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  • 1 Department of Chemistry, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, People’s Republic of China
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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.

  • 1. Jaffe, WJ, Cook, R, Jaffe, H 1971 Piezoelectric ceramics Academic Press New York.

  • 2. Lines, ME, Glass, AM 2001 Principles and applications of ferroelectrics and related materials Oxford University Press Oxford, UK .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Scott, JF Applications of modern ferroelectrics. Science 2007 315:954959 .

  • 4. Yang, Y, Wang, XH, Sun, CK, Li, LT 2008 Photoluminescence of high-aspect-ratio PbTiO3 nanotube arrays. J Am Ceram Soc 91:38203822 .

  • 5. Garnweitner, G, Hentschel, J, Antonietti, M, Niederberger, M 2005 Nonaqueous synthesis of amorphous powder precursors for nanocrystalline PbTiO3, Pb(Zr, Ti)O3, and PbZrO3. Chem Mater 17:45944599 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Ishikawa, K, Yoshikawa, K, Okada, N 1998 Size effect on the ferroelectric phase transition in PbTiO3 ultrafine particles. Phys Rev B 37:58525855 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Zhong, WL, Wang, YG, Zhang, PL, Wu, BD 1994 Phenomenological study of the size effect on phase transitions in ferroelectric particles. Phys Rev B 50:698703 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Liu, C, Zou, BS, Rondinone, AJ, Zhang, ZJ 2001 Sol-gel synthesis of free-standing ferroelectric lead zirconate titanate nanoparticles. J Am Chem Soc 123:43444345 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. 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 2010 PbTiO3 nanofibers with edge-shared TiO6 octahedra. J Am Chem Soc 132:55725573 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Teff, DJ, Caulton, KG 1998 Hydrolytic synthesis of lead oxo isopropoxides and their reaction with M((OPr)Pri)4 (M = Ti, Zr): comparisons and contrasts. Inorg Chem 37:25542562 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Veith, M Molecular precursors for (nano) materials—a one step strategy. J Chem Soc Dalton Trans 2002 32:24052412 .

  • 12. Hubert-Pfalzgraf, LG 2003 Some trends in the design of homo- and heterometallic molecular precursors of high-tech oxides. Inorg Chem Commun 6:102120 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Kessler, VG 2003 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 39:12131222 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Veith, M, Haas, M, Huch, V 2005 Single source precursor approach for the sol–gel synthesis of nanocrystalline ZnFe2O4 and zinc-iron oxide composites. Chem Mater 17:95101 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Li, JG, Yang, X, Ishigaki, T 2006 Urea coordinated titanium trichloride TiIII[OC(NH)2]6Cl3: a single molecular precursor yielding highly visible light responsive TiO2 nanocrystallites. J Phys Chem B 110:1461114618 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Hamid, M, Tahir, AA, Mazhar, M, Zeller, M, Hunter, AD 2007 Heterobimetallic molecular cages for the deposition of Cu/Ti and Cu/Zn mixed-metal oxides. Inorg Chem 46:41204127 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Malghe, YS, Dharwadkar, SR 2008 LaCrO3 powder from lanthanum trisoxalatochromate(III) (LTCR) precursor-Microwave aided synthesis and thermal characterization. J Therm Anal Calorim 95:915918 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Thomas, P, Dwarakanath, K, Varma, KBR, Kutty, TRN 2009 Synthesis of nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route. J Therm Anal Calorim 95:267272 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Tahir, AA, Mazhar, M, Hamid, M, Wijayantha, KGU, Molloy, KC 2009 Photooxidation of water by NiTiO3 deposited from single source precursor [Ni2Ti2(OEt)2(μ-OEt)6(acac)4] by AACVD. Dalton Trans 38:36743680 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Gonsalves, LR, Verenkar, VMS, Mojumdar, SC 2009 Preparation and characterization of Co0.5Zn0.5Fe2(C4H2O4)3·6N2H4. J Therm Anal Calorim 96:5357 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Gawas, UB, Mojumdar, SC, Verenkar, VMS 2010 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 100:867871 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Thurston, J, Whitmire, KH 2002 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 41:41944205 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Zhang, HT, Yang, JH, Shpanchenko, RV, Abakumov, AM, Hadermann, J, Clérac, R, Dikarev, EV 2009 New class of single-source precursors for the synthesis of main group-transition metal oxides: heterobimetallic Pb–Mn β-diketonates. Inorg Chem 48:84808488 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Chae, HK, Payne, DA, Xu, Z, Ma, L 1994 Molecular structure of a new lead titanium bimetallic alkoxide complex, [PbTi24-O)(OOCCH3)(OCH2CH3)]2: evolution of structure on heat treatment and the formation of thin-layer dielectrics. Chem Mater 6:15891592 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Daniele, S, Papiernik, R, Hubert-Pfalzgraf, LG, Jagner, S, Håkansson, M 1995 Single-source precursors of lead titanate: synthesis, molecular structure and reactivity of Pb2Ti24-O) (μ3-O-i-Pr)2(μ-O-iPr)(O-i-Pr)4. Inorg Chem 34:628632 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Hubert-Pfalzgraf, LG, Daniele, S, Papiernik, R, Massiani, MC, Septe, B, Vaissermann, J, Daran, JC 1997 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 Pb2Ti24-O)(OAc)2(OPri)8 and of PbZr34-O)(OAc)2(OPri)10. J Mater Chem 7:753762 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Boulmaâz, S, Papiernik, R, Hubert-Pfalzgraf, LG, Septe, B, Vaissermann, J 1997 J Mater Chem 7:2053 .

