{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23170"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23170","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part I. Chemical processing of barium titanates. Part II. The chemistry of sulfotitanic acids, molecular analogues of sulfated metal oxide superacids","abstract":"Made available in DSpace on 2011-05-07T14:04:39Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702583.pdf: 5005183 bytes, checksum: c1cd26b9c7ea8b20868f9b4a84d3ca52 (MD5) Previous issue date: 1996","abstract_html":"Made available in DSpace on 2011-05-07T14:04:39Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702583.pdf: 5005183 bytes, checksum: c1cd26b9c7ea8b20868f9b4a84d3ca52 (MD5) Previous issue date: 1996","abstract_has_math":false,"creators":["Liang, Shurong"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Klemperer, Walter G."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:04:39Z","date_published":"2011-05-07T14:04:39Z","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Inorganic","Engineering, Materials Science"],"languages":["eng"],"rights":["Copyright 1996 Liang, Shurong"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088496","AAI9702583","(UMI)AAI9702583"],"render_values":[{"text":"9780591088496","href":null,"code":true},{"text":"AAI9702583","href":null,"code":true},{"text":"(UMI)AAI9702583","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23170","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":["Liang, Shurong"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:04:39Z","10000-01-01","1996"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"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","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 Liang, Shurong"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088496","AAI9702583","(UMI)AAI9702583","http://hdl.handle.net/2142/23170"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Made available in DSpace on 2011-05-07T14:04:39Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702583.pdf: 5005183 bytes, checksum: c1cd26b9c7ea8b20868f9b4a84d3ca52 (MD5) Previous issue date: 1996","Part I. Several new barium titanium alkoxides, $\\rm BaTi(OPh)\\sb6\\cdot2DMF$ (BTP), (Ba(HOCH$\\sb2$-CH$\\rm\\sb2OH)\\sb4(H\\sb2O)\\rbrack\\lbrack Ti(OCH\\sb2CH\\sb2O)\\sb3\\rbrack (BTG),\\ BaTi\\sb2)O(OBz)\\sb8\\cdot$BzOH (Bz = benzyl) and $\\rm BaTi\\sb4(OR)\\sb{18}\\ (R = Et,\\ \\sp{n}Pr),$ have been synthesized and structurally characterized. The BTP complex, as a single-source precursor, is well-suited for the sol-gel processing of BaTiO$\\sb3$ in the form of gels, powders, and thin films. The BTG complex is a viable precursor for the processing of BaTiO$\\sb3$ powders by thermal decomposition. Calcination of BTG at 600$\\sp\\circ$C yields submicron BaTiO$\\sb3$ powders, which can be sintered into BaTiO$\\sb3$ ceramics at 1300$\\sp\\circ$C. Gels and xerogels have been prepared from the complexes $\\rm BaTi\\sb2O(OBz)\\sb8\\cdot$BzOH and $\\rm BaTi\\sb4(OEt)\\sb{18}.$ Heat treatment of the xerogels derived from $\\rm BaTi\\sb2O(OBz)\\sb8\\cdot$BzOH at 1100$\\sp\\circ$C yields $\\rm BaTi\\sb2O\\sb5$ and a small amount of $\\rm BaTiO\\sb3.$ Phase pure BaTi$\\rm 4O\\sb9$ is obtained after firing the xerogels prepared from $\\rm BaTi\\sb4(OEt)\\sb{18}$ at temperatures above 1200$\\sp\\circ$C.","Part II. The sulfotitanic acids $\\rm H\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OR)\\sb{10}\\rbrack\\ (R = Et, Pr\\sp{n}),$ the first titanium heteropolyacids, are prepared by reaction of Ti(OR)$\\sb4$ with aqueous sulfuric acid in alcohol solution. Their conjugate bases, $\\rm (Et\\sb3NH)\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OR)\\sb{10}\\rbrack,$ are obtained by reaction of the acids with Et$\\sb3$N. According to single crystal X-ray diffraction studies of the ethoxide acid $\\rm H\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OEt)\\sb{10}\\rbrack$ and its triethylamine salt $\\rm (Et\\sb3NH)\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OEt)\\sb{10}\\rbrack,$ both compounds have the same anion structure containing tridentate sulfate ligands, each bonded to three Ti(IV) centers. The proton in the ethoxide acid is bonded to a terminal ethoxide oxygen. The sulfate stretching vibrations in the ethoxide acid have been identified by infrared spectroscopy using $\\sp{18}$O-labeled sulfate. Comparison of