Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins

Abstract

The electrochemical reduction of carbon dioxide is studied herein by using conducting polymers based on metallotetraruthenated porphyrins (MTRPs). The polymers on glassy carbon electrodes were obtained by electropolymerization processes of the monomeric MTRP. The linear sweep voltammetry technique resulted in polymeric films that showed electrocatalytic activity toward carbon dioxide reduction with an onset potential of -0.70 V. The reduction products obtained were hydrogen, formic acid, formaldehyde, and methanol, with a tendency for a high production of methanol with a maximum value of turnover frequency equal to 15.07 when using a zinc(II) polymeric surface. Studies of the morphology (AFM) and electrochemical impedance spectroscopy results provide an adequate background to explain that the electrochemical reduction is governed by the roughness of the polymer, for which the possible mechanism involves a series of one-electron reduction reactions.

Enhanced Electrochemical Reduction of CO2 to CO upon Immobilization onto Carbon Nanotubes Using an Iron‐Porphyrin Dimer

“…In this project, a new urea iron-tetraphenylporphyrin-dimer (Fe-TPP-Dimer) was synthesized and applied for electrocatalytic CO 2 reduction under both homogeneous and heterogeneous conditions to selectively reduce CO 2 to CO. Immobilization of the catalyst onto carbon nanotubes (CNTs) in aqueous solution resulted in remarkable enhancement of its electrocatalytic abilities, with exceptional turnover frequencies (10 s À 1 ), high faradic efficiency (FE) of ∼ 90%, and a current density of 16 mA/cm 2 at À 0.88 V vs. RHE. [12][13][14][15][16][17][18][19][20] Extensive research has been conducted on both homogeneous and heterogeneous molecular catalysts for CO 2 RR. [1][2][3][4][5] Although the capture and conversion of CO 2 to value-added synthons has become a desirable solution to this problem, challenges in regard to the species' general lack of reactivity and the costs associated with deployment and stability of such strategies remain prevalent.…”

“…[1][2][3][4][5] Although the capture and conversion of CO 2 to value-added synthons has become a desirable solution to this problem, challenges in regard to the species' general lack of reactivity and the costs associated with deployment and stability of such strategies remain prevalent. [12][13][14][15][16][17][18][19][20] Extensive research has been conducted on both homogeneous and heterogeneous molecular catalysts for CO 2 RR. [12][13][14][15][16][17][18][19][20] Extensive research has been conducted on both homogeneous and heterogeneous molecular catalysts for CO 2 RR.…”

Electrochemical Conversion of Carbon Dioxide into CHO‐Containing Compounds on Multimetallic Porphyrins

“…Recent reports state that film morphology (monitored by AFM) is affected after being used as an electrocatalyst, suggesting mobility of the electroactive species on electrode surface that affects the morphology of the modified surfaces ,…”

“…The electrochemical reduction of CO 2 is a promising process for this aim; depending on the number of electrons transferred; it is possible to obtain several products, being the most interesting when two or more electrons are transferred producing formic acid or formaldehyde; or even better, generating methane, methanol or ethanol . In order to obtain these products, electrocatalysts based on transition metals complexes containing multiple metal centers have been used to achieve multielectron transfer ,.…”

Quick and Easy Modification of Glassy Carbon Electrodes with Ionic Liquid and Tetraruthenated Porphyrins for the Electrochemical Determination of Atrazine in Water

“…These kind of macrocycles are particularly attractive because they display unusual electrocatalytic and photoelectrochemical properties . In particular, these porphyrins have been used in the electroanalytical detection of S (IV) oxoanions and electrocatalytic reduction of O 2 and CO 2 . In all cases, a multielectron transfer is essential to enhance the catalytic activity .…”