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Title: Surface and Structural Investigation of a MnO x Birnessite-Type Water Oxidation Catalyst Formed under Photocatalytic Conditions

Abstract

Catalytically active MnOx species have been reported to form in situ from various Mn-complexes during electrocatalytic and solution-based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnOx catalysts form without supports in situ under photocatalytic conditions. Our most active (MnOx)-Mn-4 catalyst (similar to 0.84 mmol O-2 mol Mn-1 s(-1)) forms from a Mn4O4 bearing a metal-organic framework. 4MnO(x) is characterized by pair distribution function analysis PDF), Raman spectroscopy, and HR-TEM as a disordered, layered Mn-oxide with high surface area (216 m(2)g(-1)) and small regions of crystallinity and layer flexibility. In contrast, the (MnOx)-Mn-S formed from Mn2+ salt gives an amorphous species of lower surface area (80 m(2)g(-1)) and lower activity (similar to 0.15 mmol O-2 mol Mn(-1)s(-1)). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p(3/2) core levels detects enriched Mn3+ and Mn2+ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392563
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 40; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
birnessite structure; manganese oxide; metal-organic frameworks; water oxidation catalyst; water splitting

Citation Formats

Deibert, Benjamin J., Zhang, Jingming, Smith, Paul F., Chapman, Karena W., Rangan, Sylvie, Banerjee, Debasis, Tan, Kui, Wang, Hao, Pasquale, Nicholas, Chen, Feng, Lee, Ki-Bum, Dismukes, G. Charles, Chabal, Yves J., and Li, Jing. Surface and Structural Investigation of a MnO x Birnessite-Type Water Oxidation Catalyst Formed under Photocatalytic Conditions. United States: N. p., 2015. Web. doi:10.1002/chem.201501930.
Deibert, Benjamin J., Zhang, Jingming, Smith, Paul F., Chapman, Karena W., Rangan, Sylvie, Banerjee, Debasis, Tan, Kui, Wang, Hao, Pasquale, Nicholas, Chen, Feng, Lee, Ki-Bum, Dismukes, G. Charles, Chabal, Yves J., & Li, Jing. Surface and Structural Investigation of a MnO x Birnessite-Type Water Oxidation Catalyst Formed under Photocatalytic Conditions. United States. doi:10.1002/chem.201501930.
Deibert, Benjamin J., Zhang, Jingming, Smith, Paul F., Chapman, Karena W., Rangan, Sylvie, Banerjee, Debasis, Tan, Kui, Wang, Hao, Pasquale, Nicholas, Chen, Feng, Lee, Ki-Bum, Dismukes, G. Charles, Chabal, Yves J., and Li, Jing. Tue . "Surface and Structural Investigation of a MnO x Birnessite-Type Water Oxidation Catalyst Formed under Photocatalytic Conditions". United States. doi:10.1002/chem.201501930.
@article{osti_1392563,
title = {Surface and Structural Investigation of a MnO x Birnessite-Type Water Oxidation Catalyst Formed under Photocatalytic Conditions},
author = {Deibert, Benjamin J. and Zhang, Jingming and Smith, Paul F. and Chapman, Karena W. and Rangan, Sylvie and Banerjee, Debasis and Tan, Kui and Wang, Hao and Pasquale, Nicholas and Chen, Feng and Lee, Ki-Bum and Dismukes, G. Charles and Chabal, Yves J. and Li, Jing},
abstractNote = {Catalytically active MnOx species have been reported to form in situ from various Mn-complexes during electrocatalytic and solution-based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnOx catalysts form without supports in situ under photocatalytic conditions. Our most active (MnOx)-Mn-4 catalyst (similar to 0.84 mmol O-2 mol Mn-1 s(-1)) forms from a Mn4O4 bearing a metal-organic framework. 4MnO(x) is characterized by pair distribution function analysis PDF), Raman spectroscopy, and HR-TEM as a disordered, layered Mn-oxide with high surface area (216 m(2)g(-1)) and small regions of crystallinity and layer flexibility. In contrast, the (MnOx)-Mn-S formed from Mn2+ salt gives an amorphous species of lower surface area (80 m(2)g(-1)) and lower activity (similar to 0.15 mmol O-2 mol Mn(-1)s(-1)). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p(3/2) core levels detects enriched Mn3+ and Mn2+ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.},
doi = {10.1002/chem.201501930},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 40,
volume = 21,
place = {United States},
year = {2015},
month = {8}
}

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