Influencing factors on heterogeneous water oxidation catalysis by di-μ-oxo dimanganese complex on mica as a synthetic model of photosystem II

Influencing factors on heterogeneous water oxidation catalysis by di-μ-oxo dimanganese complex... The influencing factors on heterogeneous water oxidation catalysis (WOC) were investigated in a synthetic photosystem II model developed by adsorbing [(OH2)(terpy)MnIII(μ-O)2MnIV(terpy)(OH2)]3+ (terpy = 2,2′:6′,2″-terpyridine) (1) as an oxygen evolving center onto mica. For chemical WOC using a Ce4+ oxidant, the catalytic activity of 1 on mica increased by a factor of 2.3 or 1.4 by co-adsorption (0.015 mmol g−1) of redox-inactive trications of Al3+ or Ce3+ with 1 (0.15 mmol g−1), respectively, whereas it decreased by co-adsorption (0.25 mmol g−1) of excess Al3+ or Ce3+. The cooperative catalysis by two equivalents of the adsorbed 1 for water oxidation could be facilitated by enrichment of 1 by trications at their low co-adsorption conditions. The decreased catalytic activity at high trications co-adsorption conditions could be explained by impeded penetration of Ce4+ oxidant ions into a mica interlayer. For photochemical WOC containing a [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) photoexcitation center in mica, the drying treatment at 65 °C under the vacuum after 1 adsorption was required in adsorbate preparation, possibly to maintain favorable arrangement of 1 and [Ru(bpy)3]2+ in a mica interlayer. The drying treatment at 65 °C under the vacuum after [Ru(bpy)3]2+ adsorption inactivated the photochemical WOC. The proton-coupled electron transport from interior [Ru(bpy)3]2+ centers to ones near the surface in mica is considered to be suppressed by the drying treatment, which could be responsible for the inactivated photochemical WOC. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Influencing factors on heterogeneous water oxidation catalysis by di-μ-oxo dimanganese complex on mica as a synthetic model of photosystem II

Loading next page...
 
/lp/springer_journal/influencing-factors-on-heterogeneous-water-oxidation-catalysis-by-di-d1awUg2VAT
Publisher
Springer Netherlands
Copyright
Copyright © 2014 by Springer Science+Business Media Dordrecht
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-014-1826-z
Publisher site
See Article on Publisher Site

Abstract

The influencing factors on heterogeneous water oxidation catalysis (WOC) were investigated in a synthetic photosystem II model developed by adsorbing [(OH2)(terpy)MnIII(μ-O)2MnIV(terpy)(OH2)]3+ (terpy = 2,2′:6′,2″-terpyridine) (1) as an oxygen evolving center onto mica. For chemical WOC using a Ce4+ oxidant, the catalytic activity of 1 on mica increased by a factor of 2.3 or 1.4 by co-adsorption (0.015 mmol g−1) of redox-inactive trications of Al3+ or Ce3+ with 1 (0.15 mmol g−1), respectively, whereas it decreased by co-adsorption (0.25 mmol g−1) of excess Al3+ or Ce3+. The cooperative catalysis by two equivalents of the adsorbed 1 for water oxidation could be facilitated by enrichment of 1 by trications at their low co-adsorption conditions. The decreased catalytic activity at high trications co-adsorption conditions could be explained by impeded penetration of Ce4+ oxidant ions into a mica interlayer. For photochemical WOC containing a [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) photoexcitation center in mica, the drying treatment at 65 °C under the vacuum after 1 adsorption was required in adsorbate preparation, possibly to maintain favorable arrangement of 1 and [Ru(bpy)3]2+ in a mica interlayer. The drying treatment at 65 °C under the vacuum after [Ru(bpy)3]2+ adsorption inactivated the photochemical WOC. The proton-coupled electron transport from interior [Ru(bpy)3]2+ centers to ones near the surface in mica is considered to be suppressed by the drying treatment, which could be responsible for the inactivated photochemical WOC.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 15, 2014

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off