Abstract
A new heterobimetallic nitrilotriacetatoperoxotitanate complex of titanium and lead [Pb(H2O)3]2[Ti2(O2)2O(nta)2]·4H2O (C6H6O6N=H3nta) was isolated in pure crystals directly from the solution containing tetrabutyl orthotitanate, hydrogen peroxoide, lead acetate, and nitrilotriacetic acid at pH = 2.0–4.0. The isolated complex was characterized by elemental analyses, IR spectrum, thermal analysis (TG), and single-crystal X-ray diffraction. The single-crystal X-ray structural analysis revealed that the titanium atom is N,O,O′,O′′-chelated by the nitrilotriacetate and O,O′-chelated by the peroxo group and was coordinated to the bridging O atom in an overall pentagonal-bipyramidal geometry. The thermal decomposition of this precursor led to the formation of phase-pure lead titanate (PbTiO3) at ≥450 °C. The morphology, microstructure, and crystalline of the resulting PbTiO3 product have been characterized by BET, transmission electron microscopy, and powder X-ray diffraction. The TEM micrographs revealed that the size of the as-synthesized crystallines to be 50–100 nm range. The BET measurement revealed that the PbTiO3 powders had a surface area of 5.6 m2/g.
Similar content being viewed by others
References
Jaffe WJ, Cook R, Jaffe H. Piezoelectric ceramics. New York: Academic Press; 1971.
Lines ME, Glass AM. Principles and applications of ferroelectrics and related materials. Oxford, UK: Oxford University Press; 2001.
Scott JF. Applications of modern ferroelectrics. Science. 2007;315:954–9.
Yang Y, Wang XH, Sun CK, Li LT. Photoluminescence of high-aspect-ratio PbTiO3 nanotube arrays. J Am Ceram Soc. 2008;91:3820–2.
Garnweitner G, Hentschel J, Antonietti M, Niederberger M. Nonaqueous synthesis of amorphous powder precursors for nanocrystalline PbTiO3, Pb(Zr, Ti)O3, and PbZrO3. Chem Mater. 2005;17:4594–9.
Ishikawa K, Yoshikawa K, Okada N. Size effect on the ferroelectric phase transition in PbTiO3 ultrafine particles. Phys Rev B. 1998;37:5852–5.
Zhong WL, Wang YG, Zhang PL, Wu BD. Phenomenological study of the size effect on phase transitions in ferroelectric particles. Phys Rev B. 1994;50:698–703.
Liu C, Zou BS, Rondinone AJ, Zhang ZJ. Sol-gel synthesis of free-standing ferroelectric lead zirconate titanate nanoparticles. J Am Chem Soc. 2001;123:4344–5.
Ren ZH, Xu G, Liu Y, Wei X, Zhu YH, Zhang XB, Lv GL, Wang YW, Zeng YW, Du PY, Weng WJ, Shen G, Jiang JZ, Han GR. PbTiO3 nanofibers with edge-shared TiO6 octahedra. J Am Chem Soc. 2010;132:5572–3.
Teff DJ, Caulton KG. Hydrolytic synthesis of lead oxo isopropoxides and their reaction with M((OPr)Pri)4 (M = Ti, Zr): comparisons and contrasts. Inorg Chem. 1998;37:2554–62.
Veith M. Molecular precursors for (nano) materials—a one step strategy. J Chem Soc Dalton Trans. 2002;32:2405–12.
Hubert-Pfalzgraf LG. Some trends in the design of homo- and heterometallic molecular precursors of high-tech oxides. Inorg Chem Commun. 2003;6:102–20.
Kessler VG. Molecular structure design and synthetic approaches to the heterometallic alkoxide complexes (soft chemistry approach to inorganic materials by the eyes of a crystallographer). Chem Commun. 2003;39:1213–22.
Veith M, Haas M, Huch V. Single source precursor approach for the sol–gel synthesis of nanocrystalline ZnFe2O4 and zinc-iron oxide composites. Chem Mater. 2005;17:95–101.
