Next Article in Journal
NOx Removal by Selective Catalytic Reduction with Ammonia over a Hydrotalcite-Derived NiFe Mixed Oxide
Previous Article in Journal
Theoretical Study on the Hydrogenation Mechanisms of Model Compounds of Heavy Oil in a Plasma-Driven Catalytic System
Previous Article in Special Issue
High Performance of Manganese Porphyrin Sensitized p-Type CuFe2O4 Photocathode for Solar Water Splitting to Produce Hydrogen in a Tandem Photoelectrochemical Cell
Article Menu
Issue 9 (September) cover image

Export Article

Open AccessArticle
Catalysts 2018, 8(9), 382; https://doi.org/10.3390/catal8090382

Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster

1
Departamento de Química Inorgánica, Facultade de Ciencias, Universidade de Santiago de Compostela, 27002 Lugo, Spain
2
Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
3
Departament of Pharmacology, Faculty of Veterinary, University of Santiago de Compostela, 27002 Lugo, Spain
4
Centro de Investigacións Científicas Avanzadas (CICA) and Departamento de Química, Campus Zapateira, Universidade da Coruña, 15008 A Coruña, Spain
*
Author to whom correspondence should be addressed.
Received: 28 July 2018 / Revised: 25 August 2018 / Accepted: 3 September 2018 / Published: 7 September 2018
(This article belongs to the Special Issue Photocatalytic Water Splitting)
Full-Text   |   PDF [3056 KB, uploaded 7 September 2018]   |  

Abstract

The oxygen-evolving complex (OEC) is the native enzyme that catalyzes the oxidation of water in natural photosynthesis. Two new classes of manganese cluster complexes of formula Ba2Mn2L12(H3L1)2(CH3OH)4 1 and Mn4L26Cl2 2 were prepared (H4L1 = N,N′-(ethane-1,2-diyl)bis(2-hydroxybenzamide); L2 = methyl picolinimidate) and characterized by standard techniques including microanalysis, IR spectroscopy, ESI spectrometry, and magnetic susceptibility measurements. X-ray diffraction studies of these complexes revealed (i) a box-type structure for 1 formed by two redox-active manganese(III) ions and two barium(II) ions connected by two bridging bisamido-bisphenoxy ligand molecules; and (ii) a planar-diamond array for Mn4N6 cluster 2 where the picolinimidates act as chelating ligands through the two nitrogen atoms. The ability of 1 and 2 to split water has been studied by means of water photolysis experiments. In these experiments, the oxygen evolution was measured in aqueous media in the presence of p-benzoquinone (acting as the hydrogen acceptor), the reduction of which was followed by UV-spectroscopy. The relevant photolytic activity found for 1 is in contrast to the inactivity of 2 in the photolytic experiments. This different behavior is discussed on the basis of the structure of the biomimetic models and the proposed reaction mechanism for this process supported by DFT calculations. View Full-Text
Keywords: artificial photosynthesis; photocatalyst; water splitting; manganese artificial photosynthesis; photocatalyst; water splitting; manganese
Figures

Graphical abstract

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

SciFeed

Share & Cite This Article

MDPI and ACS Style

Rouco, L.; Fernández-García, M.I.; Pedrido, R.; Botana, L.M.; Esteban-Gómez, D.; Platas-Iglesias, C.; Maneiro, M. Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster. Catalysts 2018, 8, 382.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Catalysts EISSN 2073-4344 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top