these sulfate vibrational spectra with data reported for sulfated titania reveals several common features, implicating tridentate sulfate coordination in sulfated titania. Accordingly, a structural model is proposed for sulfated titania in which sulfate ions adopt a tridentate coordination mode, five-coordinate Ti(IV) centers are the Lewis acid sites, and water molecules coordinated to the Ti(IV) centers are the Bronsted acid sites.","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:02:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:48-05:00 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":["Part I. Chemical processing of barium titanates. Part II. The chemistry of sulfotitanic acids, molecular analogues of sulfated metal oxide superacids"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Liang, Shurong"],"dc:date":["2011-05-07T14:04:39Z","10000-01-01","1996"],"dc:description":["Made available in DSpace on 2011-05-07T14:04:39Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702583.pdf: 5005183 bytes, checksum: c1cd26b9c7ea8b20868f9b4a84d3ca52 (MD5) Previous issue date: 1996","Part I. Several new barium titanium alkoxides, $\\rm BaTi(OPh)\\sb6\\cdot2DMF$ (BTP), (Ba(HOCH$\\sb2$-CH$\\rm\\sb2OH)\\sb4(H\\sb2O)\\rbrack\\lbrack Ti(OCH\\sb2CH\\sb2O)\\sb3\\rbrack (BTG),\\ BaTi\\sb2)O(OBz)\\sb8\\cdot$BzOH (Bz = benzyl) and $\\rm BaTi\\sb4(OR)\\sb{18}\\ (R = Et,\\ \\sp{n}Pr),$ have been synthesized and structurally characterized. The BTP complex, as a single-source precursor, is well-suited for the sol-gel processing of BaTiO$\\sb3$ in the form of gels, powders, and thin films. The BTG complex is a viable precursor for the processing of BaTiO$\\sb3$ powders by thermal decomposition. Calcination of BTG at 600$\\sp\\circ$C yields submicron BaTiO$\\sb3$ powders, which can be sintered into BaTiO$\\sb3$ ceramics at 1300$\\sp\\circ$C. Gels and xerogels have been prepared from the complexes $\\rm BaTi\\sb2O(OBz)\\sb8\\cdot$BzOH and $\\rm BaTi\\sb4(OEt)\\sb{18}.$ Heat treatment of the xerogels derived from $\\rm BaTi\\sb2O(OBz)\\sb8\\cdot$BzOH at 1100$\\sp\\circ$C yields $\\rm BaTi\\sb2O\\sb5$ and a small amount of $\\rm BaTiO\\sb3.$ Phase pure BaTi$\\rm 4O\\sb9$ is obtained after firing the xerogels prepared from $\\rm BaTi\\sb4(OEt)\\sb{18}$ at temperatures above 1200$\\sp\\circ$C.","Part II. The sulfotitanic acids $\\rm H\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OR)\\sb{10}\\rbrack\\ (R = Et, Pr\\sp{n}),$ the first titanium heteropolyacids, are prepared by reaction of Ti(OR)$\\sb4$ with aqueous sulfuric acid in alcohol solution. Their conjugate bases, $\\rm (Et\\sb3NH)\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OR)\\sb{10}\\rbrack,$ are obtained by reaction of the acids with Et$\\sb3$N. According to single crystal X-ray diffraction studies of the ethoxide acid $\\rm H\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OEt)\\sb{10}\\rbrack$ and its triethylamine salt $\\rm (Et\\sb3NH)\\sb2\\lbrack Ti\\sb6O\\sb4(SO\\sb4)\\sb4(OEt)\\sb{10}\\rbrack,$ both compounds have the same anion structure containing tridentate sulfate ligands, each bonded to three Ti(IV) centers. The proton in the ethoxide acid is bonded to a terminal ethoxide oxygen. The sulfate stretching vibrations in the ethoxide acid have been identified by infrared spectroscopy using $\\sp{18}$O-labeled sulfate. Comparison of these sulfate vibrational spectra with data reported for sulfated titania reveals several common features, implicating tridentate sulfate coordination in sulfated titania. Accordingly, a structural model is proposed for sulfated titania in which sulfate ions adopt a tridentate coordination mode, five-coordinate Ti(IV) centers are the Lewis acid sites, and water molecules coordinated to the Ti(IV) centers are the Bronsted acid sites.","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:02:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:48-05:00 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":["9780591088496","AAI9702583","(UMI)AAI9702583","http://hdl.handle.net/2142/23170"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Liang, Shurong"],"dc:subject":["Chemistry, Inorganic","Engineering, Materials Science"],"dc:title":["Part I. Chemical processing of barium titanates. Part II. The chemistry of sulfotitanic acids, molecular analogues of sulfated metal oxide superacids"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:21Z"}