Photoelectrochemical reduction of a Cu(I) complex to copper metal by hot electrons at p-InP
The chemically irreversible reduction of copper(I) (trans-diene)/sup +/ to copper metal has been used to confirm the existence of hot-electron processes at the p-InP/acetonitrile interface. Although hot-carrier processes have been previously reported, this is the first observation of a chemical prod...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1989-03, Vol.111 (6), p.2004-2010 |
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| container_end_page | 2010 |
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| container_issue | 6 |
| container_start_page | 2004 |
| container_title | J. Am. Chem. Soc.; (United States) |
| container_volume | 111 |
| creator | KOVAL, C. A SEGAR, P. R |
| description | The chemically irreversible reduction of copper(I) (trans-diene)/sup +/ to copper metal has been used to confirm the existence of hot-electron processes at the p-InP/acetonitrile interface. Although hot-carrier processes have been previously reported, this is the first observation of a chemical product produced by a hot-carrier reaction in a photoelectrochemical cell. Band-edge positions have been determined by capacitance measurements done under conditions identical with the hot-carrier copper-plating experiments. Supraband-edge production of Cu(O) occurred at high-doped (1.2 /times/ 10/sup 18/ cm/sup /minus/3/) p-InP but was observed at low-doped (8 /times/ 10/sup 15/ cm/sup /minus/3/) samples. For the high-doped electrode, a quantum yield for production of copper by hot electrons of 0.25% was measured, but this represents only a lower limit to the actual quantum yield for hot electrons since the hot-carrier probe reaction must complete with other processes. Nearly identical quantum yields were measured with both 632.8- and 543.5-nm illumination; however, the intensity profile across the electrode surface has a dramatic effect on the quantum yield. |
| doi_str_mv | 10.1021/ja00188a009 |
| format | Article |
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A ; SEGAR, P. R</creator><creatorcontrib>KOVAL, C. A ; SEGAR, P. R ; Univ. of Colorado, Boulder (USA)</creatorcontrib><description>The chemically irreversible reduction of copper(I) (trans-diene)/sup +/ to copper metal has been used to confirm the existence of hot-electron processes at the p-InP/acetonitrile interface. Although hot-carrier processes have been previously reported, this is the first observation of a chemical product produced by a hot-carrier reaction in a photoelectrochemical cell. Band-edge positions have been determined by capacitance measurements done under conditions identical with the hot-carrier copper-plating experiments. Supraband-edge production of Cu(O) occurred at high-doped (1.2 /times/ 10/sup 18/ cm/sup /minus/3/) p-InP but was observed at low-doped (8 /times/ 10/sup 15/ cm/sup /minus/3/) samples. For the high-doped electrode, a quantum yield for production of copper by hot electrons of 0.25% was measured, but this represents only a lower limit to the actual quantum yield for hot electrons since the hot-carrier probe reaction must complete with other processes. Nearly identical quantum yields were measured with both 632.8- and 543.5-nm illumination; however, the intensity profile across the electrode surface has a dramatic effect on the quantum yield.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00188a009</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400400 - Electrochemistry ; 400500 - Photochemistry ; ACETONITRILE ; CHEMICAL REACTIONS ; CHEMISTRY ; COMPLEXES ; COPPER COMPLEXES ; DATA ; EFFICIENCY ; ELECTROCHEMISTRY ; Exact sciences and technology ; EXPERIMENTAL DATA ; General and physical chemistry ; High temperature electrochemistry (including molten salts) ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; INTERFACES ; MATERIALS ; NITRILES ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC NITROGEN COMPOUNDS ; P-TYPE CONDUCTORS ; PHOTOCHEMICAL REACTIONS ; PHOTOELECTRIC EFFECT ; PHOTOELECTROMAGNETIC EFFECTS ; QUANTUM EFFICIENCY ; REDUCTION ; SEMICONDUCTOR MATERIALS ; TRANSITION ELEMENT COMPLEXES</subject><ispartof>J. 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Soc.; (United States)</title><description>The chemically irreversible reduction of copper(I) (trans-diene)/sup +/ to copper metal has been used to confirm the existence of hot-electron processes at the p-InP/acetonitrile interface. Although hot-carrier processes have been previously reported, this is the first observation of a chemical product produced by a hot-carrier reaction in a photoelectrochemical cell. Band-edge positions have been determined by capacitance measurements done under conditions identical with the hot-carrier copper-plating experiments. Supraband-edge production of Cu(O) occurred at high-doped (1.2 /times/ 10/sup 18/ cm/sup /minus/3/) p-InP but was observed at low-doped (8 /times/ 10/sup 15/ cm/sup /minus/3/) samples. For the high-doped electrode, a quantum yield for production of copper by hot electrons of 0.25% was measured, but this represents only a lower limit to the actual quantum yield for hot electrons since the hot-carrier probe reaction must complete with other processes. Nearly identical quantum yields were measured with both 632.8- and 543.5-nm illumination; however, the intensity profile across the electrode surface has a dramatic effect on the quantum yield.