Electrocatalytic reduction of nitrate in sodium hydroxide solution in the presence of low-valent cobalt-cyclam species

Journal Article · Wed Mar 08 04:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00304a013· OSTI ID:5080107

Li, Hulin; Anderson, W C; Chambers, J Q ^[1]; Hobbs, D T ^[2]

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1. Univ. of Tennessee, Knoxville (USA)
2. E.I. du Pont de Nemours and Co., Inc., Aiken, SC (USA)

In concentrated NaOH solution nitrate and nitrite ions are efficiently reduced to a mixture of products including hydroxylamine and ammonia via an electrocatalytic process in the presence of cobalt complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam). A key mechanistic role is proposed for Co{sup I}(cyclam)NO{sub 3}, which is generated in the diffusion layer at ca. -1.3 V vs SCE. The lack of dependent on pH of either the catalytic peak potential or the peak current indicates that metal hydride intermediate species are not involved in the initial steps of the reduction process. Both Co{sup I} and Co{sup III} intermediates in the nitrate reduction are detected in collection experiments with a gold ring-disk electrode. 18 refs., 8 figs., 2 tabs.

• OSTI ID: 5080107
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:5; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKANES
AMINES
AMMONIA
AQUEOUS SOLUTIONS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
CYCLOALKANES
DATA
DISPERSIONS
ELECTROLYSIS
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXIDES
HYDROXYLAMINE
INFORMATION
LYSIS
MIXTURES
NITRATES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PRODUCTION
REDUCTION
SODIUM COMPOUNDS
SODIUM HYDROXIDES
SOLUTIONS
TRANSITION ELEMENT COMPLEXES