The cobalt corrole catalyzed hydrogen evolution reaction: surprising electronic effects and characterization of key reaction intermediates

Mahammed, Atif; Mondal, Biswajit; Rana, Atanu; Dey, Abhishek; Gross, Zeev

doi:10.1039/c3cc48462a

Cited by 145 publications

(112 citation statements)

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“…[10][11][12][13] Our investigation of the latter catalytic process disclosed cobalt(I) corroles as key reaction intermediates,a nd also that the introduction of halide substituents on the corrole periphery shifts the catalytic onset potential to the highly desired positive voltage direction. [14] One significant shortcoming was that while the derivative with eight fluorine atoms on the bpyrrole positions was the most active catalyst, its Co I /Co II redox potential and consequentially its catalytic onset potential were less positive than that of the derivatives with either eight chlorine or eight bromine atoms.T he reason was elucidated to be ac onsequence of the strongest s-withdrawing effect of fluorine being more than counterbalanced by its most effective p-donation ability.Inthe course of our search for metallocorroles whose redox potentials are more positively shifted than those of the halide-substituted derivatives, we decided to turn our attention to corroles with purely electron-withdrawing CF 3 substituents.…”

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Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles

et al. 2017

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Gold corroles are not readily accessible and they display no interesting physical or chemical properties. A facile methodology has now been developed for obtaining selectively CF -substituted gold(III) corroles and the introduction of these groups has been found to have an immense effect on the structures of the complexes, their photophysical and redox properties, and on their ability to participate in catalytic processes.

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Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles

et al. 2017

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“…A class of such hydrogen evolution electrocatalyst is cobaloxime complexes Co(dmgh) 2 XY with the bidentate dimethylglyoxime (dmgH) or its derivatives as the equatorial ligands. The commonly used axial ligands X and Y are acetonitrile, pyridine, water and chloride [1][2][3][4][5].…”

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Proton reduction using cobalt glyoximes with isothiocyanate and aniline axial ligands

2015

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“…[1][2][3] During the last decade,avariety of molecular complexes based on earth-abundant transition-metal elements including Mn, [4][5][6][7] Fe, [8][9][10][11][12][13][14] Co, [15][16][17][18][19][20][21] Ni, [22][23][24][25][26][27][28] and Cu [29][30][31][32][33] have been identified as catalystsf or these two reactions. [1][2][3] During the last decade,avariety of molecular complexes based on earth-abundant transition-metal elements including Mn, [4][5][6][7] Fe, [8][9][10][11][12][13][14] Co, [15][16][17...…”

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Convenient Immobilization of Cobalt Corroles on Carbon Nanotubes through Covalent Bonds for Electrocatalytic Hydrogen and Oxygen Evolution Reactions

Lei

et al. 2019

ChemSusChem

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Twod ifferentm ethods were used to immobilize Co corroles on carbon nanotubes (CNTs) through covalent bonds. The resulting CNTse ngineered with Co corroles were used as electrocatalysts for the hydrogen evolutionr eaction (HER) and the oxygen evolution reaction (OER) in aqueous solutions of pH 0, 7, and 14. For both HER andO ER in all solutions, the hybrids obtained by attaching Co corroles on CNTst hrough amidation coupling showedb etter performance. This is likely because the large surface area and good electricalc onductivity of CNTsc an be well preserved during the amidationr eactionu nder mild conditions.The development of inexpensive, efficient, and robust electrocatalysts for the hydrogen evolutionr eaction (HER) and the oxygen evolution reaction( OER) has attracted increasing interest because of their appealing applicationsi nn ew energy technologies. [1][2][3] During the last decade,avariety of molecular complexes based on earth-abundant transition-metal elements including Mn, [4][5][6][7] Fe, [8][9][10][11][12][13][14] Co, [15][16][17][18][19][20][21] Ni, [22][23][24][25][26][27][28] and Cu [29][30][31][32][33] have been identified as catalystsf or these two reactions. To make these well-designed molecular catalysts useful in practice, they need to be immobilizedo ne lectrode materials. [34][35][36][37][38] Covalent immobilizationi su seful to improvec atalyst stabilitya nd performance and benefitst he recycling of electrocatalysts. [39][40][41][42][43] Despite these progresses,h owever, convenient methods for covalenti mmobilization under mild conditions are still needed.Carbon nanotubes (CNTs) are broadly used as supports for electrochemical applications because of their large surface areas and good electrical conductivities. [37,[44][45][46][47][48][49] Thep resence of abundant carboxyl groups on the surface of oxidized CNTsprovides ideal sites to attach catalystm olecules bearing amine groups through the amidation reaction. The resulting amide bonds tolerateb oth acidic and basic media and have sufficient stabilityu nder reductive and oxidative conditions. These features make CNTsp romising electrode materials for molecular engineering. However, the direct reaction of carboxyl and amine groupst of orm amide bonds is challenging. Therefore, carboxyl groups are usually converted to acyl chloride groups for subsequent amidation reaction.Herein, we report the convenient immobilization of Co corroles on CNTst hrough amidation coupling under mild conditions. Co corroles have been shown to be highly active and stable as catalysts for HERa nd OER under various conditions, [3,19] andt hust hey were chosen as model complexes in this work. The resulting hybrid can catalyze both HER and OER in aqueous solutionso fp H0,7 ,a nd 14. Compared with the traditional amidation by activating carboxyl groups with sulfinyl dichloride (SOCl 2 ), the directa midation coupling is simpler and more straightforward, and the resulting hybrid shows much better performance. This work is significant to showt he importance of the co...

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The cobalt corrole catalyzed hydrogen evolution reaction: surprising electronic effects and characterization of key reaction intermediates

Cited by 145 publications

References 18 publications

Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles

Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles

Proton reduction using cobalt glyoximes with isothiocyanate and aniline axial ligands

Convenient Immobilization of Cobalt Corroles on Carbon Nanotubes through Covalent Bonds for Electrocatalytic Hydrogen and Oxygen Evolution Reactions

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The cobalt corrole catalyzed hydrogen evolution reaction: surprising electronic effects and characterization of key reaction intermediates

Cited by 145 publications

References 18 publications

Effect of Selective CF3 Substitution on the Physical and Chemical Properties of Gold Corroles

Effect of Selective CF3 Substitution on the Physical and Chemical Properties of Gold Corroles

Proton reduction using cobalt glyoximes with isothiocyanate and aniline axial ligands

Convenient Immobilization of Cobalt Corroles on Carbon Nanotubes through Covalent Bonds for Electrocatalytic Hydrogen and Oxygen Evolution Reactions

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Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles

Effect of Selective CF₃ Substitution on the Physical and Chemical Properties of Gold Corroles