Density Functional Theory Study of Transitional Metal Macrocyclic Complexes' Dioxygen-Binding Abilities and Their Catalytic Activities toward Oxygen Reduction Reaction

Shi, Zheng; Zhang, Jiujun

doi:10.1021/jp0671749

Cited by 154 publications

(151 citation statements)

References 47 publications

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“…The adsorption of oxygen molecules, stretching of O-O bond, and the binding energy of OOH (E ad ) on the active sites are the key parameters which may determine the rate of the ORR process 7,37 . As a result of rehybridization of 3d orbitals with the states of the axial ligand and charge transfer, the geometrical and electronic structure of the five-ligated FePc-Py-CNT system is found to be very different from those of the four-ligated FePc-CNT system.…”

Section: Discussionmentioning

confidence: 99%

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst

et al. 2013

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Electrocatalysts for oxygen reduction are a critical component that may dramatically enhance the performance of fuel cells and metal-air batteries, which may provide the power for future electric vehicles. Here we report a novel bio-inspired composite electrocatalyst, iron phthalocyanine with an axial ligand anchored on single-walled carbon nanotubes, demonstrating higher electrocatalytic activity for oxygen reduction than the state-of-the-art Pt/C catalyst as well as exceptional durability during cycling in alkaline media. Theoretical calculations suggest that the rehybridization of Fe 3d orbitals with the ligand orbitals coordinated from the axial direction results in a significant change in electronic and geometric structure, which greatly increases the rate of oxygen reduction reaction. Our results demonstrate a new strategy to rationally design inexpensive and durable electrochemical oxygen reduction catalysts for metal-air batteries and fuel cells.

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Section: Discussionmentioning

confidence: 99%

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst

et al. 2013

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“…Here, we present a worked example of CoTPP adsorbed on Au (111), which has been the focus of some previous study [140,149,150,151,152,153,154], interacting with molecular and atomic oxygen adsorbates. This system helps illustrate some of the outstanding challenges and possible solutions for the computational chemist wishing to study surface chemistry.…”

Section: Background On Worked Examplementioning

confidence: 99%

Density functional theory for modelling large molecular adsorbate–surface interactions: a mini-review and worked example

Janet

Zhao

Ioannidis

et al. 2016

Molecular Simulation

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First-principles simulation has played an ever-increasing role in the discovery and interpretation of the chemical properties of surface-adsorbate interactions.Nevertheless, key challenges remain for the computational chemist wishing to study surface chemistry: modelling the full extent of experimental conditions, managing computational cost, minimizing human effort in simulation setup, and maximizing accuracy. This article introduces new tools for streamlining surface chemistry simulation setup and reviews some of the challenges in first-principles, density functional theory (DFT) simulation of surface phenomena. Furthermore, we provide a worked example of Co tetraphenylporphyrin (CoTPP) on Au (111) in which we both analyze electronic and energetic properties with both semi-local DFT and compare to predictions made from hybrid functional and the so-called DFT+U correction. Through both review and the worked example, we aim to provide a pedagogical introduction to both the challenges and the insight that first-principles simulation can provide in surface chemistry.

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“…We have optimized the geometrical structures of several substituted cobalt-phthalocyanines and of cobalt-tetrapyridinophorphyrazine. All the CoPcs were characterized as a Doublet ground state [60,61] …”

Section: Computational Detailsmentioning

confidence: 99%

“…Theoretical calculations to simulate this interaction are in progress and need to take into consideration the role of the solvent, which will likely affect the energy of the frontier orbitals of SCN À . However, ab initio calculation of ionization potentials of the complexes could also be useful for these comparisons as shown before for the reduction of O 2 mediated by metallophthalocyanines [60].…”

Section: Catalytic Effect For Thiocyanate Oxidationmentioning

confidence: 99%

Optimizing the Electrocatalytic Activity of Surface Confined Co Macrocyclics for the Electrooxidation of Thiocyanate at pH 4

et al. 2011

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We have studied the trends in catalytic activity of several Co macrocyclics confined on the surface graphite electrodes for the oxidation of thiocyanate. A plot of log i (at constant E) versus the formal potential of the catalyst gives a volcano correlation, indicating that the Co(II/I) redox potential needs to be tuned, in order to achieve maximum reactivity. Graphite electrodes modified with Co phthalocyanine at pH 4 exhibit linear amperometric response for thiocyanate concentration in the range 10 À7 and 10 À3 M. Theoretical calculations show that electrocatalytic activity (as log i at constant E) plotted versus the energy of the LUMO of the Co complex also gives a volcano correlation.

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Density Functional Theory Study of Transitional Metal Macrocyclic Complexes' Dioxygen-Binding Abilities and Their Catalytic Activities toward Oxygen Reduction Reaction

Cited by 154 publications

References 47 publications

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst

Density functional theory for modelling large molecular adsorbate–surface interactions: a mini-review and worked example

Optimizing the Electrocatalytic Activity of Surface Confined Co Macrocyclics for the Electrooxidation of Thiocyanate at pH 4

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