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Titanium phosphonate oxo-alkoxide "clusters": solution stability and facile hydrolytic transformation into nano titania

Svensson, Fredric and Daniel, Geoffrey and Tai, Cheuk-Wai and Seisenbaeva, Gulaim and Kessler, Vadim (2020). Titanium phosphonate oxo-alkoxide "clusters": solution stability and facile hydrolytic transformation into nano titania. RSC Advances. 10 , 6873-6883
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Abstract

Titanium (oxo-) alkoxide phosphonate complexes were synthesized using different titanium precursors and tert-butylphosphonic acid (tBPA) as molecular models for interaction between phosphonates and titania surfaces and to investigate the solution stability of these species. Reflux of titanium(IV) ethoxide ortitanium(IV)(diisopropoxide)bis(2,4-pentadionate) withtert-butylphosphonic acid in toluene–ethanolmixture or acetone yielded seven titanium alkoxide phosphonate complexes; [Ti5(m3-O)(m2-O)-(m-HOEt)2(m-OEt)3(m2-OEt)(m3-tBPA)3(m3-HtBPA)(m2-tBPA)2(m2-HtBPA)]$3EtOH,1, [Ti4O(m-OEt)5(m2-OEt)7-(m3-tBPA)],2,[Ti4(m2-O)2(m-OEt)2(m-HOEt)2(m2-tPBA)2(m2-HtPBA)6]$4EtOH,3,[Ti4(m2-O)2(m-OEt)2(m-HOEt)2-(m2-tPBA)2(m2-HtPBA)6]$2EtOH,4,[Ti6(m2-O)(m3-O)2(m2-OEt)5(m-OEt)6(m3-tBPA)3(m3-HtBPA)],5,[Ti4(m-iOPr)4(acac)4(m2-tBPA)4],6 and [Ti5(m4-O)(m2-O)3(m2-OEt)4(m-OEt)6(m-HOEt)(m3-tBPA)]2,7. The binding mode of tBPAtothetitanium oxo-core were either double or triple bridging or a combination of the two. No monodentate or chelating coordination was observed.31P NMR spectrometry of dissolved single crystals indicates that 1 and 5 retain their solid-state structures in solution, the latter even on moderate heating, while 6 and 7 dissolved into several other forms. The complexes were found to be sensitive towards hydrolysis, proceeding in a topotacticfashion with densification of the material into plates and lamellae resulting finally in “core–shell”nanoparticles with a crystalline core (anatase) and an amorphous outer shell upon contact with water at room temperature as observed by HRTEM and AFM analyses.31P NMR data supported degradation after addition of water to solutions of the complexes. Hydrolysis under different conditions affords complex oxide structures of different morphologies.

Authors/Creators:Svensson, Fredric and Daniel, Geoffrey and Tai, Cheuk-Wai and Seisenbaeva, Gulaim and Kessler, Vadim
Title:Titanium phosphonate oxo-alkoxide "clusters": solution stability and facile hydrolytic transformation into nano titania
Year of publishing :2020
Volume:10
Page range:6873-6883
Number of Pages:11
Publisher:The Royal Society of Chemistry
ISSN:2046-2069
Language:English
Publication Type:Journal article
Article category:Scientific peer reviewed
Version:Published version
Copyright:Creative Commons: Attribution-Noncommercial 4.0
Full Text Status:Public
Subjects:(A) Swedish standard research categories 2011 > 1 Natural sciences > 104 Chemical Sciences > Inorganic Chemistry
(A) Swedish standard research categories 2011 > 1 Natural sciences > 104 Chemical Sciences > Physical Chemistry
Keywords:Titanium (oxo-) alkoxide phosphonate complexes, interaction, phosphonates, titania surfaces, solution stability
URN:NBN:urn:nbn:se:slu:epsilon-p-105109
Permanent URL:
http://urn.kb.se/resolve?urn=urn:nbn:se:slu:epsilon-p-105109
Additional ID:
Type of IDID
DOI10.1039/c9ra10691j
Web of Science (WoS)000517310200017
ID Code:16850
Faculty:NJ - Fakulteten för naturresurser och jordbruksvetenskap
S - Faculty of Forest Sciences
Department:(NL, NJ) > Department of Molecular Sciences
(S) > Department of Forest Biomaterials and Technology
Deposited By: SLUpub Connector
Deposited On:04 May 2020 12:19
Metadata Last Modified:04 May 2020 12:19

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