  • 28. Mishra S , Daniele S, Hubert-Pfalzgraf LG. Metal 2-ethylhexanoates and related compounds as useful precursors in materials science. Chem Soc Rev. 2007;37: 177087. and reference therein.

    • Search Google Scholar
    • Export Citation
  • 29. Zhou, ZH, Deng, YF, Jiang, YQ, Wan, HL, Ng, SW 2003 The first structural examples of tricitratotitanate [Ti(H2cit)3]2− dianions. Dalton Trans 33:26362638 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30. Deng, YF, Zhou, ZH, Wan, HL, Tsai, KR 2004 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 7:169172 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 31. Deng, YF, Zhou, ZH, Wan, HL 2004 pH-Dependent isolations and spectroscopic, structural, and thermal studies of titanium citrate complexes. Inorg Chem 43:62666273 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32. Deng, YF, Zhang, HL, Hong, QM, Weng, WZ, Wan, HL, Zhou, ZH 2007 Titanium-based mixed oxides from a series of titanium(IV) citrate complexes. J Solid State Chem 180:31523159 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 33. Deng, YF, Zhou, ZH 2008 A stable water-soluble molecular precursor for the preparation of stoichiometric strontium titanate. Inorg Chem Commun 11:10641066 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 34. Zhou, ZH, Hong, QM, Deng, YF 2004 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 62:23792385.

    • Search Google Scholar
    • Export Citation
  • 35. Deng, YF, Tang, SD, Lao, LQ, Zhan, SZ 2010 Synthesis of magnesium titanate nanocrystallites from a cheap and water-soluble single source precursor. Inorg Chim Acta 363:827829 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 36. Deng, YF, Tang, SD, Wu, SP 2010 Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor. Solid State Sci 12:339344 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37. Deng, YF, Lv, QY, Wu, SP, Zhan, SZ 2010 Heterobimetallic peroxo-titanium(IV) nitrilotriacetate complexes as single source precursors for preparation of MTiO3 (M = Co, Ni and Zn). Dalton Trans 39:24972503 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38. Sheldrick, GM 1997 Schelxl-97, Program for refinement of crystal structure University of Göttingen Göttingen, Germany.

  • 39. Kakihana, M, Tada, M, Shiro, M, Petrykin, V, Osda, M, Nakamura, Y 2001 Structure and stability of water soluble (NH4)8[Ti4(C6H4O7)4(O2)4]·8H2O. Inorg Chem 40:891894 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 40. Kourgiantakis, M, Matzapetakis, M, Raptopoulou, CP, Terzis, A, Salifoglou, A 2000 Lead-citrate chemistry. Synthesis, spectroscopic and structural studies of a novel lead(II)-citrate aqueous complex. Inorg Chim Acta 297:134138 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 41. Moon, J, Li, T, Randall, CA, Adair, JH 1997 Low temperature synthesis of lead titanate by a hydrothermal method. J Mater Res 12:189197 .

  • 42. Selbach, SM, Wang, GZ, Einarsrud, MA, Grande, T 2007 Decomposition and crystallization of a sol–gel-derived PbTiO3 precursor. J Am Ceram Soc 90:26492652 .

    • Crossref
    • Search Google Scholar
    • Export Citation

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
per Year
24
Founder Akadémiai Kiadó
Founder's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)