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@ARTICLE{Hocking:173062,
author = {Hocking, Rosalie K. and Malaeb, Rafah and Gates, Will P.
and Patti, Antonio F. and Chang, Lan-Yun and Devlin, Glyn
and MacFarlane, Douglas R. and Spiccia, Leone},
title = {{F}ormation of a {N}anoparticulate {B}irnessite - {L}ike
{P}hase in {P}urported {M}olecular {W}ater {O}xidation
{C}atalyst {S}ystems},
journal = {ChemCatChem},
volume = {6},
issn = {1867-3880},
address = {Weinheim},
publisher = {WILEY-VCH Verlag},
reportid = {FZJ-2014-06475},
pages = {2028 - 2038},
year = {2014},
abstract = {The fate of [MnIII/IV2(μ-O)2(terpy)2(H2O)2]3+ (1) under
conditions typically applied to test its ability to catalyze
water oxidation was studied by X-ray absorption spectroscopy
and UV/Vis spectrophotometry by using
[MnIII/IV2(μ-O)2(bipy)4]3+ (2) and Mn2+ as controls
(terpy=2,2′:6′,2“-terpyridine,
bipy=2,2′-bipyridine). The sample matrix, pH and choice of
oxidizing agent were found to have a significant effect on
the species formed under catalytic conditions. At low range
pH values (4–6), homogeneous catalysis testing in oxone
implied that 1 remains intact, whereas in clay intercalate
there is strong evidence that 1 breaks down to a
birnessite-like phase. In homogeneous solutions at higher
pH, the results are consistent with the same birnessite-like
structure identified in the clay intercalate. The use of the
molecular complexes, as a source of manganese instead of
simple MnII salts, was found to have the effect of slowing
down oxide formation and particle aggregation in solution.
The original analytical results that implied the systems are
molecular are discussed in the context of these new
observations.},
cin = {PGI-5},
ddc = {540},
cid = {I:(DE-Juel1)PGI-5-20110106},
pnm = {424 - Exploratory materials and phenomena (POF2-424)},
pid = {G:(DE-HGF)POF2-424},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000340573200027},
doi = {10.1002/cctc.201400066},
url = {https://juser.fz-juelich.de/record/173062},
}