Hydrogen-nitric oxide cell for the synthesis of hydroxylamine

Article abstract of DOI:10.1149/1.1837242

A H₂-NO fuel cell was designed for the synthesis of hydroxylamine in the gas phase. The hydroxylamine produced was trapped in an aqueous solution of H₂SO₄ held in a silica-wool disk used as an electrolyte barrier for H₂ and NO. Among the cathode electrocatalysts tested, iron-phthalocyanine (Fe-Pc) impregnated in graphite was the most favorable one for selective synthesis of hydroxylamine. Active carbon and carbon whiskers used to support the Fe-Pc enhanced the formation of hydroxylamine remarkably. The carbon itself slightly catalyzed the formation of N₂O and NH₃. Excluding the effects of the support, Fe-Pc catalyzed the electrochemical synthesis of hydroxylamine with high selectivity (≈100%). Applied voltage across the cell did not appreciably enhance the formation of hydroxylamine. The reaction under short-circuit conditions was most favorable for the synthesis of hydroxylamine. It is suggested at the reduction of NO occurs on the Fe²⁺ site of Fe-Pc with protons and electrons transferred from the anode. The very selective synthesis of hydroxylamine over Fe-Pc must be ascribed to an Fe²⁺ site isolated by phthalocyanine ring. This isolation prohibits both the formation of N₂O through the intramolecular elimination of H₂O from the adjacent NHO intermediates and the formation of N₂ and NH₃ through the breaking of N-O bonds.

Full text of DOI:10.1149/1.1837242

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Downloaded on 2015-06-20 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).