Li JG, Yang X, Ishigaki T. Urea coordinated titanium trichloride TiIII[OC(NH)2]6Cl3: a single molecular precursor yielding highly visible light responsive TiO2 nanocrystallites. J Phys Chem B. 2006;110:14611–8.
Hamid M, Tahir AA, Mazhar M, Zeller M, Hunter AD. Heterobimetallic molecular cages for the deposition of Cu/Ti and Cu/Zn mixed-metal oxides. Inorg Chem. 2007;46:4120–7.
Malghe YS, Dharwadkar SR. LaCrO3 powder from lanthanum trisoxalatochromate(III) (LTCR) precursor-Microwave aided synthesis and thermal characterization. J Therm Anal Calorim. 2008;95:915–8.
Thomas P, Dwarakanath K, Varma KBR, Kutty TRN. Synthesis of nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route. J Therm Anal Calorim. 2009;95:267–72.
Tahir AA, Mazhar M, Hamid M, Wijayantha KGU, Molloy KC. Photooxidation of water by NiTiO3 deposited from single source precursor [Ni2Ti2(OEt)2(μ-OEt)6(acac)4] by AACVD. Dalton Trans. 2009;38:3674–80.
Gonsalves LR, Verenkar VMS, Mojumdar SC. Preparation and characterization of Co0.5Zn0.5Fe2(C4H2O4)3·6N2H4. J Therm Anal Calorim. 2009;96:53–7.
Gawas UB, Mojumdar SC, Verenkar VMS. Synthesis, characterization, infrared studies, and thermal analysis of Mn0.6Zn0.4(C4H2O4)3·6N2H4 and its decomposition product Mn0.6Zn0.4Fe2O4. J Therm Anal Calorim. 2010;100:867–71.
Thurston J, Whitmire KH. Heterobimetal lic bismuth-transition metal salicylate complexes as molecular precursors for ferroelectric materials. Synthesis and structure of Bi2M2(sal)4(Hsal)4(OR)4 (M = Nb, Ta; R = CH2CH3, CH(CH3)2, Bi2Ti3(sal)8(Hsal)2, and Bi2Ti4((OPr)Pri)(sal)10(Hsal) (sal = O2CC6H4–2–O; Hsal = O2CC6H4–2–OH). Inorg Chem. 2002;41:4194–205.
Zhang HT, Yang JH, Shpanchenko RV, Abakumov AM, Hadermann J, Clérac R, Dikarev EV. New class of single-source precursors for the synthesis of main group-transition metal oxides: heterobimetallic Pb–Mn β-diketonates. Inorg Chem. 2009;48:8480–8.
Chae HK, Payne DA, Xu Z, Ma L. Molecular structure of a new lead titanium bimetallic alkoxide complex, [PbTi2(μ4-O)(OOCCH3)(OCH2CH3)]2: evolution of structure on heat treatment and the formation of thin-layer dielectrics. Chem Mater. 1994;6:1589–92.
Daniele S, Papiernik R, Hubert-Pfalzgraf LG, Jagner S, Håkansson M. Single-source precursors of lead titanate: synthesis, molecular structure and reactivity of Pb2Ti2(μ4-O) (μ3-O-i-Pr)2(μ-O-iPr)(O-i-Pr)4. Inorg Chem. 1995;34:628–32.
Hubert-Pfalzgraf LG, Daniele S, Papiernik R, Massiani MC, Septe B, Vaissermann J, Daran JC. Solution routes to lead titanate: synthesis, molecular structure and reactivity of the Pb–Ti and Pb–Zr species formed between various lead oxide precursors and titanium or zirconium alkoxides. Molecular structure of Pb2Ti2(μ4-O)(OAc)2(OPri)8 and of PbZr3 (μ4-O)(OAc)2(OPri)10. J Mater Chem. 1997;7:753–62.
