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A high open\u2010circuit potential of 0.68\u2005V was achieved by using Fe<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] on a carbon cloth as the cathode and a Ni mesh as the anode of a H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> fuel cell by using an aqueous solution of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> (0.30\u2009 <jats:sc>M<\/jats:sc>, pH\u20053) with a maximum power density of 0.45\u2005mW\u2009cm<jats:sup>\u22122<\/jats:sup>. The open\u2010circuit potential and maximum power density of the H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> fuel cell were further increased to 0.78\u2005V and 1.2\u2005mW\u2009cm<jats:sup>\u22122<\/jats:sup>, respectively, by operation under these conditions at pH\u20051. No catalytic activity of Co<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] and Co<jats:sub>3<\/jats:sub>[{Fe<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] towards H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> reduction suggests that the N\u2010bound Fe ions are active species for H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> reduction. H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> fuel cells that used Fe<jats:sub>3<\/jats:sub>[{Mn<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] and Fe<jats:sub>3<\/jats:sub>[{Cr<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] as the cathode exhibited lower performance compared with that using Fe<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] as a cathode, because ligand isomerization of Fe<jats:sub>3<\/jats:sub>[{M<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] into (FeM<jats:sub>2<\/jats:sub>)[{Fe<jats:sup>II<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] (M=Cr or Mn) occurred to form inactive Fe\uf8ffC bonds under ambient conditions, whereas no ligand isomerization of Fe<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] occurred under the same reaction conditions. The importance of stable Fe<jats:sup>2+<\/jats:sup>\uf8ffN bonds was further indicated by the high performance of the H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> fuel cells with Fe<jats:sub>3<\/jats:sub>[{Ir<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] and Fe<jats:sub>3<\/jats:sub>[{Rh<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>], which also contained stable Fe<jats:sup>2+<\/jats:sup>\uf8ffN bonds. The stable Fe<jats:sup>2+<\/jats:sup>\uf8ffN bonds in Fe<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>], which lead to high activity for the electrocatalytic reduction of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>, allow Fe<jats:sub>3<\/jats:sub>[{Co<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>}<jats:sub>2<\/jats:sub>] to act as a superior cathode in one\u2010compartment H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> fuel cells.<\/jats:p>","DOI":"10.1002\/chem.201300783","type":"journal-article","created":{"date-parts":[[2013,7,19]],"date-time":"2013-07-19T06:52:38Z","timestamp":1374216758000},"page":"11733-11741","source":"Crossref","is-referenced-by-count":99,"title":["A Robust One\u2010Compartment Fuel Cell with a Polynuclear Cyanide Complex as a Cathode for Utilizing H<sub>2<\/sub>O<sub>2<\/sub> as a Sustainable Fuel at Ambient 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