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Title: Water oxidation catalysis via immobilization of the dimanganese complex [Mn2(μ-O)2Cl(μ-O2CCH3)(bpy)2(H2O)](NO3)2 onto silica

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/c3dt51472b· OSTI ID:1570977
 [1];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Chemical Engineering ; Lawrence Berkeley National Lab., Berkeley, CA (United States). Chemical Sciences Division
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Adsorption of a dinuclear μ-oxo bridged Mn complex onto mesoporous silica was observed when SBA15 was treated with an acetonitrile solution of [Mn2(μ-O)2Cl(μ-O2CCH3)(H2O)(bpy)2](NO3)2 (1). This complex was immobilized via the displacement of NO3-into solution, and characterization by spectroscopic (DRIFTS and DRUV-vis) and magnetic data indicates that the intact dication is electrostatically bound to the silica surface. Loadings of up to 4.1% by weight of [Mn2(μ-O)2Cl(μ-O2CCH3)(H2O)(bpy)2]2+ were achieved. TEM images of the grafted material revealed retention of the mesoporous structure of SBA15, and no clusters of manganese greater than ca. 10 nm were observed. The SBA15-supported dimanganese complex functions as a catalyst for the oxidation of H2O with (NH4)2Ce(NO3)6 as stoichiometric oxidant. In contrast, homogenous aqueous solutions of 1 do not evolve oxygen upon treatment with (NH4)2Ce(NO3)6. Labeling studies with H218O confirm that the oxygen formed in this catalysis is derived from water. Monitoring the O2 evolution allowed determination of an initial rate for the catalysis (TOFi = 1.1 × 10-3s-1). Finally, these studies also reveal a first order dependence on manganese surface concentration, and a zero order rate dependence for (NH4)Ce(NO3)6. Spectroscopic investigations were employed to investigate the difference in activities between dissolved and supported dimanganese complexes.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
AC02-05CH11231
OSTI ID:
1570977
Journal Information:
Dalton Transactions, Vol. 42, Issue 34; ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

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