Tricopper-polyoxometalate catalysts for water oxidation: Redox-inertness of copper center

A cobalt oxide catalyst prepared by a flame-assisted deposition method on the surface of FTO and hematite for electrochemical and photoelectrochemical water oxidation, respectively.

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OBSERVATION OF TRANSIENT HIGH-VALENT STATES IN THE WATER OXIDATION CATALYST CoIII4O4 CUBANE VIA EXTREME ULTRAVIOLET SPECTROSCOPY

Proceedings of the 74th International Symposium on Molecular Spectroscopy ◽

10.15278/isms.2019.we04 ◽

2019 ◽

Author(s):

Yusef Shari'ati ◽

Josh Vura-Weis

Keyword(s):

Water Oxidation ◽

Extreme Ultraviolet ◽

Oxidation Catalyst ◽

Ultraviolet Spectroscopy ◽

High Valent

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Impact Of Synthesis Route on the Water Oxidation Kinetics of Hematite Photoanodes

10.26434/chemrxiv.12505742.v1 ◽

2020 ◽

Author(s):

Camilo A. Mesa ◽

Ludmilla Steier ◽

Benjamin Moss ◽

Laia Francàs ◽

James E. Thorne ◽

...

Keyword(s):

Oxygen Vacancy ◽

Reaction Kinetics ◽

Water Oxidation ◽

Oxidation Kinetics ◽

Oxidation Reaction ◽

Charge Accumulation ◽

Optical Signals ◽

Current Voltage ◽

Voltage Performance ◽

Kinetics Of

Operando spectroelectrochemical analysis is used to determine the water oxidation reaction kinetics for hematite photoanodes prepared using four different synthetic procedures. Whilst these photoanodes exhibit very different current / voltage performance, their underlying water oxidation kinetics are found to be almost invariant. Lower photoanode performance was found to correlate with the observation of optical signals indicative of charge accumulation in mid-gap oxygen vacancy states, indicating these states do not contribute directly to water oxidation.

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Tris(pyrazolyl)borate Copper Hydroxide Complexes Featuring Tunable Intramolecular H-bonding

10.26434/chemrxiv.7878065.v1 ◽

2019 ◽

Author(s):

Evan Gardner ◽

Caitlyn Cobb ◽

Jeffery A. Bertke ◽

Timothy H. Warren

Keyword(s):

Single Crystal ◽

Copper Hydroxide ◽

X Ray ◽

Modular Synthesis ◽

Pendant Arm ◽

Copper Center ◽

Vibrational Studies

A modular synthesis provides access to a series of new tris(pyrazolyl)borate ligands XpyMeTpK that possess a single functionalized pendant pyridyl (py) or pyrimidyl (pyd) arm designed to engage in tunable intramolecular H-bonding to metal–bound functionalities. To illustrate such H-bonding interactions, a series of [XpyMeTpCu]2(𝜇–OH)2(6a–6e) complexes were synthesized from the corresponding XpyMeTpCu–OAc (5a–5e) complexes. Single crystal X-ray structures of three new dinuclear [XpyMeTpCu]2(𝜇–OH)2complexes reveal H-bonding between the pendant heterocycle and bridging hydroxide ligands while the donor arm engages the copper center in an unusual monomeric DMAPMeTpCu–OH complex. Vibrational studies (IR) of each bridging hydroxide complex reveal reduced 𝜈OH frequencies that tracks with the H-bond accepting ability of the pendant arm.

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Tris(pyrazolyl)borate Copper Hydroxide Complexes Featuring Tunable Intramolecular H-bonding

10.26434/chemrxiv.7878065 ◽

2019 ◽

Author(s):

Evan Gardner ◽

Caitlyn Cobb ◽

Jeffery A. Bertke ◽

Timothy H. Warren

Keyword(s):

Single Crystal ◽

Copper Hydroxide ◽

X Ray ◽

Modular Synthesis ◽

Pendant Arm ◽

Copper Center ◽

Vibrational Studies

A modular synthesis provides access to a series of new tris(pyrazolyl)borate ligands XpyMeTpK that possess a single functionalized pendant pyridyl (py) or pyrimidyl (pyd) arm designed to engage in tunable intramolecular H-bonding to metal–bound functionalities. To illustrate such H-bonding interactions, a series of [XpyMeTpCu]2(𝜇–OH)2(6a–6e) complexes were synthesized from the corresponding XpyMeTpCu–OAc (5a–5e) complexes. Single crystal X-ray structures of three new dinuclear [XpyMeTpCu]2(𝜇–OH)2complexes reveal H-bonding between the pendant heterocycle and bridging hydroxide ligands while the donor arm engages the copper center in an unusual monomeric DMAPMeTpCu–OH complex. Vibrational studies (IR) of each bridging hydroxide complex reveal reduced 𝜈OH frequencies that tracks with the H-bond accepting ability of the pendant arm.

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