Understanding the factors governing the water oxidation reaction pathway of mononuclear and binuclear cobalt phthalocyanine catalysts

Huang, Qinge; Luan, Peng; Ding, Chunmei; Li, Can

doi:10.1039/d2sc02213c

Cited by 6 publications

(9 citation statements)

References 51 publications

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“…The optimized Fe–N bond lengths in Fe-Pc and bi-FePc are 1.95 and 1.93 Å, respectively, while those of the Co–N bond in Co-Pc and bi-CoPc are approximately 1.90 and 1.93 Å. These values are in good agreement with the reported number of the Fe–N and Co–N bonds, which attests to the accuracy of the adopted models and the computational strategies employed in this study.…”

supporting

confidence: 85%

“…The detailed structure data are shown in Table 1. The optimized Fe−N bond lengths in Fe-Pc 36 which attests to the accuracy of the adopted models and the computational strategies employed in this study.…”

mentioning

confidence: 56%

“…35 The bimetallic cobalt phthalocyanine (bi-CoPc) reported by this group has proven to be an excellent alkaline OER catalyst. 36 Bi-CoPc supported on a carbon substrate (bi-CoPc/carbon) displayed an overpotential of 357 mV at 10 mA cm −2 , significantly lower than that of mono-CoPc/carbon (>450 mV). Moreover, even though MPc and bi-MPc have been mostly emphasized as OER catalysts, few reports are still available on the origin of the synergistic effects between different central metals in bi-MPc.…”

mentioning

confidence: 94%

“…Sannegowda et al reported that, when nickel foam coated with CoPc polymers was employed as an OER catalyst, it exhibited a low overpotential of 0.37 V at a current density of 10 mA cm –2 . The bimetallic cobalt phthalocyanine (bi-CoPc) reported by this group has proven to be an excellent alkaline OER catalyst . Bi-CoPc supported on a carbon substrate (bi-CoPc/carbon) displayed an overpotential of 357 mV at 10 mA cm –2 , significantly lower than that of mono-CoPc/carbon (>450 mV).…”

mentioning

confidence: 99%

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Binuclear Metal Phthalocyanines with Enhanced Activity in the Oxygen Evolution Reaction: A First-Principles Study

Chen,

Liu,

Duan

et al. 2024

J. Phys. Chem. Lett.

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The rational design of efficient catalysts for the electrochemical oxygen evolution reaction (OER) critically relies on a comprehensive understanding of the reaction mechanisms. Herein, the alkaline OER on planar mononuclear metal phthalocyanines (MPc, where M = Mn, Co, Fe, and Ni) and binuclear metal phthalocyanines (bi-MPc) is studied using density functional theory (DFT) methods. Both FePc and bi-CoPc exhibit enhanced stability and OER activity, with the energy required for the leaching of central metal being as high as 2.28 and 2.45 eV and the overpotentials of the OER being 0.48 and 0.57 V, respectively. Through electronic structure analysis, it is found that, in the OER process of bi-MPc, the large macrocyclic ligand and metal ions not bonding with the intermediate can serve as hole reservoirs. Intermediate species are further stabilized by the dispersal of a positive charge, reducing the free energy. These findings underscore the significance of macrocyclic ligands in the rate-determining step of the OER catalyst.

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supporting

confidence: 85%

mentioning

confidence: 56%

mentioning

confidence: 94%

mentioning

confidence: 99%

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Binuclear Metal Phthalocyanines with Enhanced Activity in the Oxygen Evolution Reaction: A First-Principles Study

Chen,

Liu,

Duan

et al. 2024

J. Phys. Chem. Lett.

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“…Based on this rationale, we anticipate that high-valence metal-oxo species can be generated in MPc under anodic potential and potentially used for electrochemical oxidation reactions . However, MPc is more widely recognized as an active catalyst in electrochemical reductions such as 2e – ORR (refs , ) and CO 2 RR (refs , ), with scarce explorations on electrochemical oxidations except for a few studies on oxygen evolution reaction (OER, refs , ).…”

Section: Introductionmentioning

confidence: 99%

One-Step Electrochemical Ethylene-to-Ethylene Glycol Conversion over a Multitasking Molecular Catalyst

Li,

Yuan,

et al. 2024

J. Am. Chem. Soc.

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Ethylene glycol is an essential commodity chemical with high demand, which is conventionally produced via thermocatalytic oxidation of ethylene with huge fossil fuel consumption and CO 2 emission. The one-step electrochemical approach offers a sustainable route but suffers from reliance on noble metal catalysts, low activity, and mediocre selectivity. Herein, we report a one-step electrochemical oxidation of ethylene to ethylene glycol over an earth-abundant metal-based molecular catalyst, a cobalt phthalocyanine supported on a carbon nanotube (CoPc/CNT). The catalyst delivers ethylene glycol with 100% selectivity and 1.78 min −1 turnover frequency at room temperature and ambient pressure, more competitive than those obtained over palladium catalysts. Experimental data demonstrate that the catalyst orchestrates multiple tasks in sequence, involving electrochemical water activation to generate high-valence Co-oxo species, ethylene epoxidation to afford an ethylene oxide intermediate via oxygen transfer, and eventually ring-opening of ethylene oxide to ethylene glycol facilitated by in situ formed Lewis acid site. This work offers a great opportunity for commodity chemicals synthesis based on a one-step, earth-abundant metal-catalyzed, and renewable electricity-driven route.

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Exploring the Cooperation of the Redox Non‐Innocent Ligand and Di‐Cobalt Center for the Water Oxidation Reaction Catalyzed by a Binuclear Complex

Li,

Liao

2024

ChemSusChem

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Water oxidation is a crucial reaction in the artificial photosynthesis system. In the present work, density functional calculations were employed to decipher the mechanism of water oxidation catalyzed by a binuclear cobalt complex, which was disclosed to be a homogeneous water oxidation catalyst in pH=7 phosphate buffer. The calculations showed that the catalytic cycle starts from the CoIII,III‐OH2 species. Then, a proton‐coupled electron transfer followed by a one‐electron transfer process leads to the generation of the formal CoIV,IV‐OH intermediate. The subsequent PCET produces the active species, namely the formal CoIV,V=O intermediate (4). The oxidation processes mainly occur on the ligand moiety, including the coordinated water moiety, implying a redox non‐innocent behavior. Two cobalt centers keep their oxidation states and provide one catalytic center for water activation during the oxidation process. 4 triggers the O‐O bond formation via the water nucleophilic attack pathway, in which the phosphate buffer ion functions as the proton acceptor. The O‐O bond formation is the rate‐limiting step with a calculated total barrier of 17.7 kcal/mol. The last electron oxidation process coupled with an intramolecular electron transfer results in the generation of O2.

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Understanding the factors governing the water oxidation reaction pathway of mononuclear and binuclear cobalt phthalocyanine catalysts

Abstract: The rational design of efficient catalysts for electrochemical water oxidation highly depends on the understanding of reaction pathways, which still remains a challenge. Herein, mononuclear and binuclear cobalt phthalocyanine (mono-CoPc...

Cited by 6 publications

References 51 publications

Binuclear Metal Phthalocyanines with Enhanced Activity in the Oxygen Evolution Reaction: A First-Principles Study

Binuclear Metal Phthalocyanines with Enhanced Activity in the Oxygen Evolution Reaction: A First-Principles Study

One-Step Electrochemical Ethylene-to-Ethylene Glycol Conversion over a Multitasking Molecular Catalyst

Exploring the Cooperation of the Redox Non‐Innocent Ligand and Di‐Cobalt Center for the Water Oxidation Reaction Catalyzed by a Binuclear Complex

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