Formation of cobalt-oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(II) center

2021 ◽  
Author(s):  
Deesha D. Malik ◽  
Anirban Chandra ◽  
Mi Sook Seo ◽  
Yong-Min Lee ◽  
Erik R. Farquhar ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Dioxygen Activation ◽  
Oxygen Intermediates

A mononuclear nonheme cobalt(II) complex, [(TMG3tren)CoII(OTf)](OTf) (1), activates dioxygen in the presence of hydrogen atom donor substrates, such as tetrahydrofuran and cyclohexene, resulting in the generation of a cobalt(II)-alkylperoxide intermediate...

Nonredox Metal-Ions-Enhanced Dioxygen Activation by Oxidovanadium(IV) Complexes toward Hydrogen Atom Abstraction

2017 ◽  
Vol 56 (2) ◽  
pp. 834-844 ◽  
Author(s):  
Jisheng Zhang ◽  
Hang Yang ◽  
Tingting Sun ◽  
Zhuqi Chen ◽  
Guochuan Yin
Keyword(s):  
Hydrogen Atom ◽  
Metal Ions ◽  
Dioxygen Activation ◽  
Hydrogen Atom Abstraction

scholarly journals Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction

2020 ◽  
Author(s):  
Lichen Bai ◽  
seunghwa lee ◽  
Xile Hu
Keyword(s):  
Hydrogen Atom ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Oxygen Intermediates ◽  
Bifunctional Mechanism ◽  
Bond Forming ◽  
Highly Active ◽  
Scaling Relationship

The oxygen evolution reaction (OER) is an essential anodic reaction in many energy storage processes. OER is most often proposed to occur via a mechanism involving four consecutive proton-coupled electron transfer (PCET) steps, which imposes a performance limit due to the scaling relationship of various oxygen intermediates. A bifunctional OER mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH-NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH-NiOOH operates by a bifunctional mechanism where the rate-determining O-O bond forming step is the OH- attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII-O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive PCET steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.<br>

scholarly journals Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction

2020 ◽  
Author(s):  
Lichen Bai ◽  
seunghwa lee ◽  
Xile Hu
Keyword(s):  
Hydrogen Atom ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Oxygen Intermediates ◽  
Bifunctional Mechanism ◽  
Bond Forming ◽  
Highly Active ◽  
Scaling Relationship

The oxygen evolution reaction (OER) is an essential anodic reaction in many energy storage processes. OER is most often proposed to occur via a mechanism involving four consecutive proton-coupled electron transfer (PCET) steps, which imposes a performance limit due to the scaling relationship of various oxygen intermediates. A bifunctional OER mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH-NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH-NiOOH operates by a bifunctional mechanism where the rate-determining O-O bond forming step is the OH- attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII-O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive PCET steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.<br>

scholarly journals Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction

2020 ◽  
Author(s):  
Lichen Bai ◽  
seunghwa lee ◽  
Xile Hu
Keyword(s):  
Hydrogen Atom ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Oxygen Intermediates ◽  
Bifunctional Mechanism ◽  
Bond Forming ◽  
Highly Active ◽  
Scaling Relationship

The oxygen evolution reaction (OER) is an essential anodic reaction in many energy storage processes. OER is most often proposed to occur via a mechanism involving four consecutive proton-coupled electron transfer (PCET) steps, which imposes a performance limit due to the scaling relationship of various oxygen intermediates. A bifunctional OER mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH-NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH-NiOOH operates by a bifunctional mechanism where the rate-determining O-O bond forming step is the OH- attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII-O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive PCET steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.<br>

Dioxygen Activation by Mononuclear Nonheme Iron(II) Complexes Generates Iron−Oxygen Intermediates in the Presence of an NADH Analogue and Proton

2009 ◽  
Vol 131 (39) ◽  
pp. 13910-13911 ◽  
Author(s):  
Seungwoo Hong ◽  
Yong-Min Lee ◽  
Woonsup Shin ◽  
Shunichi Fukuzumi ◽  
Wonwoo Nam
Keyword(s):  
Nonheme Iron ◽  
Dioxygen Activation ◽  
Oxygen Intermediates
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