The surface atomic oxyradical mechanism for Ag-catalyzed olefin epoxidation
We report comprehensive, quantitative, ab initio theoretical estimates for the energetics involved in the Ag-catalyzed epoxidation of olefins. From these estimates, a detailed mechanism is proposed. This mechanism (based on theoretical quantum chemical studies of the interaction of atomic and molecu...
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| Veröffentlicht in: | Journal of catalysis 1988, Vol.112 (1), p.80-92 |
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| container_title | Journal of catalysis |
| container_volume | 112 |
| creator | Carter, Emily A. Goddard, William A. |
| description | We report comprehensive, quantitative, ab initio theoretical estimates for the energetics involved in the Ag-catalyzed epoxidation of olefins. From these estimates, a detailed mechanism is proposed. This mechanism (based on theoretical quantum chemical studies of the interaction of atomic and molecular adsorbates with clusters of Ag atoms) proposes that a
surface atomic oxyradical anion is the active oxygen species for forming epoxide. This mechanism explains the role of electronegative (Cl
−) and electropositive (Cs
+) promoters and explains why selectivity (toward epoxide) is far higher for ethylene than for propene and other higher olefins. Recent experiments which suggested O
2(ad) as the active species are reinterpreted within the context of this new atomic oxygen radical mechanism. |
| doi_str_mv | 10.1016/0021-9517(88)90122-4 |
| format | Article |
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surface atomic oxyradical anion is the active oxygen species for forming epoxide. This mechanism explains the role of electronegative (Cl
−) and electropositive (Cs
+) promoters and explains why selectivity (toward epoxide) is far higher for ethylene than for propene and other higher olefins. Recent experiments which suggested O
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surface atomic oxyradical anion is the active oxygen species for forming epoxide. This mechanism explains the role of electronegative (Cl
−) and electropositive (Cs
+) promoters and explains why selectivity (toward epoxide) is far higher for ethylene than for propene and other higher olefins. Recent experiments which suggested O
2(ad) as the active species are reinterpreted within the context of this new atomic oxygen radical mechanism.</description><subject>Catalysis</subject><subject>Catalysts: preparations and properties</subject><subject>Catalytic reactions</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>General. Nomenclature, chemical documentation, computer chemistry</subject><subject>Theory of reactions, general kinetics</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><issn>0021-9517</issn><issn>1090-2694</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1988</creationdate><recordtype>article</recordtype><recordid>eNo9kDtPwzAUhS0EEuXxDxg8MMAQuLYTx1mQqoqXqMRSZuv6RY3SpLIDavn1pBQxneXT0TkfIRcMbhgweQvAWdFUrL5S6roBxnlRHpAJgwYKLpvykEz-kWNykvMHAGNVpSbkZbH0NH-mgNZTHPpVtLTfbBO6aLGlK2-X2MW8oqFPdPpeWByw3X57R_vWh9hRv-430eEQ--6MHAVssz__y1Py9nC_mD0V89fH59l0Xngu6qGQzkumZODAKsmN4TzUgEJCYEHx0ooSWSVqNMZYYaQoTePAWeORlTheEqfkct-7xjyODAk7G7Nep7jCtNU11KAEG7G7PebHLV_RJ51t9J31LiZvB-36qBnonUG906N3erRS-tegLsUPJXlkqQ</recordid><startdate>1988</startdate><enddate>1988</enddate><creator>Carter, Emily A.</creator><creator>Goddard, William A.</creator><general>Elsevier Inc</general><general>Elsevier</general><scope>IQODW</scope></search><sort><creationdate>1988</creationdate><title>The surface atomic oxyradical mechanism for Ag-catalyzed olefin epoxidation</title><author>Carter, Emily A. ; Goddard, William A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-e237t-6de6186f201562bb22f70a360f1f824c34a1537abbbc3b634b9d0dcbea14a0903</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1988</creationdate><topic>Catalysis</topic><topic>Catalysts: preparations and properties</topic><topic>Catalytic reactions</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>General. Nomenclature, chemical documentation, computer chemistry</topic><topic>Theory of reactions, general kinetics</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Carter, Emily A.</creatorcontrib><creatorcontrib>Goddard, William A.</creatorcontrib><collection>Pascal-Francis</collection><jtitle>Journal of catalysis</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Carter, Emily A.</au><au>Goddard, William A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The surface atomic oxyradical mechanism for Ag-catalyzed olefin epoxidation</atitle><jtitle>Journal of catalysis</jtitle><date>1988</date><risdate>1988</risdate><volume>112</volume><issue>1</issue><spage>80</spage><epage>92</epage><pages>80-92</pages><issn>0021-9517</issn><eissn>1090-2694</eissn><coden>JCTLA5</coden><abstract>We report comprehensive, quantitative, ab initio theoretical estimates for the energetics involved in the Ag-catalyzed epoxidation of olefins. From these estimates, a detailed mechanism is proposed. This mechanism (based on theoretical quantum chemical studies of the interaction of atomic and molecular adsorbates with clusters of Ag atoms) proposes that a
surface atomic oxyradical anion is the active oxygen species for forming epoxide. This mechanism explains the role of electronegative (Cl
−) and electropositive (Cs
+) promoters and explains why selectivity (toward epoxide) is far higher for ethylene than for propene and other higher olefins. Recent experiments which suggested O
2(ad) as the active species are reinterpreted within the context of this new atomic oxygen radical mechanism.</abstract><cop>Amsterdam</cop><pub>Elsevier Inc</pub><doi>10.1016/0021-9517(88)90122-4</doi><tpages>13</tpages></addata></record> |
| fulltext | fulltext |
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| ispartof | Journal of catalysis, 1988, Vol.112 (1), p.80-92 |
| issn | 0021-9517 1090-2694 |
| language | eng |
| recordid | cdi_pascalfrancis_primary_7070831 |
| source | ScienceDirect Journals (5 years ago - present) |
| subjects | Catalysis Catalysts: preparations and properties Catalytic reactions Chemistry Exact sciences and technology General and physical chemistry General. Nomenclature, chemical documentation, computer chemistry Theory of reactions, general kinetics Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| title | The surface atomic oxyradical mechanism for Ag-catalyzed olefin epoxidation |
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