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

Evan M.W. Rumberger; Hyun S. Ahn; Alexis T. Bell; T. Don Tilley

doi:10.1039/c3dt51472b

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

Evan M.W. Rumberger, Hyun S. Ahn, Alexis T. Bell, T. Don Tilley

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

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)(H ₂O)(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 (TOF_i = 1.1 × 10^-3 s^-1). 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.

Original language	English
Pages (from-to)	12238-12247
Number of pages	10
Journal	Dalton Transactions
Volume	42
Issue number	34
DOIs	https://doi.org/10.1039/c3dt51472b
Publication status	Published - 2013 Sept 14

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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@article{ca165db5e2ac4684b5f50b2c7a17781f,

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

abstract = "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)(H 2O)(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 × 10-3 s-1). 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.",

author = "Rumberger, {Evan M.W.} and Ahn, {Hyun S.} and Bell, {Alexis T.} and Tilley, {T. Don}",

year = "2013",

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doi = "10.1039/c3dt51472b",

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T1 - Water oxidation catalysis via immobilization of the dimanganese complex [Mn2(μ-O)2Cl(μ-O2CCH3)(bpy) 2(H2O)](NO3)2 onto silica

AU - Rumberger, Evan M.W.

AU - Ahn, Hyun S.

AU - Bell, Alexis T.

AU - Tilley, T. Don

PY - 2013/9/14

Y1 - 2013/9/14

N2 - 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)(H 2O)(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 × 10-3 s-1). 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.

AB - 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)(H 2O)(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 × 10-3 s-1). 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.

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U2 - 10.1039/c3dt51472b

DO - 10.1039/c3dt51472b

M3 - Article

C2 - 23861177

AN - SCOPUS:84881425234

SN - 1477-9226

VL - 42

SP - 12238

EP - 12247

JO - Dalton Transactions

JF - Dalton Transactions

IS - 34

ER -

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

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