Title of Invention

AN IMPROVED SOL-GEL PROCESS FOR THE PREPARATION OF NANOCRYSTALLINE CETI2O6 POWDER

Abstract

The present invention provides an improved sol-gel process for the preparation of nanocrystalline CeTi2O6 compound, which has applications in the area of photocatalytic activity. This compound can be obtained by completely drying the solution, which comprises both titanium and cerium precursors into a xerogel and sintering it at a temperature of 1400°C for 5 min. in air. The Ce:Ti mole ratio in the precursor sol for the preparation of this compound is identified in the range of 0.33:1 and 0.6:1.

Full Text

Field of the invention The present invention relates to an improved sol-gel process for the preparation of nanocrystalline CeTi2O6 powder. Particularly, the present invention provides an improved process for the preparation of highly chemically stable nanocrystalline CeTi2Oe state. Background of the invention In the developmental process of WOs based transmissive ECDs, we are concentrating our efforts for developing ion storage counter electrode films with a high transmittance for visible light both in the charged and discharged state and an ion storage capacity exceeding 20 mCcm"2 or comparable to WO3 to provide sufficient number of ions for deep colouration. Therefore, work has been undertaken in this direction for the synthesis of CeO2 precursors doped with TiO2 via a wet chemistry route. The widely used sol-gel process offers numerous advantages over the other conventional deposition techniques, which include tailor making of the film's properties, introduction of porosity in the films, low process cost and possible processing at low temperature. Preparation of CeO2 based films by sol-gel technique has been attempted following various routes. The use of alkoxides, the most popular precursor material in sol-gel processing has been reported by D. Keomany, C. Poinsignon, D. Deroo. in Sol. Energy Mater. Sol. Cells 33 (1994) 429-441. Alternately salts of cerium, like CeCI3.7H2O, [(NH4)2{Ce(N03)6}] in combination with Ti alkoxides have been shown by A. Makishima, M. Asami and K. Wada, in J. Non-Cryst. Solids 121 (1990) 310-314 as one of the routes to get CeO2-TiO2 films. Based on the earlier reports on these materials, A. Makishima, M. Asami and K. Wada, in J. Non-Cryst. Solids 121 (1990) 310-314 have performed a study in which the type of alkoxyl group of titanium alkoxide and the kind of catalyst have been varied in order to study their influence on the properties of the films. The films deposited by the authors have been sintered at 500°C and the XRD patterns of these films are characterized by the appearance of diffraction peaks of the CeO2 phase alone. In our earlier invention, we have reported the preparation of CeTi2O6 compound in thin film form using a sol-gel process employing the same precursor materials as in the present invention. CeTi2O6 thin films have the potential to be used as passive counter electrodes in electrochromic devices. In the sol-gel process, using alkoxide compounds, hydrolysis and condensation reactions are crucial for obtaining a gel. Through hydroxylation-condensation reactions, oxopolymers from transition metal alkoxides (TMA) can be grown into an oxide network as has been reported by D.C. Bradley, R.C. Mehrotra and DP. Gaur in Metal Alkoxides (Academic Press, New York, 1978). The normal course of the reaction for transition metal alkoxides dissolved in a solvent leads to precipitation of the polymers. Control of the reactivity of TMA is necessary in order to obtain sols and gels. In titanium-based systems, this control is achieved through the addition of complexing agents and salts such as eerie ammonium nitrate and cerium chloride. Photocatalytic reaction sensitized by TiO2 and other semiconducting materials has attracted extensive interest as a potential way of solving energy and environmental issues. Several cerium titanates have been investigated for photocatalytic activity. Yellow colored cerium titanate, CeTi2O6 with mainly Ce4+ state is known to cause photobleaching of methylene blue aqueous solution with irradiation of Xe discharge light as reported by S.O-Y-Matsuo, T.Omata, M.Yoshimura in J. Alloys and Compounds, 376 (2004) 262-267. Mixed CeO2-TiO2 films are reported by Q.N.Zhao, C.L.Li, X.J.Zhao in Key Engineen'ng Materials 249 (2003) 451-456 to decolorize methyl orange solutions upon irradiation of the UV light. Brannerite, UTi2O6 is an accessory phase in the titanate-based crystalline ceramics of synroc as reported by A.E. Ringwood, S.E. Kession, N.G. Ware, W. Hibberson, A. Major in Nature (London) 278 (1979) 219. The ideal formula of natural brannerite is (U,Th)1.xTi2+xO6 with a uranium deficiency and excess titanium. Possible cation substitutions identified in natural brannerite for uranium are Pb, Ca, Th, Y, Ce and for titanium are Si, Al, Fe. Stoichiometric brannerite is monoclinic with space group C2/m. There are two different distorted octahedra in CeTi2Oe structure. Distorted TiO6 octahedra form a zigzag sheet by sharing common edges, and each Ti octahedron shares three edges with titanium octahedra and three corners with cerium octahedra. The sheets of TiO6 octahedra are identical with those of the anatase structure parallel to (101) plane. The Ce cations located at the interlayer sites connect adjacent sheets. Each cerium octahedron shares two common edges with neighboring cerium octahedra and four corners with TiO6 octahedra. As has been reported by K.B. Helean, A. Navrotsky, G.R. Lumpkin, M. Colella, J. Lian, R.C. Ewing, B. Ebbinghaus and J.G. Catalano in J. Nucl. Mater. 