Luminescence effects at the electrode/solution interface

Miscellaneous · Wed Jan 01 00:00:00 EST 1992

OSTI ID:7101924

McCord, S P

Three types of electron transfer reactions resulting in luminescence have been studied. Each study is unique in the mechanism by which light emission (luminescence) occurs. Chemiluminescence (CL) is the light emission that results after the oxidation-reduction reaction of two chemical species. If either one of the reacting species is produced electrochemically, the result is electrogenerated chemiluminescence (ECL). The third type of luminescence is charge transfer reaction inverse photoemission (CTRIP). This is luminescence from the electrode while undergoing heterogeneous electron transfer. The electrogenerated chemiluminescence (ECL) of Ru(dp-bpy)[sup 2+][sub 3] (dp-bpy = 4,4[prime]-diphenyl-2,2[prime]-bipyridine) and Ru(dp-phen)[sup 2+][sub 3] (dp-phen = 4,7-diphenyl-1,10-phenanthroline) in acetonitrile and aqueous solutions was studied. The diphenyl-substituted compounds produced a more intense emission than the nonsubstituted Ru(bpy)[sup 2+][sub 3] in acetonitrile. The charge-transfer reaction inverse photoemission (CTRIP) from the metal/solution interface in acetonitrile and aqueous solutions has been studied. Inverse photoemission was observed during the reduction of peroxydisulfate in both acetontrile and water. Inverse photoemission was observed during the oxidation of oxalate but was less intense. The use of CTRIP spectroscopy to characterize radicals in solution is discussed. Treatment of anodized or chemically etched silicon (porous silicon) with dilute nitric acid or persulfate solution results in weak chemiluminescence (CL) in the visible region. When porous Si produced by anodization is treated with concentrated nitric acid, the reaction is violent and produces a bright flash of light. The fact that very similar reactions occur with siloxene (Si[sub 6]H[sub 6]O[sub 3]) prepared from CaSi[sub 2] suggests that the visible emission seen with porous Si can be attributed to this substance.

• Research Organization: Texas Univ., Austin, TX (United States)
• OSTI ID: 7101924
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ELECTRODES
ELECTRON TRANSFER
LUMINESCENCE
ACETONITRILE
AQUEOUS SOLUTIONS
CHEMILUMINESCENCE
ELECTROCHEMISTRY
ELECTROLUMINESCENCE
INTERFACES
PHOTOLUMINESCENCE
SILICON
CHEMISTRY
DISPERSIONS
ELEMENTS
MIXTURES
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SEMIMETALS
SOLUTIONS
400400* - Electrochemistry
664200 - Spectra of Atoms & Molecules & their Interactions with Photons- (1992-)