Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 461 - 466 |
| Number of pages | 6 |
| Journal | Nature Chemistry |
| Volume | 3 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 2011 |
Cite this
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Water-oxidation catalysis by manganese in a geochemical-like cycle. / Hocking, Rosalie; Brimblecombe, Robin; Chang, Lan-Yun; Singh, Archana; Cheah, Mun Hon; Glover, Chris; Casey, William; Spiccia, Leone.
In: Nature Chemistry, Vol. 3, No. 6, 2011, p. 461 - 466.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Water-oxidation catalysis by manganese in a geochemical-like cycle
AU - Hocking, Rosalie
AU - Brimblecombe, Robin
AU - Chang, Lan-Yun
AU - Singh, Archana
AU - Cheah, Mun Hon
AU - Glover, Chris
AU - Casey, William
AU - Spiccia, Leone
PY - 2011
Y1 - 2011
N2 - Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn(4)CaO(4) cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn(2+).
AB - Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn(4)CaO(4) cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn(2+).
UR - http://www.nature.com/nchem/journal/v3/n6/pdf/nchem.1049.pdf
U2 - 10.1038/NCHEM.1049
DO - 10.1038/NCHEM.1049
M3 - Article
VL - 3
SP - 461
EP - 466
JO - Nature Chemistry
JF - Nature Chemistry
SN - 1755-4330
IS - 6
ER -