scholarly journals Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co–Hbpp Water Oxidation Catalyst

2016 ◽  
Vol 138 (47) ◽  
pp. 15291-15294 ◽  
Author(s):  
Carolina Gimbert-Suriñach ◽  
Dooshaye Moonshiram ◽  
Laia Francàs ◽  
Nora Planas ◽  
Varinia Bernales ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Spectroscopic Characterization ◽  
Oxidation Catalyst ◽  
Reaction Intermediates

Characterization of Intermediary Redox States of the Water Oxidation Catalyst, [Ru(bpy)2(OH2)]2O4+

2009 ◽  
Vol 48 (10) ◽  
pp. 4400-4410 ◽  
Author(s):  
Jonathan L. Cape ◽  
Sergei V. Lymar ◽  
Travis Lightbody ◽  
James K. Hurst
Keyword(s):  
Water Oxidation ◽  
Oxidation Catalyst ◽  
Redox States

scholarly journals Using small molecule complexes to elucidate features of photosynthetic water oxidation

2007 ◽  
Vol 363 (1494) ◽  
pp. 1271-1281 ◽  
Author(s):  
Kristof Meelich ◽  
Curtis M Zaleski ◽  
Vincent L Pecoraro
Keyword(s):  
Water Oxidation ◽  
Spectroscopic Characterization ◽  
Structural Features ◽  
Oxygen Evolving Complex ◽  
Model Complexes ◽  
Small Model ◽  
Oxygen Evolving ◽  
Photosynthetic Water Oxidation ◽  
Insight Into

The molecular oxygen produced in photosynthesis is generated via water oxidation at a manganese–calcium cluster called the oxygen-evolving complex (OEC). While studies in biophysics, biochemistry, and structural and molecular biology are well known to provide deeper insight into the structure and workings of this system, it is often less appreciated that biomimetic modelling provides the foundation for interpreting photosynthetic reactions. The synthesis and characterization of small model complexes, which either mimic structural features of the OEC or are capable of providing insight into the mechanism of O 2 evolution, have become a vital contributor to this scientific field. Our group has contributed to these findings in recent years through synthesis of model complexes, spectroscopic characterization of these systems and probing the reactivity in the context of water oxidation. In this article we describe how models have made significant contributions ranging from understanding the structure of the water-oxidation centre (e.g. contributions to defining a tetrameric Mn 3 Ca-cluster with a dangler Mn) to the ability to discriminate between different mechanistic proposals (e.g. showing that the Babcock scheme for water oxidation is unlikely).

Characterization of peroxo reaction intermediates in the water oxidation process on hematite surfaces

2018 ◽  
Vol 24 (10) ◽  
Author(s):  
Lodvert Tchibota Poaty ◽  
Kanchan Ulman ◽  
Nicola Seriani ◽  
Bernard M’Passi-Mabiala ◽  
Ralph Gebauer
Keyword(s):  
Water Oxidation ◽  
Oxidation Process ◽  
Reaction Intermediates

Photophysical Characterization of a Helical Peptide Chromophore–Water Oxidation Catalyst Assembly on a Semiconductor Surface Using Ultrafast Spectroscopy

2014 ◽  
Vol 118 (12) ◽  
pp. 6029-6037 ◽  
Author(s):  
Stephanie E. Bettis ◽  
Derek M. Ryan ◽  
Melissa K. Gish ◽  
Leila Alibabaei ◽  
Thomas J. Meyer ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Ultrafast Spectroscopy ◽  
Oxidation Catalyst ◽  
Semiconductor Surface ◽  
Helical Peptide

scholarly journals Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni–Mn3O4 nanoparticles during water oxidation catalysis

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Sunghak Park ◽  
Kyoungsuk Jin ◽  
Hyung Kyu Lim ◽  
Jin Kim ◽  
Kang Hee Cho ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Heterogeneous Catalysts ◽  
Spectroscopic Characterization ◽  
Transition Metal Catalysts ◽  
Oxidation Catalysis ◽  
Ligand Field ◽  
Intermediate Species ◽  
Spin Configuration ◽  
High Valent

Abstract High-valent metal-oxo moieties have been implicated as key intermediates preceding various oxidation processes. The critical O–O bond formation step in the Kok cycle that is presumed to generate molecular oxygen occurs through the high-valent Mn-oxo species of the water oxidation complex, i.e., the Mn4Ca cluster in photosystem II. Here, we report the spectroscopic characterization of new intermediates during the water oxidation reaction of manganese-based heterogeneous catalysts and assign them as low-spin Mn(IV)-oxo species. Recently, the effects of the spin state in transition metal catalysts on catalytic reactivity have been intensely studied; however, no detailed characterization of a low-spin Mn(IV)-oxo intermediate species currently exists. We demonstrate that a low-spin configuration of Mn(IV), S = 1/2, is stably present in a heterogeneous electrocatalyst of Ni-doped monodisperse 10-nm Mn3O4 nanoparticles via oxo-ligand field engineering. An unprecedented signal (g = 1.83) is found to evolve in the electron paramagnetic resonance spectrum during the stepwise transition from the Jahn–Teller-distorted Mn(III). In-situ Raman analysis directly provides the evidence for Mn(IV)-oxo species as the active intermediate species. Computational analysis confirmed that the substituted nickel species induces the formation of a z-axis-compressed octahedral C4v crystal field that stabilizes the low-spin Mn(IV)-oxo intermediates.

Sign in / Sign up

Export Citation Format

Share Document