Boulmaâz S, Papiernik R, Hubert-Pfalzgraf LG, Septe B, Vaissermann J. J Mater Chem. 1997;7:2053.
Mishra S, Daniele S, Hubert-Pfalzgraf LG. Metal 2-ethylhexanoates and related compounds as useful precursors in materials science. Chem Soc Rev. 2007;37:1770–87. and reference therein.
Zhou ZH, Deng YF, Jiang YQ, Wan HL, Ng SW. The first structural examples of tricitratotitanate [Ti(H2cit)3]2− dianions. Dalton Trans. 2003;33:2636–8.
Deng YF, Zhou ZH, Wan HL, Tsai KR. Ammonium barium citrato peroxotitanate(IV) Ba2(NH4)2[Ti4(O2)4(Hcit)2(cit)2]·10H2O: a molecular precursor of stoichiometric BaTi2O5. Inorg Chem Commun. 2004;7:169–72.
Deng YF, Zhou ZH, Wan HL. pH-Dependent isolations and spectroscopic, structural, and thermal studies of titanium citrate complexes. Inorg Chem. 2004;43:6266–73.
Deng YF, Zhang HL, Hong QM, Weng WZ, Wan HL, Zhou ZH. Titanium-based mixed oxides from a series of titanium(IV) citrate complexes. J Solid State Chem. 2007;180:3152–9.
Deng YF, Zhou ZH. A stable water-soluble molecular precursor for the preparation of stoichiometric strontium titanate. Inorg Chem Commun. 2008;11:1064–6.
Zhou ZH, Hong QM, Deng YF. Pure Ti-based mixed oxides prepared from the thermal decompositions of molecular precursors of peroxo complexes coordinated with tris(hydroxycarbonylmethyl) amine trivalent anion Titanate(IV). Acta Chim Sinica. 2004;62:2379–85.
Deng YF, Tang SD, Lao LQ, Zhan SZ. Synthesis of magnesium titanate nanocrystallites from a cheap and water-soluble single source precursor. Inorg Chim Acta. 2010;363:827–9.
Deng YF, Tang SD, Wu SP. Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor. Solid State Sci. 2010;12:339–44.
Deng YF, Lv QY, Wu SP, Zhan SZ. Heterobimetallic peroxo-titanium(IV) nitrilotriacetate complexes as single source precursors for preparation of MTiO3 (M = Co, Ni and Zn). Dalton Trans. 2010;39:2497–503.
Sheldrick GM. Schelxl-97, Program for refinement of crystal structure. Göttingen, Germany: University of Göttingen; 1997.
Kakihana M, Tada M, Shiro M, Petrykin V, Osda M, Nakamura Y. Structure and stability of water soluble (NH4)8[Ti4(C6H4O7)4(O2)4]·8H2O. Inorg Chem. 2001;40:891–4.
Kourgiantakis M, Matzapetakis M, Raptopoulou CP, Terzis A, Salifoglou A. Lead-citrate chemistry. Synthesis, spectroscopic and structural studies of a novel lead(II)-citrate aqueous complex. Inorg Chim Acta. 2000;297:134–8.
Moon J, Li T, Randall CA, Adair JH. Low temperature synthesis of lead titanate by a hydrothermal method. J Mater Res. 1997;12:189–97.
Selbach SM, Wang GZ, Einarsrud MA, Grande T. Decomposition and crystallization of a sol–gel-derived PbTiO3 precursor. J Am Ceram Soc. 2007;90:2649–52.
Acknowledgements
We thank “The Fundamental Research Funds for the Central Universities, SCUT (No. 2009ZM0313)”. We also thank “The National Science Foundation of China (No. B5080320)” and the “SRP” of South China University of Technology.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tang, S., Deng, Y. & Zhan, S. Chloro-free route to mixed-metal oxides. Synthesis of lead titanate nanoparticles from a single-source precursor route. J Therm Anal Calorim 104, 653–659 (2011). https://doi.org/10.1007/s10973-010-0999-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-010-0999-y