Water Oxidation Catalysis by Synthetic Manganese Oxides with Different Structural Motifs: A Comparative Study

Chemistry : a European Journal
Carolin E Frey, Philipp Kurz

Abstract

Manganese oxides are considered to be very promising materials for water oxidation catalysis (WOC), but the structural parameters influencing their catalytic activity have so far not been clearly identified. For this study, a dozen manganese oxides (MnOx ) with various solid-state structures were synthesised and carefully characterised by various physical and chemical methods. WOC by the different MnOx was then investigated with Ce(4+) as chemical oxidant. Oxides with layered structures (birnessites) and those containing large tunnels (todorokites) clearly gave the best results with reaction rates exceeding 1250 ${{\rm{mmol}}_{{\rm{O}}_{\rm{2}} } }$ ${{\rm{mol}}_{{\rm{Mn}}}^{ - 1} }$ h(-1) or about 50 μmolO2 m(-2) h(-1) . In comparison, catalytic rates per mole of Mn of oxides characterised by well-defined 3D networks were rather low (e.g., ca. 90 ${{\rm{mmol}}_{{\rm{O}}_{\rm{2}} } }$ ${{\rm{mol}}_{{\rm{Mn}}}^{ - 1} }$ h(-1) for bixbyite, Mn2 O3 ), but impressive if normalised per unit surface area (>100 ${{\rm{{\rm \mu} mol}}_{{\rm{O}}_{\rm{2}} } }$ m(-2) h(-1) for marokite, CaMn2 O4 ). Thus, two groups of MnOx emerge from this screening as hot candidates for manganese-based WOC materials: 1) amorphous oxides with tunnelled st...Continue Reading

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Mar 20, 2013·Accounts of Chemical Research·Nicholas CoxWolfgang Lubitz
Nov 15, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Carolin E FreyPhilipp Kurz
Feb 25, 2015·Inorganic Chemistry·Gökhan ElmaciBirgül Zümreoğlu-Karan

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Citations

Jan 20, 2017·Chemistry : a European Journal·Qysar MaqboolAasheesh Srivastava
Dec 29, 2017·Inorganic Chemistry·Hamed SimchiSuzanne E Mohney
Apr 7, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Davide BarrecaPaolo Fornasiero

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