Electrically Tunable Reactivity of Substrate‐Supported Cobalt Oxide Nanocrystals

Sánchez‐Grande, Ana; Nguyën, Huu Chuong; Lauwaet, Koen; Rodrı́guez-Fernández, Jonathan; Carrasco, Esther; Cirera, Borja; Sun, Zhen; Urgel, José I.; Miranda, Rodolfo; Lauritsen, Jeppe V.; Gallego, José M.; López, Núria; Écija, David

doi:10.1002/smll.202106407

Cited by 5 publications

(9 citation statements)

References 42 publications

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“…This transition becomes even lower for IS *Co–OH to LS *Co–O (third pathway in Table S3 and Figure S3c), which is also spin-allowed, with an overpotential η = 0.26 V (Δ G = 1.49 eV). These overpotentials agree better with the experimental value of 0.3 eV. − This also is in line with previous findings, in which Co in a higher spin state lowered the PCET transition energies. ,,,, The reason for lowering the energy barrier of OER 2 is that IS *Co–OH possesses unpaired electrons in its e g orbital, as well as to a small extent localized on the hydroxy group, which can be seen in its spin density in Figure b. This allows for a more efficient, spin-selective electron transfer and proton abstraction from IS *Co–OH.…”

supporting

confidence: 91%

Lowering the Water Oxidation Overpotential by Spin-Crossover in Cobalt Hexacyanoferrate

Hegner

Galán‐Mascarós

López

2022

J. Phys. Chem. Lett.

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The oxygen evolution reaction (OER) is limited by the inherent linear scaling relationships of its reaction intermediates. Manipulating the spin configuration of the water oxidation intermediates allows us to overcome these constraints. Cobalt hexacyanoferrate (CoFe–PB) is an efficient and robust water oxidation catalyst and further known as a magnetic switch. Its versatile electronic structure renders it a potential candidate for magnetic tuning of the OER. Herein, we used first-principles density functional theory calculations to describe the OER on two different CoFe–PB model systems and evaluated the possibility for spin-crossover (SCO) of their resting states. We show that SCO during OER can significantly lower the overpotential by 0.7 V, leading to an overpotential of around 0.3 V, which is in agreement with the experimentally measured value. Applying an external potential >1.5 V vs SHE, the SCO-assisted pathway becomes largely favored and most likely the predominant reaction pathway.

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confidence: 91%

Lowering the Water Oxidation Overpotential by Spin-Crossover in Cobalt Hexacyanoferrate

Hegner

Galán‐Mascarós

López

2022

J. Phys. Chem. Lett.

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“…[26,27] The metal complex with first-row transition metal and ligand generally exhibits with lower energy in its structure. [28,29] The metal-centered (MC) transition is more dynamic than the ligandcentered (LC), especially for the Ni(0), Cu(I) or Zn(II) complex. As an important first-row transition metal, copper is an abundant and used as an essential metal in many fields.…”

Section: Introductionmentioning

confidence: 99%

Virus‐Like Magnetic Heterostructure: an Outstanding Metal‐Complex Active Platform Enables High‐Efficiency Separation and Catalysis

Guo¹,

Zhang²,

He³

et al. 2023

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Assembled heterostructure systems, as emerging functional materials, have broad applications ranging from enzyme and drug payload to catalysis and purification. However, these require trial‐ and ‐error design process and complex experimental environment to generate heterostructure materials. Here, this study describes an easy‐to‐execute strategy to fabricate magnetic heterostructure as multifunctional delivery system. We utilize first‐row transition metal copper and nitroso/amino ligand as modules to assemble around Fe3O4 magnetic nanoparticles by excessed mild stimuli and fabricate the magnetic heterostructure materials (Fe3O4@ TACN NPs (tetraamminecopper (II) nitrate)). Notably, the Fe3O4@ TACN NPs present with cat's‐whisker structure containing ligand and metal center. The nitroso‐group ligands exhibit strong binding affinity to heme‐structure enzyme, ensuring effective capture and isolate of cytochrome C (Cyt‐c), resulting in their excellent isolation property. The copper complex‐powered magnetic heterostructure materials can effectively isolation Cyt‐c from complex biological sample (pork heart). Importantly, the Fe3O4@ TACN NPs coordinated with heme‐structure, induced methionine 80 (Met80) disassociates from heme prosthetic group, and contributed to peroxidase‐like (POD‐like) activities increasing. These results exhibit that copper complex‐powered magnetic heterostructure materials can not only satisfy the Cyt‐c isolation and immobilization in an alkaline medium, but also be of the potential for improving the immobilization enzyme reactor performance.

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“…Earlier studies focused on structural properties, mainly using STM. Their electronic features have also been investigated, but mostly through nonlocally resolved photoemission methods [13,14], with only one STS study published on the single-bilayer system that did not include the important edge sites [15]. It is therefore highly relevant to make an in-depth STS study of all three systems to map out the local electronic structure of the different cobalt oxide structures on Au(111).…”

Section: Introductionmentioning

confidence: 99%

Unraveling the electronic structure of cobalt oxide nanoislands on Au(111)

Ørsted,

Salling,

Diekhöner

2023

Phys. Rev. B

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This study utilizes spatially resolved low-temperature scanning tunneling microscopy and spectroscopy to investigate cobalt oxide nanoislands on Au(111) single-crystal surfaces. The electronic structure of bilayer, trilayer, and multilayer islands is measured, and the findings are correlated with structural variations across the islands, at oxygen defect lines on the islands, and at the island step edges. Of particular importance is the identification of electronic features below the Fermi level unique to certain island edges that are well-known to exhibit increased chemical reactivity. The results advance the understanding of the electronic properties of surface-supported cobalt oxide nanostructures, which are known to be important for catalytic applications. Furthermore, on the trilayer island structures a distinct peak in the density of states at the Fermi level is measured that adds to theoretical predictions of superconductivity in CoO 2 layers.

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Electrically Tunable Reactivity of Substrate‐Supported Cobalt Oxide Nanocrystals

Cited by 5 publications

References 42 publications

Lowering the Water Oxidation Overpotential by Spin-Crossover in Cobalt Hexacyanoferrate

Lowering the Water Oxidation Overpotential by Spin-Crossover in Cobalt Hexacyanoferrate

Virus‐Like Magnetic Heterostructure: an Outstanding Metal‐Complex Active Platform Enables High‐Efficiency Separation and Catalysis

Unraveling the electronic structure of cobalt oxide nanoislands on Au(111)

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