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- W2017000306 abstract "Experimental results on the electroreduction of CO2 on gas diffusion electrodes modified by MPc, reported in a previous paper [N. Furuya and K. Matsui, J. electroanal. Chem.271 181 (1989)], are interpreted qualitatively by means of Taube's theory based on the Hückel model [R. Taube, Z. Chem.6, 8 (1966); R. Taube, Pure appl. Chem38, 429 (1974)]. The reason why some of the MPc produce CO or CH4 while others yield HCOOH is explained by the electron configurations in the metallic atoms. The reduction of CO2 to CO is attributed to the strongly electron-donating HOMO of [MPc]n− arising from the electron-accepting LUMO of neutral MPc which spreads over the nitrogen atoms surrounding M. The final production of CO occurs when the created CO is promptly desorbed from the metallic atom M having such a bare d-shell with the doubly occupied 2a1 g (dz2) orbital. If, on the contrary, the CO molecule is bound to the metallic atom by a -bonding, the reduction may proceed up to CH4 production. In metals having outermost s or p electrons, the electron occupation of the spread LUMO by ionization will not take place and such a strong reduction as to produce CO may not be possible. Then the electron transfer from MPc to CO2 will result in the production of [CO2]− followed by HCOOH creation instead of CO. The anion [CO2]− bents as ∠ OC−O=134°, and the C− will probably form a -bond with dz2 or pz of M, making the so-called carbondioxide complex, until further reduction to HCOOH." @default.
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- W2017000306 title "Electroreduction of carbon dioxide by metal phthalocyanines" @default.
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- W2017000306 doi "https://doi.org/10.1016/0013-4686(91)80010-6" @default.
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