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Title: A hydrogen-nitric oxide cell for the synthesis of hydroxylamine

Abstract

A H{sub 2}-NO fuel cell was designed for the synthesis of hydroxylamine in the gas phase. The hydroxylamine produced was trapped in an aqueous solution of H{sub 2}SO{sub 4} held in a silica-wool disk used as an electrolyte barrier for H{sub 2} 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 N{sub 2}O and NH{sub 3}. Excluding the effects of the support, Fe-Pc catalyzed the electrochemical synthesis of hydroxylamine with high selectivity ({approx} 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 that the reduction of NO occurs on the Fe{sup 2+} 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 Fe{sup 2+} site isolated by phthalocyanine ring. This isolation prohibits both the formation of N{sub 2}O through the intramolecular elimination of H{sub 2}O from the adjacentmore » NHO intermediates and the formation of N{sub 2} and NH{sub 3} through the breaking of N-O bonds.« less

Authors:
; ;  [1]
  1. Tokyo Inst. of Tech. (Japan). Dept. of Chemical Engineering
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
428161
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 143; Journal Issue: 11; Other Information: PBD: Nov 1996
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; HYDROXYLAMINE; SYNTHESIS; HYDROGEN FUEL CELLS; OPERATION; NITRIC OXIDE; HYDROGENATION; BATTERY SEPARATORS; ELECTROCATALYSTS; CHEMICAL REACTION KINETICS; POWER GENERATION; CHEMICAL FEEDSTOCKS; DUAL-PURPOSE POWER PLANTS

Citation Formats

Otsuka, Kiyoshi, Sawada, Hidenori, and Yamanaka, Ichiro. A hydrogen-nitric oxide cell for the synthesis of hydroxylamine. United States: N. p., 1996. Web. doi:10.1149/1.1837242.
Otsuka, Kiyoshi, Sawada, Hidenori, & Yamanaka, Ichiro. A hydrogen-nitric oxide cell for the synthesis of hydroxylamine. United States. doi:10.1149/1.1837242.
Otsuka, Kiyoshi, Sawada, Hidenori, and Yamanaka, Ichiro. Fri . "A hydrogen-nitric oxide cell for the synthesis of hydroxylamine". United States. doi:10.1149/1.1837242.
@article{osti_428161,
title = {A hydrogen-nitric oxide cell for the synthesis of hydroxylamine},
author = {Otsuka, Kiyoshi and Sawada, Hidenori and Yamanaka, Ichiro},
abstractNote = {A H{sub 2}-NO fuel cell was designed for the synthesis of hydroxylamine in the gas phase. The hydroxylamine produced was trapped in an aqueous solution of H{sub 2}SO{sub 4} held in a silica-wool disk used as an electrolyte barrier for H{sub 2} 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 N{sub 2}O and NH{sub 3}. Excluding the effects of the support, Fe-Pc catalyzed the electrochemical synthesis of hydroxylamine with high selectivity ({approx} 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 that the reduction of NO occurs on the Fe{sup 2+} 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 Fe{sup 2+} site isolated by phthalocyanine ring. This isolation prohibits both the formation of N{sub 2}O through the intramolecular elimination of H{sub 2}O from the adjacent NHO intermediates and the formation of N{sub 2} and NH{sub 3} through the breaking of N-O bonds.},
doi = {10.1149/1.1837242},
journal = {Journal of the Electrochemical Society},
number = 11,
volume = 143,
place = {United States},
year = {1996},
month = {11}
}