{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23673"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23673","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Polyoxotitanates and their role in titania sol-gel polymerization","abstract":"Hydrolysis of Ti(OBu$\\sp{\\rm t})\\sb4$ with 1 equiv of water in t-BuOH at 100$\\sp\\circ$C yielded a new polyoxotitanate complex $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{17}$. A single crystal X-ray diffraction study of its t-BuOH solvate revealed a $\\rm Ti\\sb{18}O\\sb{45}$ metal-oxygen framework having a pentacapped Keggin structure Reaction of the complex with t-amyl alcohol led to the product $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{12}(OAm\\sp{t})\\sb5$, identified using NMR spectroscopy.","abstract_html":"Hydrolysis of Ti(OBu$\\sp{\\rm t})\\sb4$ with 1 equiv of water in t-BuOH at 100$\\sp\\circ$C yielded a new polyoxotitanate complex $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{17}$. A single crystal X-ray diffraction study of its t-BuOH solvate revealed a $\\rm Ti\\sb{18}O\\sb{45}$ metal-oxygen framework having a pentacapped Keggin structure Reaction of the complex with t-amyl alcohol led to the product $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{12}(OAm\\sp{t})\\sb5$, identified using NMR spectroscopy.","abstract_has_math":true,"creators":["Chen, Yuewu"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry, Inorganic","degree_department":null,"school":null,"contributors":["Klemperer, Walter G."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:22:49Z","date_published":"2011-05-07T14:22:49Z","updated_at":"2026-07-22T22:25:22Z","subjects":["Chemistry, Inorganic","Chemistry, Polymer","Engineering, Materials Science"],"languages":["eng"],"rights":["Copyright 1996 Chen, Yuewu"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591197716","AAI9712230","(UMI)AAI9712230"],"render_values":[{"text":"9780591197716","href":null,"code":true},{"text":"AAI9712230","href":null,"code":true},{"text":"(UMI)AAI9712230","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23673","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Klemperer, Walter G."]},{"key":"dc:creator","label":"Author","values":["Chen, Yuewu"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:22:49Z","10000-01-01","1996"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry, Inorganic","Chemistry, Polymer","Engineering, Materials Science"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic","Chemistry, Polymer","Engineering, Materials Science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1996 Chen, Yuewu"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591197716","AAI9712230","(UMI)AAI9712230","http://hdl.handle.net/2142/23673"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Hydrolysis of Ti(OBu$\\sp{\\rm t})\\sb4$ with 1 equiv of water in t-BuOH at 100$\\sp\\circ$C yielded a new polyoxotitanate complex $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{17}$. A single crystal X-ray diffraction study of its t-BuOH solvate revealed a $\\rm Ti\\sb{18}O\\sb{45}$ metal-oxygen framework having a pentacapped Keggin structure Reaction of the complex with t-amyl alcohol led to the product $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{12}(OAm\\sp{t})\\sb5$, identified using NMR spectroscopy.","Partial hydrolysis and condensation of titanium alkoxides were studied in situ by using solution 170 NMR spectroscopy. The speciation and rates of formation were found to be greatly affected by reaction conditions such as the choice of alkoxide ligand, degree of hydrolysis, solvent and pH. The low molecular weight species formed did not appear to be intermediates formed under sol-gel polymerization conditions.","Solution $\\sp{17}$O NMR and static light scattering techniques were used to examine molecular size distributions in hydrolyzed Ti(OEt)$\\sb4$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ solutions under acidic and basic (or neutral) conditions as a function of the degree of hydrolysis. Sol-gel polymerization of Ti(OEt)$\\sb4$ was observed to involve the initial formation of stable polyoxotitanates which then serve as monomers for sol-gel polymerization.","A building block approach in titania sol-gel polymerization was explored using two polyoxotitanates, $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$, as potential precursors. First, the stability of the $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ core structures toward ethanol was studied. Ethanolic solution of $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ showed significant decomposition of the $\\rm\\lbrack Ti\\sb7O\\sb4$) core structure, while solution of $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ showed no signs of decomposition under the same conditions. Solid state $\\sp{17}$O MAS NMR experiments using selective $\\sp{17}$O labeling techniques indicated that the $\\rm\\lbrack Ti\\sb{16}O\\sb{16}$) core was largely preserved during sol-gel polymerization. Dynamic light scattering studies comparing kinetics of $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$, $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ and Ti(OEt)$\\sb4$ sol-gel polymerization revealed that two different molecular growth pathways were followed. Nitrogen adsorption studies showed different porosities for $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$-, $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$- and Ti(OEt)$\\sb4$-derived xerogels arising from the different precursors employed.","Made available in DSpace on 2011-05-07T14:22:49Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712230.pdf: 7272217 bytes, checksum: 6b2f95bad72a58418461c6b718255985 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:06:04Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:42-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Polyoxotitanates and their role in titania sol-gel polymerization"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Chen, Yuewu"],"dc:date":["2011-05-07T14:22:49Z","10000-01-01","1996"],"dc:description":["Hydrolysis of Ti(OBu$\\sp{\\rm t})\\sb4$ with 1 equiv of water in t-BuOH at 100$\\sp\\circ$C yielded a new polyoxotitanate complex $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{17}$. A single crystal X-ray diffraction study of its t-BuOH solvate revealed a $\\rm Ti\\sb{18}O\\sb{45}$ metal-oxygen framework having a pentacapped Keggin structure Reaction of the complex with t-amyl alcohol led to the product $\\rm\\lbrack Ti\\sb{18}O\\sb{28}H\\rbrack (OBu\\sp{t})\\sb{12}(OAm\\sp{t})\\sb5$, identified using NMR spectroscopy.","Partial hydrolysis and condensation of titanium alkoxides were studied in situ by using solution 170 NMR spectroscopy. The speciation and rates of formation were found to be greatly affected by reaction conditions such as the choice of alkoxide ligand, degree of hydrolysis, solvent and pH. The low molecular weight species formed did not appear to be intermediates formed under sol-gel polymerization conditions.","Solution $\\sp{17}$O NMR and static light scattering techniques were used to examine molecular size distributions in hydrolyzed Ti(OEt)$\\sb4$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ solutions under acidic and basic (or neutral) conditions as a function of the degree of hydrolysis. Sol-gel polymerization of Ti(OEt)$\\sb4$ was observed to involve the initial formation of stable polyoxotitanates which then serve as monomers for sol-gel polymerization.","A building block approach in titania sol-gel polymerization was explored using two polyoxotitanates, $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$, as potential precursors. First, the stability of the $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ and $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ core structures toward ethanol was studied. Ethanolic solution of $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$ showed significant decomposition of the $\\rm\\lbrack Ti\\sb7O\\sb4$) core structure, while solution of $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ showed no signs of decomposition under the same conditions. Solid state $\\sp{17}$O MAS NMR experiments using selective $\\sp{17}$O labeling techniques indicated that the $\\rm\\lbrack Ti\\sb{16}O\\sb{16}$) core was largely preserved during sol-gel polymerization. Dynamic light scattering studies comparing kinetics of $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$, $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$ and Ti(OEt)$\\sb4$ sol-gel polymerization revealed that two different molecular growth pathways were followed. Nitrogen adsorption studies showed different porosities for $\\rm\\lbrack Ti\\sb7O\\sb4\\rbrack (OEt)\\sb{20}$-, $\\rm\\lbrack Ti\\sb{16}O\\sb{16}\\rbrack (OEt)\\sb{32}$- and Ti(OEt)$\\sb4$-derived xerogels arising from the different precursors employed.","Made available in DSpace on 2011-05-07T14:22:49Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712230.pdf: 7272217 bytes, checksum: 6b2f95bad72a58418461c6b718255985 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:06:04Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:42-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["9780591197716","AAI9712230","(UMI)AAI9712230","http://hdl.handle.net/2142/23673"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Chen, Yuewu"],"dc:subject":["Chemistry, Inorganic","Chemistry, Polymer","Engineering, Materials Science"],"dc:title":["Polyoxotitanates and their role in titania sol-gel polymerization"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry, Inorganic","Chemistry, Polymer","Engineering, Materials Science"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:22Z"}