</description><subject>400400 - Electrochemistry</subject><subject>400500 - Photochemistry</subject><subject>ACETONITRILE</subject><subject>CHEMICAL REACTIONS</subject><subject>CHEMISTRY</subject><subject>COMPLEXES</subject><subject>COPPER COMPLEXES</subject><subject>DATA</subject><subject>EFFICIENCY</subject><subject>ELECTROCHEMISTRY</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>General and physical chemistry</subject><subject>High temperature electrochemistry (including molten salts)</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>INTERFACES</subject><subject>MATERIALS</subject><subject>NITRILES</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC NITROGEN COMPOUNDS</subject><subject>P-TYPE CONDUCTORS</subject><subject>PHOTOCHEMICAL REACTIONS</subject><subject>PHOTOELECTRIC EFFECT</subject><subject>PHOTOELECTROMAGNETIC EFFECTS</subject><subject>QUANTUM EFFICIENCY</subject><subject>REDUCTION</subject><subject>SEMICONDUCTOR MATERIALS</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1989</creationdate><recordtype>article</recordtype><recordid>eNotj8tKw0AUhgdRsFZXvsAgLnQRnVvmspTipVCwC125CJOTE5qSZEJmCvr2DrRwOBf4-Dg_IbecPXEm-PPeM8atzd2dkQUvBStKLvQ5WTDGRGGslpfkKsZ9PpWwfEF-truQAvYIaQ6ww6ED39MZmwOkLow0tNTT1eFh_UghDFOPvzSFvE4TznTAlOH6j2YHPTnGSH2iU7Eet9fkovV9xJvTXJLvt9ev1Uex-Xxfr142RRCcpwIYNLVjRjfaovKG89axVivVNo4DYCkayw0oqa1yqKRTaHLlQLrGui7lktwdvSGmrorQJYQdhHHMD1WlLYXUMkP3R2jyMUdsZz9CF6tp7gY__1XaOGOVlv_PZmAF</recordid><startdate>19890315</startdate><enddate>19890315</enddate><creator>KOVAL, C. 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R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-o211t-c0cdb9076d68e4a711f90f644fd91cce52d817c436849e4394e74e70026bebb53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1989</creationdate><topic>400400 - Electrochemistry</topic><topic>400500 - Photochemistry</topic><topic>ACETONITRILE</topic><topic>CHEMICAL REACTIONS</topic><topic>CHEMISTRY</topic><topic>COMPLEXES</topic><topic>COPPER COMPLEXES</topic><topic>DATA</topic><topic>EFFICIENCY</topic><topic>ELECTROCHEMISTRY</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>General and physical chemistry</topic><topic>High temperature electrochemistry (including molten salts)</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>INTERFACES</topic><topic>MATERIALS</topic><topic>NITRILES</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC NITROGEN COMPOUNDS</topic><topic>P-TYPE CONDUCTORS</topic><topic>PHOTOCHEMICAL REACTIONS</topic><topic>PHOTOELECTRIC EFFECT</topic><topic>PHOTOELECTROMAGNETIC EFFECTS</topic><topic>QUANTUM EFFICIENCY</topic><topic>REDUCTION</topic><topic>SEMICONDUCTOR MATERIALS</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>KOVAL, C. A</creatorcontrib><creatorcontrib>SEGAR, P. R</creatorcontrib><creatorcontrib>Univ. of Colorado, Boulder (USA)</creatorcontrib><collection>Pascal-Francis</collection><collection>OSTI.GOV</collection><jtitle>J. Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>KOVAL, C. A</au><au>SEGAR, P. R</au><aucorp>Univ. of Colorado, Boulder (USA)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoelectrochemical reduction of a Cu(I) complex to copper metal by hot electrons at p-InP</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><date>1989-03-15</date><risdate>1989</risdate><volume>111</volume><issue>6</issue><spage>2004</spage><epage>2010</epage><pages>2004-2010</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The chemically irreversible reduction of copper(I) (trans-diene)/sup +/ to copper metal has been used to confirm the existence of hot-electron processes at the p-InP/acetonitrile interface. Although hot-carrier processes have been previously reported, this is the first observation of a chemical product produced by a hot-carrier reaction in a photoelectrochemical cell. Band-edge positions have been determined by capacitance measurements done under conditions identical with the hot-carrier copper-plating experiments. Supraband-edge production of Cu(O) occurred at high-doped (1.2 /times/ 10/sup 18/ cm/sup /minus/3/) p-InP but was observed at low-doped (8 /times/ 10/sup 15/ cm/sup /minus/3/) samples. For the high-doped electrode, a quantum yield for production of copper by hot electrons of 0.25% was measured, but this represents only a lower limit to the actual quantum yield for hot electrons since the hot-carrier probe reaction must complete with other processes. Nearly identical quantum yields were measured with both 632.8- and 543.5-nm illumination; however, the intensity profile across the electrode surface has a dramatic effect on the quantum yield.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ja00188a009</doi><tpages>7</tpages></addata></record> |
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| issn | 0002-7863 1520-5126 |
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| source | American Chemical Society Journals |
| subjects | 400400 - Electrochemistry 400500 - Photochemistry ACETONITRILE CHEMICAL REACTIONS CHEMISTRY COMPLEXES COPPER COMPLEXES DATA EFFICIENCY ELECTROCHEMISTRY Exact sciences and technology EXPERIMENTAL DATA General and physical chemistry High temperature electrochemistry (including molten salts) INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY INTERFACES MATERIALS NITRILES NUMERICAL DATA ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS P-TYPE CONDUCTORS PHOTOCHEMICAL REACTIONS PHOTOELECTRIC EFFECT PHOTOELECTROMAGNETIC EFFECTS QUANTUM EFFICIENCY REDUCTION SEMICONDUCTOR MATERIALS TRANSITION ELEMENT COMPLEXES |
| title | Photoelectrochemical reduction of a Cu(I) complex to copper metal by hot electrons at p-InP |
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