Walsh James J, Smith Charlotte L, Neri Gaia, Whitehead George F S, Robertson Craig M, Cowan Alexander J
Department of Chemistry, Stephenson Institute for Renewable Energy, The University of Liverpool, L69 7ZD, Liverpool, UK.
Faraday Discuss. 2015;183:147-60. doi: 10.1039/c5fd00071h.
Immobilization of [Mn(bpy)(CO)3Br], (1) and [Mn(bpy((t)Bu)2)(CO)3Br] (2, where (bpy((t)Bu)2) = 4,4'-di-tert-butyl-2,2'-bipyridine) in Nafion/multi-walled carbon nanotubes (MWCNT) on glassy carbon yielded highly active electrodes for the reduction of CO2 to CO in aqueous solutions at pH 7. Films incorporating have significantly improved selectivity towards CO2, with CO : H2 ∼ 1 at -1.4 V vs. SCE, exceeding that for the previously reported /MWCNT/Nafion electrode. Furthermore, we report the synthesis and subsequent electrochemical characterization of two new substituted Mn(i) bipyridine complexes, [Mn(bpy(COOH)2)(CO)3Br] (3) and [Mn(bpy(OH)2)(CO)3Br] (4) (where (bpy(COOH)2) = 4,4'-di-carboxy-2,2'-bipyridine and (bpy(OH)2) = 4,4'-di-hydroxy-2,2'-bipyridine). Both 3 and 4 were found to have some activity towards CO2 in acetonitrile solutions; however once immobilized in Nafion membranes CO2 reduction was found to not occur at significant levels.
将[Mn(bpy)(CO)₃Br]（1）和[Mn(bpy((t)Bu)₂)(CO)₃Br]（2，其中(bpy((t)Bu)₂) = 4,4'-二叔丁基-2,2'-联吡啶）固定在玻碳电极上的Nafion/多壁碳纳米管（MWCNT）中，可得到在pH为7的水溶液中将CO₂还原为CO的高活性电极。掺入这些物质的薄膜对CO₂的选择性有显著提高，在相对于饱和甘汞电极（SCE）为-1.4 V时，CO∶H₂约为1，超过了先前报道的/MWCNT/Nafion电极。此外，我们报道了两种新的取代Mn(i)联吡啶配合物[Mn(bpy(COOH)₂)(CO)₃Br]（3）和[Mn(bpy(OH)₂)(CO)₃Br]（4）（其中(bpy(COOH)₂) = 4,4'-二羧基-2,2'-联吡啶，(bpy(OH)₂) = 4,4'-二羟基-2,2'-联吡啶）的合成及后续电化学表征。发现3和4在乙腈溶液中对CO₂都有一定活性；然而，一旦固定在Nafion膜中，发现CO₂还原反应不会大量发生。
