Porphyrin-catalyzed electrochemical hydrogen evolution reaction. Metal-centered and ligand-centered mechanisms

Castro-Cruz, Hiram M.; Macı́as-Ruvalcaba, Norma A.

doi:10.1016/j.ccr.2022.214430

Cited by 60 publications

(28 citation statements)

References 97 publications

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“…Metal porphyrins have shown great potential as molecular catalysts for the electrochemically triggered hydrogen evolution reaction (HER) due to their ability to participate in different proton-coupled electron transfer process (PCET) in the past few decades [ 46 , 47 , 48 ]. These processes generate intermediates that can donate hydrides to free protons, thus releasing hydrogen.…”

Section: Resultsmentioning

confidence: 99%

Investigation of Molecular Mechanism of Cobalt Porphyrin Catalyzed CO2 Electrochemical Reduction in Ionic Liquid by In-Situ SERS

Jiang

Yang

et al. 2023

Molecules

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This study explores the electrochemical reduction in CO2 using room temperature ionic liquids as solvents or electrolytes, which can minimize the environmental impact of CO2 emissions. To design effective CO2 electrochemical systems, it is crucial to identify intermediate surface species and reaction products in situ. The study investigates the electrochemical reduction in CO2 using a cobalt porphyrin molecular immobilized electrode in 1-n-butyl-3-methyl imidazolium tetrafluoroborate (BMI.BF4) room temperature ionic liquids, through in-situ surface-enhanced Raman spectroscopy (SERS) and electrochemical technique. The results show that the highest faradaic efficiency of CO produced from the electrochemical reduction in CO2 can reach 98%. With the potential getting more negative, the faradaic efficiency of CO decreases while H2 is produced as a competitive product. Besides, water protonates porphyrin macrocycle, producing pholorin as the key intermediate for the hydrogen evolution reaction, leading to the out-of-plane mode of the porphyrin molecule. Absorption of CO2 by the ionic liquids leads to the formation of BMI·CO2 adduct in BMI·BF4 solution, causing vibration modes at 1100, 1457, and 1509 cm−1. However, the key intermediate of CO2−· radical is not observed. The υ(CO) stretching mode of absorbed CO is affected by the electrochemical Stark effect, typical of CO chemisorbed on a top site.

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Section: Resultsmentioning

confidence: 99%

Investigation of Molecular Mechanism of Cobalt Porphyrin Catalyzed CO2 Electrochemical Reduction in Ionic Liquid by In-Situ SERS

Jiang

Yang

et al. 2023

Molecules

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“…28,[32][33][34][35][36][37] Moreover, the groups present at the porphyrin periphery (electron-withdrawing or electron-releasing), their position, oxidation state as well as the electronic nature of the central metal ion, and core structure, have a considerable effect on the redox characteristics of synthetic porphyrins. [38][39][40][41] Porphyrins show a strong absorption in the visible-light region, due to their protracted p-electron systems with considerable thermochemical stability, and thus are used as components of advanced materials. 42,43 Tetraphenylporphyrins that bear one, four and eight bromine substituents at the b-pyrrole positions have been extensively synthesized and explored on account of such facile and direct bromination at the porphyrin periphery.…”

Section: Introductionmentioning

confidence: 99%

Regioselective 2,3-disubstituted porphyrins: synthesis, spectral, structural and electrochemical properties

Arif

Kumar

2023

New J. Chem.

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“…[37][38][39][40] For alkaline HER, the water dissociation process (H 2 O + e − → OH − + H ad , the Volmer step) usually shows sluggish kinetics restricted by the shortage of appropriate sites for the H-OH bond breakage and hydroxyl (OH − ) adsorption, being regarded as the ratedetermining step (RDS). 41 To reduce the energy barrier of the alkaline HER RDS, the nanoscaled integration of TMPs with metal oxide species could confer the formed catalyst with enhanced electrocatalytic activity due to the better hydrophilicity and favorable OH − binding energy of metal oxide species in alkaline media, making the dissociative adsorption of water thermodynamically favorable and rapid. 42,43 On the other hand, nanoarchitectonics design also enables improvement of the accessibility and utilization of active sites, reduction of the resistance of mass diffusion, and improvement of the electron-transfer efficiency.…”

Section: Introductionmentioning

confidence: 99%

Reactive template‐derived interfacial engineering of CoP/CoO heterostructured porous nanotubes towards superior electrocatalytic hydrogen evolution

et al. 2022

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The development of economical, efficient, and robust electrocatalysts toward the hydrogen evolution reaction (HER) is highly imperative for the rapid advancement of renewable H 2 energy-associated technologies. Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites. Herein, we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes (abbreviated as CoP/CoO PNTs hereafter) using a self-sacrificial template-engaged strategy. Precise control over the Kirkendall diffusion process of the presynthesized cobalt-aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures. The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes. The establishment of CoP/ CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity, which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity. Simultaneously, the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability, drastically promoting the reaction kinetics. Consequently, when used as HER electrocatalysts, the Carbon Energy.

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Porphyrin-catalyzed electrochemical hydrogen evolution reaction. Metal-centered and ligand-centered mechanisms

Cited by 60 publications

References 97 publications

Investigation of Molecular Mechanism of Cobalt Porphyrin Catalyzed CO2 Electrochemical Reduction in Ionic Liquid by In-Situ SERS

Investigation of Molecular Mechanism of Cobalt Porphyrin Catalyzed CO2 Electrochemical Reduction in Ionic Liquid by In-Situ SERS

Regioselective 2,3-disubstituted porphyrins: synthesis, spectral, structural and electrochemical properties

Reactive template‐derived interfacial engineering of CoP/CoO heterostructured porous nanotubes towards superior electrocatalytic hydrogen evolution

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