Chemical catalysis of electrochemical reactions. Homogeneous catalysis of the electrochemical reduction of carbon dioxide by iron("0") porphyrins. Role of the addition of magnesium cations

Abstract

lron("0") porphyrins catalyze the electrochemical reduction of C02. The main reduction product is CO. In DMF, with tetraalkylammonium salts as supporting electrolyte, the porphyrin is however destroyed by carboxylation and/or hydrogenation of the ring after a few catalytic cycles. The presence of a hard electrophile such as Mg2+ ion dramatically improves the rate of the reaction, the production of CO, and, most importantly, the stability of the catalyst. The reaction mechanism involves the introduction of one molecule of C02 into the iron coordination sphere. The addition of a second molecule of C02 acts as a Lewis acid and then allows the breaking of one C-0 bond of the first C02 molecule thus leading to CO. This process is accelerated by Mg2+ ions in a way that depends upon the temperature. At low temperatures (-40 °C), the Mg2+ ions facilitate the decomposition of the complex containing two molecules of C02, whereas, at room temperature, Mg2+ ions triggers the breaking of the bond at the level of the complex containing a single molecule of C02 in its coordination sphere. The combined action of iron("0") porphyrins and of Mg2+ ions offers a remarkable example of a bimetallic catalysis where an electron-rich center starts the reduction process and an electron-deficient center assists the transformation of the bond system. catalytic reactions and on metal surfaces.

Cathodic reactivity of graphite with carbon dioxide: an efficient formation of carboxylated carbon materials

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Ultraefficient homogeneous catalyst for the CO 2 -to-CO electrochemical conversion

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