320 (2003) 231-244, CeTi2O6 in the powdered form can be prepared by sintering in air (at 1350°C for > 100 h) a pellet containing stoichiometric portions of the oxides, CeO2 and TiO2. The preparation of CeTi2O6 solid solution using cerous nitrate and titanium tetrachloride precursors has been reported by Y. Chen, X. Jiang and L. Lou in CN1565724. As reported by Chen Linchen, Lu Guanglie, and Hu Xiurong in J. Rare Earths, 21 (2003) 108 -111, the formation of CeTi2O6 powder using the sol-gel process is possible using precursor materials, Ce(NO3)3.6H2O, Ti(OBu)4 in anhydrous ethanol. The present invention reports the synthesis of CeTi2Oe compound from different precursors i.e. cerium chloride heptahydrate and titanium propoxide. In the present invention, the CeTi2Oe phase has been achieved in powdered form by the sol-gel technique, which represents a reliable, low-cost chemical route. In comparison to the powdered CeTiaOe material, which is formed by other research groups by ball milling stoichiometric portions of CeO2 and TiO2, the same material in the present invention is prepared by a simple sol-gel process wherein homogeneous solutions containing different precursors can be prepared at relative ease and greater precision. CeTi2Oe compound has the potential for use as a photocatalytic agent. The CeTi2Oe compound in the present invention has shown superior response as a photocatalyst in comparison to TiO2 powder, which is the best known photocatalytic agent as per the literature reports. Using cerium chloride heptahydrate and titanium propoxide precursors, we have reported earlier in Sol. Ener. Mater. Sol. Cells 86 (2005) 85-103, the formation of a mixed compound of CeO2 and Ti02 i.e. CeO1.6.2TiO2 in thin films at annealing temperature of 500°C from the Ce:Ti compositions, 4:1 and 2:1. Dbjects of the invention The main object of the present invention is to provide an improved sol-gel process for the preparation of nanocrystalline CeTi2O6 powder. Another object of the present invention is to have a process, which will result in CeTi2Oe powder with high chemical durability. Yet another object of the present invention is to prepare nanocrystalline CeTi206 phase in the powder form. Yet another object of the present invention is to prepare powdered CeTi2C>6 compound from different Ce/Ti compositions in the sol. Still another object of the present invention is to use a process, which involves a very few number of simple steps. Brief description of drawings Figure 1 represents the XRD pattern of the CeTi2O6 compound. Figure 2 represents the bright field micrograph and electron diffraction pattern of the CeTiaOe compound. Figure 3 represents the absorbance spectra of as-prepared eosin solution without the CeTi2C>6 compound and in the presence of CeTi2Oe compound upon UV-Visible light irradiation for 2 hrs. Figure 4 represents the absorption spectra of eosin solution in the presence of CeTi2O6 and TiO2 powder after UV-Visible light irradiation for 2 hrs. Summary of the invention Accordingly the present invention provides an improved sol-gel process for the preparation of nanocrystalline CeTi2O6 powder, the said process comprising the steps of: (a) preparing an ethanolic solution of about 0.20-0.30 M cerium chloride heptahydrate, (b) adding the above said solution obtained in step (a) to titanium propoxide to obtain a reaction mixture having concentration of titanium propoxide in the range of 0.331-0.80 M and a mole ratio of Ce to Ti in the range of 0.33:1 to 0.6:1and stirring it for a period of 4-10 min, followed by aging at a temperature of 20-30°C, for a period of about one week to obtain the xerogel, c) sintering the above said xerogel obtained in step (b) in air at a temperature in the range of 1390-1410°C, for a period of 2-10 min. to obtain the desired product. In an embodiment of the present invention the strength of the cerium chloride heptahydrate solution is 0.20-0.25 M. In yet another embodiment the concentration of titanium propoxide in solution used in step (b) is in the range of 0.338-0.860 M. In yet another embodiment the sintering temperature used in step (c) is in the range of 1395-1405 °C. In yet another embodiment the time period used for