Positional effects of second-sphere amide pendants on electrochemical CO₂ reduction catalyzed by iron porphyrins

Abstract

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.

Unexpected Effect of Intramolecular Phenolic Group on Electrocatalytic CO2 Reduction

“…Attempts to obtain single crystals of 1-Cl suitable for X-ray structure analysis were unsuccessful. Fortunately, the reaction of FeCl 2 with various porphyrins under the same conditions has been well documented in the literature, [38][39][40] showing that a Fe III ion is incorporated at the center of the porphyrin ring with an axial chloride ligand. The Fe III ion is obtained from the oxidation of Fe II with air.…”

“…Fe porphyrins have received considerable attention among these catalysts . They show high activity and stability for the selective CO 2 ‐to‐CO conversion, and they provide an ideal platform to investigate various structural effects on CO 2 RR, because the meso ‐substituents of the porphyrin ring can be systematically modified to introduce different acid/base groups and positively/negatively charged moieties .…”

Artificial photosynthesis with metal and covalent organic frameworks (MOFs and COFs): challenges and prospects in fuel‐forming electrocatalysis

“…Additional approaches may investigate how catalytic pocket hydrophobicity may play a role in influencing catalytic rates and selectivity. These principles were, in part, demonstrated with homogenous catalysts (Azcarate et al , Nichols et al ) and would serve as rational starting points for implementation within a MOF/COF framework. Furthermore, the incorporation of proton relays, previously demonstrated for HER catalysis, may promote hydrogenation of intermediates in CO 2 R (Hod et al ).…”

RhI‐Catalyzed PIII‐Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide

“…Notably,the phosphine-amide 3g furnished the best selectivity (5a/6a= 79:21). [21] Thep hosphine-diamide 4e gave good conversion and selectivity (85 %, 79:21), which is attributed to avoidance of the formation of aPd-cyclometalated phosphine complex owing to the fact that the both phosphine ortho'position are substituted. [22] Theh ybrid ligand 4h,w hich contains an ester and an amide group,a fforded as lightly better conversion with similar 5a selectivity (91 %, 80:20).…”