Journal of Electroanalytical Chemistry, Vol.395, No.1-2, 195-209, 1995
An in-Situ Fourier-Transform Infrared Study of CO2 Electroreduction Catalyzed by Ni(0)-4,4’-Dimethyl 2,2’-Bipyridine and Ni(0)-1,10-Phenanthroline Complexes
The electrochemical reduction of CO2 by electrogenerated LNi(0) and (L(.-))Ni(0) (L = 4,4’-dimethyl-2,2’-bipyridine, 1,10-phenanthroline) complexes has been studied using in-situ Fourier transform IR spectroscopy. Electrogenerated [L(2)NI] reacts slowly with CO2 to produce [Ni(L)(CO)(2)]; no intermediates could be detected in this reaction. However, the dicarbonyls with both L = Phen and L = 4,4’-dimethyl-2,2’-bipyridine (Me(2)Bipy) react with trace water to give [Ni-2(mu-H)(CO)(6)](-), providing a route that is operative at relatively high potentials. At more negative potentials (below -1.6 V vs. the saturated calomel electrode (SCE)), where a catalytic current due to CO2 reduction is seen, spectroscopic evidence for the transient formation of [Ni(Me(2)Bipy(.-))(CO)(2)] has been found. It appears that [Ni(Me(2)Bipy(.-))(CO)(2)] reacts sufficiently fast that its steady state concentration in the thin layer is very low. In contrast, [Ni(Phen(.-))(CO)(2)] is more stable. For both complexes, electrogenerated CO, which cannot escape from the thin layer, attacks the radical dicarbonyl species to form [NI(CO)(4)], which is then ultimately reduced to nickel carbonyl cluster anions. [Ni(Phen)(CO)(2)] also reacts to produce a metalloformate species, not observed with the Me(2)Bipy analogue. The OC-Ni-CO angle was calculated for each of the four [Ni(L)(CO)(2)] and [Ni(L(.-))(CO)(2)] species and was found to be 104 degrees +/- 2 degrees, in agreement with the expected tetrahedral geometry of a Ni(0) complex.
Keywords:CARBON-DIOXIDE;ELECTROCATALYTIC REDUCTION;CHEMICAL CHARACTERIZATION;ELECTROCHEMICAL REDUCTION;NICKEL;ELECTRODES;ACETONITRILE;OXIDATION