sintering in step (c) is in the range of 3-5 min. In comparison to the powdered CeTi206 material, which is prepared by other research groups by ball milling stoichiometric portions of CeO2 and TiO2 and pressing the mixture into a pellet followed by sintering, the same material in the present invention is prepared by a simple sol-gel process wherein homogeneous Ce/Ti solutions containing Ce and Ti in desirable mole ratios can be prepared at greater ease. Novelty of the present invention lies in the use of a sol-gel process for the preparation of highly chemically stable nanocrystalline CeTi2O6 by using precursor materials, which are different from the one reported in the literature. Detailed description of the invention The initial clear, colorless solution of cerium chloride heptahydrate is prepared by stirring the cerium salt in absolute ethanol until the salt dissolves completely. The solution is prepared at ambient temperature. Ti alkoxides readily hydrolyze in aqueous and alcoholic solutions. The addition of cerium based alcoholic solution to titanium propoxide such that Ce:Ti mole ratio is between 0.33:1 and 0.6:1 does not induce precipitation into the titanium propoxide. The cerium salt stabilizes the alkoxide solution and prevents the precipitation of the hydroxides. The gelation time of the solution varies depending on the content of Ti alkoxide in the solution. The gelation time for Ce:Ti mole ratio (0.6:1, 0.5:1, 0.4:1 and 0.33:1) solutions is approximately one week depending on the ambient temperature and humidity conditions. The sols after aging and complete drying have been thermally treated at 1400°C for 5 min. in air at the heating rate of 1-2° Cmin"1. Ce:Ti (0.6:1, 0.5:1, 0.4:1 and 0.33:1) solutions based on cerium chloride heptahydrate and titanium propoxide have been prepared by dissolving the alkoxide in 0.22 M cerium chloride solution. The following examples illustrate the preparation of sol preferred for the preparation of CeTiaOe powder and should not be construed to limit the scope of the present invention. Example 1 0.22 M solution of cerium chloride heptahydrate (CeCI3.7H2O, Merck) has been prepared in absolute ethanol (C2H5OH, Merck). The above clear, colorless solution has been added to titanium propoxide such that the Ce:Ti mole ratio in the solution is 0.5:1. The resultant bright yellow solution has been stirred for 5 min. After allowing the commencement of gelation in the resultant yellow solution, the sol has been kept in ambient conditions in a closed glass vessel to allow complete drying of the gel in order to yield a xerogel. Subsequently, the xerogel has been thermally treated at 1400°C for 5 min. in air at a heating rate of 1-2°Cmin"1. The XRD results (Figure 1) have shown the formation of monoclinic CeTiaOe phase in the powder form with an average crystallite size of 24.2 nm. The TEM images of the same compound are shown in Figure 2. Example 2 0.22 M solution of cerium chloride heptahydrate (CeCI3.7H2O, Merck) has been prepared in absolute ethanol (C2H5OH, Merck). The above clear, colorless solution has been added to titanium propoxide such that the Ce:Ti mole ratio in the solution is 0.6:1. The resultant bright yellow solution has been stirred for 5 min. After allowing the commencement of gelation in the resultant yellow solution, the sol has been kept in ambient conditions in a closed glass vessel to allow complete drying of the gel in order to yield a xerogel. Subsequently, the xerogel has been thermally treated at 1400°C for 5 min. in air at a heating rate of 1-2°Cmin"1. The XRD results have shown the formation of monoclinic CeTi2O6 phase in the powder form with an average crystallite size of 18.1 nm. Example 3 0.22 M solution of cerium chloride heptahydrate (CeCl3.7H2O, Merck) has been prepared in absolute ethanol (C2H5OH, Merck). The above clear, colorless solution has been added to titanium propoxide such that the Ce:Ti mole ratio in the solution is 0.4:1. The resultant bright yellow solution has been stirred for 5 min. After allowing the commencement of gelation in the resultant yellow solution, the sol has been kept in ambient conditions in a closed glass vessel to allow complete drying of the gel in order to yield a xerogel. Subsequently, the xerogel has been thermally treated at 1400°C for 5 min. in air at a heating rate of 1-2°Cmin"1. The XRD results have shown the formation of monoclinic CeTi206 phase in the powder form with an average crystallite size of 28.2 nm. Figure 3 shows the absorption spectra of eosin (yellow shade) solution in the as-prepared state and upon irradiation by 80 W mercury vapor lamp for 2 hrs. in the presence of CeTi2O6 compound. Figure 4 provides the absorption spectra of eosin solution irradiated in the presence of CeTi2Oe and TiO2 powders for 2 hrs. Example 4 0.22 M solution of cerium chloride heptahydrate (CeCI3.7H2O, Merck) has been prepared in absolute ethanol (C2H5OH, Merck). The above clear, colorless solution has been added to titanium propoxide such that the Ce:Ti mole ratio in the solution is 0.33:1. The resultant bright yellow solution has been stirred for 5 min. After allowing the commencement of gelation in the resultant yellow solution, the sol has been kept in ambient conditions in a closed glass vessel to allow complete drying of the gel in order to yield a xerogel. Subsequently, the xerogel has been thermally treated at 1400°C for 5 min. in air at a heating rate of 1-2°Cmin"1. The XRD results have shown the formation of monoclinic CeTi2O6 phase in the powder form with an average crystallite size of 16.5 nm. Table I shows the comparison of CeTi2O6 crystallite size obtained from different Ce:Ti mole ratios. Table I: Crystallite size of CeTi2O6 phase obtained from different Ce:Ti mole ratios. (Figure Removed) The main advantages of the present invention are: 1. In comparison to the powdered CeTi2O6 material, which is prepared by other research groups by ball milling stoichiometric portions of CeO2 and TiO2 and pressing that mixture into a pellet followed by sintering, the same material in the present invention is prepared by a simple sol-gel process wherein homogeneous Ce/Ti solutions containing desirable Ce/Ti mole ratios can be prepared at relative ease with greater precision. These results further confirm the advantages of the sol-gel process over other conventional techniques, since the precision in mixing of different components is possible in this process even at the atomic level. 2. The above said difficult process of mixing CeO2 and TiO2 solid precursors for the formation of CeTi2O6 compound has been replaced in the present invention by a simplified sol-gel process. It is evident that the mixing of different precursors in a solution phase is much simpler than the assimilation in a solid phase. 3. In the present invention, four simplified steps are only required for the preparation of CeTi2C>6 compound. 4. The preparation of sol used for the formation of CeTi2O6 compound takes very less time. 5. Methodology followed in the present invention does not require expensive instruments. 6. In the present invention, the sintering temperature duration for the preparation of CeTi2Oe compound is 5 min. only. Importantly, the duration of the heat treatment reported earlier for the formation of this compound is 100 h. 7. This compound finds application in area of photocatalytic activity. 8. In comparison to TiO2 powder, the CeTi2Oe compound prepared in the present invention has decolorized the eosin (yellow shade) solution at a faster rate. We claim 1. An improved sol-gel process for the preparation of nanocrystalline CeTi2O6 powder, the said process comprising the steps of: a) preparing an ethanolic solution of about 0.20-0.30 M cerium chloride heptahydrate, b) adding the above said solution obtained in step (a) to titanium propoxide to obtain a reaction mixture having concentration of titanium propoxide in the range of 0.331-0.80 M and a mole ratio of Ce to Ti in the range of 0.33:1 to 0.6:1and stirring it for a period of 4-10 min, followed by aging at a temperature of 20-30°C, for a period of about one week to obtain the xerogel, c) sintering the above said xerogel obtained in step (b) in air at a temperature in the range of 1390-1410°C, for a period of 2-10 min. to obtain the desired product. 2. A process as claimed in claim 1, wherein the strength of the cerium chloride heptahydrate solution used is preferably in the range of 0.20-0.25 M. 3. A process as claimed in claim 1, wherein the concentration of titanium propoxide in solution used in step (b) is preferably in the range of 0.338-0.860 M. 4. A process as claimed in claim 1, wherein the sintering temperature used in step (c) is preferably in the range of 1395-1405 °C. 5. A process as claimed in claim 1, wherein the time period used for sintering in step (c) is preferably in the range of 3-5°C. 6. A sol-gel process for the preparation of monoclinic CeTiaOe phase in powder form substantially as herein described with reference to the examples and drawings accompanying this specification.

Documents:

279-del-2007-abstract.pdf

279-del-2007-Claims-(30-04-2013).pdf

279-del-2007-claims.pdf

279-del-2007-Correspondance Others-(30-04-2013).pdf

279-del-2007-Correspondence Others-(14-01-2013).pdf

279-del-2007-Correspondence Others-(20-03-2013).pdf

279-del-2007-Correspondence Others-(26-08-2008).pdf

279-DEL-2007-Correspondence Others-(28-02-2012).pdf

279-del-2007-correspondence-others.pdf

279-del-2007-description (complete).pdf

279-del-2007-drawings.pdf

279-del-2007-form-1.pdf

279-del-2007-Form-18-(26-08-2008).pdf

279-del-2007-form-2.pdf

279-del-2007-Form-3-(14-01-2013).pdf

279-del-2007-Form-3-(20-03-2013).pdf

279-DEL-2007-Form-3-(28-02-2012).pdf

279-del-2007-form-3.pdf

279-del-2007-form-5.pdf

279-del-2007-Petition-137-(20-03-2013).pdf