{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21150"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21150","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Heterogeneous catalytic studies with rhenium cluster-based precursors","abstract":"When (Re(CO)$\\sb3$OH) $\\sb4$ was supported on Al$\\sb2$O$\\sb3$ followed by heating in H$\\sb2$ no decomposition gas products, CO and CH$\\sb4$, were observed below 650 K. Following the activation by infrared spectroscopy showed the formation of Re(CO)$\\rm\\sb3\\{O$-$\\rm Al\\}\\{HO$-Al$\\}\\sb2$ at 480 K. The activated sample, (Re$\\sb4$) /Al$\\sb2$O$\\sb3$, when exposed to CO/H$\\sb2$ at 298 K, produced CH$\\sb4$ near 500 K with a shoulder near 600 K in the temperature programmed reaction (TPR) profile. Elevating the CO/H$\\sb2$ treatment temperature to 500 K resulted in the formation of CH$\\sb4$ at 560 K. The adsorption of CH$\\sb3$OH or CH$\\sb3$I to the sample produced CH$\\sb4$ at 580 K. When (Re(CO)$\\sb3$OH) $\\sb4$ activated on SiO$\\sb2$, only one CH$\\sb4$ peak at 490 K was observed for CO/H$\\sb2$ adsorption. When TiO$\\sb2$ was used as a support, a spillover species was also observed from CO and H$\\sb2$ exposure at 500 K. The spillover rate appeared to be slower on TiO$\\sb2$ than was observed on Al$\\sb2$O$\\sb3$.","abstract_html":"When (Re(CO)$\\sb3$OH) $\\sb4$ was supported on Al$\\sb2$O$\\sb3$ followed by heating in H$\\sb2$ no decomposition gas products, CO and CH$\\sb4$, were observed below 650 K. Following the activation by infrared spectroscopy showed the formation of Re(CO)$\\rm\\sb3\\{O$-$\\rm Al\\}\\{HO$-Al$\\}\\sb2$ at 480 K. The activated sample, (Re$\\sb4$) /Al$\\sb2$O$\\sb3$, when exposed to CO/H$\\sb2$ at 298 K, produced CH$\\sb4$ near 500 K with a shoulder near 600 K in the temperature programmed reaction (TPR) profile. Elevating the CO/H$\\sb2$ treatment temperature to 500 K resulted in the formation of CH$\\sb4$ at 560 K. The adsorption of CH$\\sb3$OH or CH$\\sb3$I to the sample produced CH$\\sb4$ at 580 K. When (Re(CO)$\\sb3$OH) $\\sb4$ activated on SiO$\\sb2$, only one CH$\\sb4$ peak at 490 K was observed for CO/H$\\sb2$ adsorption. When TiO$\\sb2$ was used as a support, a spillover species was also observed from CO and H$\\sb2$ exposure at 500 K. The spillover rate appeared to be slower on TiO$\\sb2$ than was observed on Al$\\sb2$O$\\sb3$.","abstract_has_math":true,"creators":["Lane, Philip Douglas"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Shapley, John R."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:59:50Z","date_published":"2011-05-07T12:59:50Z","updated_at":"2026-07-22T22:25:17Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1995 Lane, Philip Douglas"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9624405","(UMI)AAI9624405"],"render_values":[{"text":"AAI9624405","href":null,"code":true},{"text":"(UMI)AAI9624405","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21150","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shapley, John R."]},{"key":"dc:creator","label":"Author","values":["Lane, Philip Douglas"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:59:50Z","10000-01-01","1995"]},{"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"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1995 Lane, Philip Douglas"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9624405","(UMI)AAI9624405","http://hdl.handle.net/2142/21150"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["When (Re(CO)$\\sb3$OH) $\\sb4$ was supported on Al$\\sb2$O$\\sb3$ followed by heating in H$\\sb2$ no decomposition gas products, CO and CH$\\sb4$, were observed below 650 K. Following the activation by infrared spectroscopy showed the formation of Re(CO)$\\rm\\sb3\\{O$-$\\rm Al\\}\\{HO$-Al$\\}\\sb2$ at 480 K. The activated sample, (Re$\\sb4$) /Al$\\sb2$O$\\sb3$, when exposed to CO/H$\\sb2$ at 298 K, produced CH$\\sb4$ near 500 K with a shoulder near 600 K in the temperature programmed reaction (TPR) profile. Elevating the CO/H$\\sb2$ treatment temperature to 500 K resulted in the formation of CH$\\sb4$ at 560 K. The adsorption of CH$\\sb3$OH or CH$\\sb3$I to the sample produced CH$\\sb4$ at 580 K. When (Re(CO)$\\sb3$OH) $\\sb4$ activated on SiO$\\sb2$, only one CH$\\sb4$ peak at 490 K was observed for CO/H$\\sb2$ adsorption. When TiO$\\sb2$ was used as a support, a spillover species was also observed from CO and H$\\sb2$ exposure at 500 K. The spillover rate appeared to be slower on TiO$\\sb2$ than was observed on Al$\\sb2$O$\\sb3$.","When both the PPN$\\sp+$ and Et$\\sb4$N$\\sp+$ forms of (Re$\\sb7$IrC(CO)$\\sb{23}\\rbrack\\sp{2-}$ and (Re$\\sb5$IrC(CO)$\\sb{17}\\{$Re(CO)$\\sb3\\}\\sb2\\rbrack\\sp{2-}$ were supported on Al$\\sb2$O$\\sb3$, their decompositions were followed by TPDE and infrared spectroscopy. For the hydrogenolysis of ethane, the most and least active catalyst samples were (Re$\\sb7$Ir(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$, and (ReIr$\\sb7$(PPN)) /Al$\\sb2$O$\\sb3$, respectively. The other two samples, (Re$\\sb5$IrRe$\\sb2$(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$ and (Re$\\sb5$IrRe$\\sb2$(PPN)) /Al$\\sb2$O$\\sb3$, showed comparable activity. All samples appeared, by infrared spectroscopy, to form Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$ and smaller nuclearity clusters on the surface during decomposition. The amount of Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$ formed at 573 K correlated with the ethane hydrogenolysis activity of the resulting catalyst. The sample most active for ethane hydrogenolysis, (Re$\\sb7$Ir(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$, produced the largest amount of Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$during activation by 573 K, 60% of the available rhenium, and the sample least active, (Re$\\sb7$IrC(CO)$\\sb{23}$(PPN)) /Al$\\sb2$O$\\sb3$, resulted in the smallest amount, 40%. All samples produced CH$\\sb4$ in the TPR profiles from the adsorption of CO in H$\\sb2$.","Made available in DSpace on 2011-05-07T12:59:50Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9624405.pdf: 4189772 bytes, checksum: b23ed82e02e9138ac208bc85631e8c31 (MD5) Previous issue date: 1995","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:48:49Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:22:09-05:00 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":["Heterogeneous catalytic studies with rhenium cluster-based precursors"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Lane, Philip Douglas"],"dc:date":["2011-05-07T12:59:50Z","10000-01-01","1995"],"dc:description":["When (Re(CO)$\\sb3$OH) $\\sb4$ was supported on Al$\\sb2$O$\\sb3$ followed by heating in H$\\sb2$ no decomposition gas products, CO and CH$\\sb4$, were observed below 650 K. Following the activation by infrared spectroscopy showed the formation of Re(CO)$\\rm\\sb3\\{O$-$\\rm Al\\}\\{HO$-Al$\\}\\sb2$ at 480 K. The activated sample, (Re$\\sb4$) /Al$\\sb2$O$\\sb3$, when exposed to CO/H$\\sb2$ at 298 K, produced CH$\\sb4$ near 500 K with a shoulder near 600 K in the temperature programmed reaction (TPR) profile. Elevating the CO/H$\\sb2$ treatment temperature to 500 K resulted in the formation of CH$\\sb4$ at 560 K. The adsorption of CH$\\sb3$OH or CH$\\sb3$I to the sample produced CH$\\sb4$ at 580 K. When (Re(CO)$\\sb3$OH) $\\sb4$ activated on SiO$\\sb2$, only one CH$\\sb4$ peak at 490 K was observed for CO/H$\\sb2$ adsorption. When TiO$\\sb2$ was used as a support, a spillover species was also observed from CO and H$\\sb2$ exposure at 500 K. The spillover rate appeared to be slower on TiO$\\sb2$ than was observed on Al$\\sb2$O$\\sb3$.","When both the PPN$\\sp+$ and Et$\\sb4$N$\\sp+$ forms of (Re$\\sb7$IrC(CO)$\\sb{23}\\rbrack\\sp{2-}$ and (Re$\\sb5$IrC(CO)$\\sb{17}\\{$Re(CO)$\\sb3\\}\\sb2\\rbrack\\sp{2-}$ were supported on Al$\\sb2$O$\\sb3$, their decompositions were followed by TPDE and infrared spectroscopy. For the hydrogenolysis of ethane, the most and least active catalyst samples were (Re$\\sb7$Ir(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$, and (ReIr$\\sb7$(PPN)) /Al$\\sb2$O$\\sb3$, respectively. The other two samples, (Re$\\sb5$IrRe$\\sb2$(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$ and (Re$\\sb5$IrRe$\\sb2$(PPN)) /Al$\\sb2$O$\\sb3$, showed comparable activity. All samples appeared, by infrared spectroscopy, to form Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$ and smaller nuclearity clusters on the surface during decomposition. The amount of Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$ formed at 573 K correlated with the ethane hydrogenolysis activity of the resulting catalyst. The sample most active for ethane hydrogenolysis, (Re$\\sb7$Ir(Et$\\sb4$N)) /Al$\\sb2$O$\\sb3$, produced the largest amount of Re(CO)$\\sb3\\{$O-Al$\\}\\{$HO-Al$\\}\\sb2$during activation by 573 K, 60% of the available rhenium, and the sample least active, (Re$\\sb7$IrC(CO)$\\sb{23}$(PPN)) /Al$\\sb2$O$\\sb3$, resulted in the smallest amount, 40%. All samples produced CH$\\sb4$ in the TPR profiles from the adsorption of CO in H$\\sb2$.","Made available in DSpace on 2011-05-07T12:59:50Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9624405.pdf: 4189772 bytes, checksum: b23ed82e02e9138ac208bc85631e8c31 (MD5) Previous issue date: 1995","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:48:49Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:22:09-05:00 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":["AAI9624405","(UMI)AAI9624405","http://hdl.handle.net/2142/21150"],"dc:language":["eng"],"dc:rights":["Copyright 1995 Lane, Philip Douglas"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Heterogeneous catalytic studies with rhenium cluster-based precursors"],"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":"2026-07-22T22:25:17Z"}