Electrocatalytic Hydrogen Evolution of Cobalt and Free‐base Triaryl Corrole Bearing Hydroxyethyl Amino Groups

Abstract

Four free-base corroles (F 15 C, F 12 C, F 10 C, F 8 C) and their cobalt(III) complexes were used as homogeneous electrocatalysts for hydrogen evolution using acetic acid, trifluoroacetic acid and water as proton sources. Free-base corrole was firstly reported as electrocatalyst for H 2 evolution. The results showed that free-base corrole was active in electrocatalytic hydrogen evolution reaction (HER) in trifluoroacetic acid. And cobalt(III) corroles bearing hydroxyethyl amino groups were more efficient in HER as compared to their benchmark corroles.[a]

Hydrogen evolution catalysis by terminal molybdenum-oxo complexes

“…Having demonstrated the facile access to low valent molybdenum metallocorroles, it attracts the interest to explore their interactions with small molecules and possible catalytic activation thereof. Effective hydrogen evaluation reaction (HER) from trifluoroacetic acid, acetic acid, acetonitrile/water, and neutral buffer solution solutions were recently reported by employing Fe IV , Co III , and Cu III corroles as electrocatalysts ( Chen et al., 2020 ; Lei et al., 2014 , 2015 ; Lin et al., 2020 ; Mahammed et al., 2014 ; Sudhakar et al., 2020 ; Sun et al., 2017 ; Zhong et al., 2019 ). On the other hand, there are no reports regarding HER catalysis by any (oxo)metal porphyrins or corroles despite of their rich redox chemistry.…”

“…Having demonstrated the facile access to low valent molybdenum metallocorroles, it attracts the interest to explore their interactions with small molecules and possible catalytic activation thereof. Effective hydrogen (Chen et al, 2020;Lei et al, 2014Lei et al, , 2015Lin et al, 2020;Mahammed et al, 2014;Sudhakar et al, 2020;Sun et al, 2017;Zhong et al, 2019). On the other hand, there are no reports regarding HER catalysis by any (oxo)metal porphyrins or corroles despite of their rich redox chemistry.…”

Corroles at work: a small macrocycle for great applications

“…36). 76 In this case, the reaction of ethanolamine with TPFCorrCo and 10-PhDPFCorrCo led to the substitution of the parafluorine atoms with ethanolamine groups.…”

“…36 Molecular structures of functionalized TPFCorrCoPPh 3 complexes. 76 facilitating hydrogen evolution. A similar pathway was observed using TFA as the proton source for TPFCorrCo and 10-PhDPFCorrCo but in the case of triethanolamine-substituted corroles, the increase in the TFA concentration led to the increase of the second reduction wave, with the direct Co III -H involvement for the H 2 production.…”

Electrocatalytic hydrogen production by CN– substituted cobalt triaryl corroles

“…33 Cobalt corroles with phosphonic and carboxyl acid pendants functioning as protondonors improve HER activity. 36 Previously, we have used ethoxycarbonyl, 37 nitro, 38 amino, 39 aldehyde and amide pyridyl group 40 substituted cobalt corroles and free-base bis-corrole in the HER. 41 However, it is unclear how the addition of one or more strongly electron-withdrawing CN groups into the corrole macrocycle influences the electrocatalytic activity of cobalt complexes.…”