Electrocatalytic Hydrogen Evolution by Water‐Soluble Cobalt (II), Copper (II) and Iron (III)<i>meso</i>‐Tetrakis(carboxyl)porphyrin

Qi, Xin; Yang, Gang; Guo, Xiaoshuang; Si, Liping; Zhang, Hao; Liu, Haiyang

doi:10.1002/ejic.202200613

Cited by 9 publications

(3 citation statements)

References 47 publications

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“…Hydrogen has garnered attention as a potential solution for reducing greenhouse gas emissions and promoting sustainability due to its clean, versatile, and renewable properties [ 1 , 2 , 3 , 4 , 5 ]. Among the various methods for hydrogen production, metallic porphyrins have emerged as promising catalysts owing to their unique electrochemical and photophysical properties [ 6 , 7 , 8 , 9 , 10 , 11 , 12 ] and their exceptional reactivity in energy-dependent small molecule activation [ 13 ].…”

Section: Introductionmentioning

confidence: 99%

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method

Li,

Feng,

et al. 2024

Molecules

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Substituents at the meso-site of metalloporphyrins profoundly influence the hydrogen evolution reaction (HER) mechanism. This study employs density functional theory (DFT) to computationally analyze NiII-porphyrin and its hydrides derived from tetrakis(pentafluorophenyl)porphyrin molecules, presenting stereoisomers in ortho- or para-positions. The results reveal that the spatial resistance effect of meso-substituted groups at the ortho- and para-positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For ortho-position substituents forming complex I, a favorable 88.88 Å³ spherical space was created, facilitating proton coordination and the formation of H2 molecules; conversely, para-position substituents forming complex II impeded H2 formation until bimolecular complexes arose. Molecular dynamics (MD) analysis and comparison were conducted on the intermediation products of I-H2 and (II-H)2, focusing on the configuration and energy changes. In the I-H2 products, H2 molecules underwent separation after 150 fs and overcame the 2.2 eV energy barrier. Subsequently, significant alterations in the spatial structure were observed as complex I deformed. In the case of (II-H)2, it was influenced by the distinctive “sandwich” configuration; the spatial structure necessitated overcoming a 6.7 eV energy barrier for H2 detachment and a process observed after 2400 fs.

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Section: Introductionmentioning

confidence: 99%

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method

Li,

Feng,

et al. 2024

Molecules

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“…Macrocyclic molecular catalysts have also been used for HER due to their unique chemical structure and tunable activity [16][17][18]. Metal porphyrins have been extensively used in elelctrocatalytic HER [19][20][21]. Corrole is a class of trianionic macrocyclic ligand in the porphyrin family.…”

Section: Introductionmentioning

confidence: 99%

“…This is conducive to electrocatalytic hydrogen evolution by lowering the overpotential [23]. Recently, lots of studies have focused on metal-corrole electrocatalysts in HER [21,24,25]. The catalytic properties of metal corroles may be modulated by modifying the groups at their meso-positions [26].…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogen Evolution of Transition Metal (Fe, Co and Cu)–Corrole Complexes Bearing an Imidazole Group

Wu,

Yao,

et al. 2023

Catalysts

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The study of the hydrogen evolution reaction (HER) by non-noble transition metals is of great significance for the production of hydrogen energy. In this work, a new 5,15-bis-(pentafluorophenyl)-10-[4-(1H-imidazole) phenyl]-corrole and its metal complexes (metal = Co, Cu, Fe) were synthesized and used for electrocatalyzed HER in DMF organic solvent and aqueous media. The prepared cobalt corrole showed the best catalytic performance in both media. Its turnover frequency (TOF) and catalytic efficiency (C.E) could reach 265 s−1 and 1.04 when TsOH was used as the proton source in a DMF solvent. In aqueous media, its TOF could also reach 405 h−1. The catalytic HER may go through an EECEC or ECEC (E: electron transfer, C: chemical step) pathway for these catalysts, depending on the acidity and concentration of the proton source. The present work successfully demonstrates that imidazole at a meso-phenyl group may improve the electrocatalytic HER activity of transition metal corroles.

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Proton Activation in the Presence of a Weak Acid Facilitated by Second Coordination Sphere Effects in Iron Porphyrins**

Ramuglia,

Budhija,

et al. 2023

ChemElectroChem

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The catalytic activity of two iron‐based porphyrin complexes containing pyridine‐functionalized second coordination spheres, referred to as Py2XPFe and CuPy2XPFe, have been investigated for the hydrogen evolution reaction (HER) and compared with the unsubstituted analog TMPFe in acetonitrile. The CuPy2XPFe incorporates a second metal center within the pyridine residues and represents a heterodinuclear system, while the structurally analogous Py2XPFe lacks an additional metal in the second coordination sphere. Both the Py2XFe and CuPy2XPFe complexes are observed to activate the weak acid, acetic acid (AcOH) at the FeII/I couple rather than at the more energy intensive FeI/0 couple observed for the unfunctionalized TMPFe complex at low acid concentrations. The ability of the monometallic Py2XPFe to activate the weak proton source at the FeII/I couple manifests as an ECEC(E)′ type electrochemical mechanism, rather than an EECC(E)′ type mechanism as observed for TMPFe. The CuPy2XPFe displays improved reactivity compared with the Py2XPFe and TMPFe under the same substrate conditions, however the mechanistic nuances into bimetallic CuPy2XPFe system are currently unclear. The concentration of AcOH was incrementally increased and the rate constants of the initial protonation step i. e. formation of a hydridic species (k1,app), as well as of the protonation of the hydridic species to produce dihydrogen (kglobal) were calculated using the Foot‐of‐the‐wave and plateau current rate equation methodologies, respectively. The kinetic analysis indicates that the activation of protons through the ECEC(E)′ type mechanism for the Py2XPFe results in a system in which k1,app< kglobal. As both the monometallic Py2XPFe and bimetallic CuPy2XPFe activate the AcOH at less cathodic potentials than TMPFe under identical conditions, the overpotentials (ηTOF/2) for these complexes are thus dramatically lower. The reactivity difference of the Py2XPFe when compared to non‐substituted iron porphyrin analogs is due to the hanging group's influence, which is believed to either act as hydrogen bond promoters for the active site or aids to stabilize a catalytic intermediate species during catalysis.

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Electrocatalytic Hydrogen Evolution by Water‐Soluble Cobalt (II), Copper (II) and Iron (III)meso‐Tetrakis(carboxyl)porphyrin

Cited by 9 publications

References 47 publications

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method

Electrocatalytic Hydrogen Evolution of Transition Metal (Fe, Co and Cu)–Corrole Complexes Bearing an Imidazole Group

Proton Activation in the Presence of a Weak Acid Facilitated by Second Coordination Sphere Effects in Iron Porphyrins**

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