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A Dinuclear Nickel Complex for Electrocatalytic Nitrite Reduction
Sheyda Partovi1, Yaroslav Losovyj1,2, Nobuyuki Yamamoto1
1Department of Chemistry, Indiana University, Bloomington 47405, Indiana, United States.
Abstract:
While many mononuclear complexes for electrocatalytic NO- reduction have been reported, there are few examples of dinuclear electrocatalysts. Here, we report on the electroreduction of NO2- by the dinuclear complex [Ni2(tpmc)(NO3)2]2+ (tpmc = 1,4,8,11-tetrakis-(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane) and a mononuclear analogue [Ni(cyclam)]2+ (cyclam = 1,4,8,11-tetraazacyclotetradecane). Notably, the presence of the second metal ion in [Ni2(tpmc)(NO3)2]2+ shifts the onset of catalysis anodically by ca. 0.3 V compared to [Ni(cyclam)]2+, while maintaining a similar electrocatalytic rate and Faradaic efficiency. Both complexes produce NH4+ as the primary reduction product. Interestingly, in some respects, Ni2+(aq) is a better electrocatalyst for NO2- than [Ni(cyclam)]2+, with faster electrocatalysis occurring at a more anodic onset potential, although the Faradaic efficiency for NH4+ is lower.
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