9]. The binary talline lanthanum oxide with different amounts of the oxide gel system was obtained by mixing the appropriate amorphous SiO2, and the second one was to determine the amounts of TEOS and a solution of La(CH3COO)3 in thermal stability and textural parameters of the samples anhydrous acetate acid. The homogenous solutions were studied. This study is a continuation of the investigation of closed in a reactor upon stirring and heated at 353 K for La2O3-SiO2 binary oxides system applied as a support for 48 h. The gels were dried at 393 K by slow evaporation metals catalysts with La/Si mole ratio between 1:0.0, and for 72 h. Synthesised binary oxide gels were ignited on the 1:0.4. The chemical stability of hexagonal La2O3 is insuf- evaporating dish, initiating a self-propagating combustion ficient, h–La2O3 usually reacts with H2O to form hydroxide process, and dark grey loose product was obtained after the lanthanum when it is left in natural air [11–13]. The pre- combustion was completed (Fig. S1 in Electronic Sup- sence of SiO2 component in the lanthanum oxide structure porting Information). The LaSi0.0 sample was synthesised can modify the bulk and surface properties of this com- by decomposition of lanthanum acetate after evaporation of pound, which could be of key importance for consideration acetate acid under reduced pressure from the solution. All of binary oxide gel as a support for metallic catalysts with a samples were placed in a muffle furnace, and preheated at crucial point of stabilisation of lanthanum oxide hydrolysis 600 °C for 4 h. All products obtained were post-annealed in in the gel network [14]. Furthermore, the presence of air atmosphere at 800 °C for 4 h. amorphous SiO2 is expected to improve textural properties – of the La2O3-SiO2 system. Traditional sol gel methods for 2.2 X-ray powder diffraction (XRD) and rietveld obtaining inorganic compounds are based on the hydrolysis- refinement polycondensation reaction of mixed metal alkoxides, strong inorganic acids and water [13]. Particularly important pro- XRD patterns were collected at room temperature by using blem is to control the reaction rate, which is very fast and a D8 Advance Diffractometer equipped with Johansson leads to a reduction in microstructural monitoring of the monochromator (λCu Kα1 = 1,5406 Å) and silicon strip final materials. An attractive solution is to use the sol–gel detector LynxEye. The intensities were measured in the process without adding water to the initial system. The 20–150o 2θ, with 0.02o step size and a measuring time of 2 sol–gel technique in a water-free environment can lead to s. per point. Crystalline phase identification was carried out improved control of the hydrolysis reaction rate, essential using the diffractometer analytical software after revision of for multicomponent systems in which the precursors applied the PDF4+ (2013) 4.11.0.3 ICDD database crystalline differ much in the kinetics of hydrolysis [9]. By controlling compounds [15]. X-ray line profile analysis was used for the hydrolysis through a slow release of esterification water, microstructural characterisation of LaSi0.0 and we prevented formation of large aggregates of the half- LaSi0.4 samples. The standard line profiles for the instru- products, and we could expect that the second component mental line broadening evaluation were obtained from the should be uniformly dispersed in binary oxide system as diffraction pattern of the standard reference material LaB6 final product of synthesis. We proposed a new procedure for (SRM 660a) [16]. The Topas 4.2 programme was used for the synthesis of binary oxide gel systems using only three quantitative Rietveld phase analysis [17]. compounds: lanthanum acetate, tetraethylorthosilicate (TEOS), and AcOH in water free environment. This method 2.3 Thermogravimetric analysis (TGA) permits a uniform distribution of the second reactant in the binary composite and makes it possible to design a new TGA was carried out in SETSYS 12 (Setaram, France) acid/base character of the surface of a catalyst or a support thermoanalyzer. The sample (20 mg), in a alumina crucibles for metal catalysts. was heated in flowing air from room temperature to 1100 °C at the rate of 5 oC/min. For all experiments, we used the fraction of the grain sizes between 100 and 200 Mesh. 2 Experimental 2.1 Synthesis of the sol–gel binary samples 2.4 Fourier transform infrared spectrum (FTIR) spectroscopy A series of La2O3–SiO2 samples were synthesised by the sol–gel method, with La to Si molar ratio of: 1:0.0; 1:0.1; FTIR spectra were recorded with a BRUKER 1:0.2; 1:0.3 and 1:0.4. The samples were marked according IFS88 spectrometer in the range of 4000–400 cm−1 with to the increasing content of silicon as LaSi0.0, LaSi0.1, 128 scans and a resolution of 1 cm−1. The samples were J Sol-Gel Sci Technol Fig. 1 The XRPD patterns of La2O3/SiO2 samples calcined under air at 600 °C prepared as pellets after dispersion in KBr matrix, and then the infrared transmission spectra were collected. 2.5 Porous structure Fig. 2 TGA curves for LaSi0.0 and LaSi0.4 samples in the air Textural parameters were obtained from the nitrogen atmosphere up to 1000 °C adsorption–desorption isotherms at 77 K, and were recorded performed using Micromeritics ASAP V2.00D analyser. reported values in PDF4+ ICDD database crystalline Prior to measurement, all samples were outgassed at 623 K compounds (PDF 00-048-1113) [15]. The low intensity at 0.4 Pa till constant weight. Both adsorption and deso- diffraction peaks indicate that the as-synthesised products rption branches of the isotherm were taken in the p/po range have poorly crystallised, therefore a study of the effect of 0–1. The specific surface area was calculated using multi- silicon incorporated in lanthanum oxycarbonate will be point BET analysis and the pore sizes were measured by the difficult. Additionally, the amorphous phase of SiO2 does Barrett–Joyner–Halenda (BJH) method of desorption. not produce additional visible reflexes in the XRD dia- grams. According to literature [19, 20] and the results of thermal analysis of the binary gel samples, the transfor- 3 Results and discussion mation of La2O2CO3 to La2O3 phase takes place. Figure 2 presents the results regarding the phase stabilities for Figure 1 shows the XRD patterns of as-synthesised La/Si LaSi0.0 and LaSi0.4. TG-TA-DTG curves for LaSi0.1, system by combustion method, and then calcined in a LaSi0.2, and LaSi0.3, respectively, are given in Fig. S2 in muffle furnace at 600 °C. All the diffraction peaks can be Electronic Supporting Information. The results obtained assigned to monoclinic phase with layered La2O2CO3-II from the range of 300–1373 K indicate that all samples have compound [18].