Study on Catalytic Water Oxidation Properties of Polynuclear Manganese Containing Polyoxometalates

Splitting of water to produce hydrogen and oxygen is a green and effective method to produce clean energy. Finding an efficient water decomposition catalyst is the key step to realize water decomposition. In this work, by choosing from the literature, six polynuclear manganese (Mn) containing polyoxometalates (Mn-POMs) with different Mn-O clusters and oxidation states of Mn, [MnIIMnIIISiW10O37(OH)(H2O)]6− (Mn2-POM), [MnII3MnIII(H2O)2(PW9O34)2]9− (Mn4-POM), [MnII4MnIII2Ge3W24O94(H2O)2]18− (Mn6-POM-1), [MnIII2MnII4(μ3-O)2(H2O)4(B-β-SiW8O31)(B-β-SiW9O34)(γ-SiW10O36)]18− (Mn6-POM-4), [{MnIII3MnIV4O4(OH)2(OH2)}2(W6O22)(H2W8O32)2(H4W13O46)2]26− (Mn14-POM), [MnII19 (OH)12(SiW10O37)6]34− (Mn19-POM) were prepared. First, the catalytic performance towards the water oxidation of six Mn-POMs was investigated in solution for the first time. Second, six Mn-POMs were fabricated on the surface of ITO electrode using layer-by-layer self-assembly (LBL) to form the composite films, which were characterized by UV-vis spectroscopy and cyclic voltammetry, and then the catalytic water oxidation performance of the composite films was studied and compared with that in solution via a series of controlled experiments, the results indicate that the Mn-POMs with three-dimensional structures, which contain variable valence Mn-O cluster similar to the structure of photocatalytic active center (PSII) exhibit better catalytic performance.

[1]  Q. Zhou,et al.  Facile multilayer assemble of a mixed-valence Mn4-containing silicotungstate and its electrochemical study with Co3O4 as co-catalyst for photoelectrocatalytic water oxidation , 2021 .

[2]  Yue Wu,et al.  Fabrication of Six Manganese Containing Polyoxometalate Modified Graphite C3N4 Nanosheets Catalysts Used to Catalyze Water Decomposition , 2021, Catalysts.

[3]  Anjali U. Patel,et al.  Modified Mn substituted POMs: Synthetic strategies, structural diversity to applications , 2021, Progress in Materials Science.

[4]  J. Ahola,et al.  Electrocatalytic performance and cell voltage characteristics of 1st-row transition metal phosphate (TM-Pi) catalysts at neutral pH , 2020 .

[5]  Yu Du,et al.  A multilayer assembly of two mixed-valence Mn16-containing polyanions and study of their electrocatalytic activities towards water oxidation. , 2018, Dalton transactions.

[6]  Yong Ding,et al.  Polyoxometalate-based manganese clusters as catalysts for efficient photocatalytic and electrochemical water oxidation , 2017 .

[7]  B. Rezaei,et al.  Nanostructure polyoxometalates containing Co, Ni, and Cu as powerful and stable catalysts for hydrogen evolution reaction in acidic and alkaline solutions , 2017 .

[8]  T. Jacob,et al.  Visible-Light-Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster. , 2016, Angewandte Chemie.

[9]  Yang-guang Li,et al.  Polyoxometalate-assisted synthesis of transition-metal cubane clusters as artificial mimics of the oxygen-evolving center of photosystem II , 2016 .

[10]  Soumyajit Roy,et al.  Enhancement of photochemical heterogeneous water oxidation by a manganese based soft oxometalate immobilized on a graphene oxide matrix , 2016 .

[11]  D. Yin,et al.  A non-nitric acid method of adipic acid synthesis: organic solvent- and promoter-free oxidation of cyclohexanone with oxygen over hollow-structured Mn/TS-1 catalysts , 2015 .

[12]  U. Kortz,et al.  Photocatalytic water oxidation by a mixed-valent Mn(III)₃Mn(IV)O₃ manganese oxo core that mimics the natural oxygen-evolving center. , 2014, Angewandte Chemie.

[13]  A. Powell,et al.  Synthesis and characterization of multinuclear manganese-containing tungstosilicates. , 2014, Inorganic Chemistry.

[14]  G. Patzke,et al.  All-inorganic 1D chain-based architecture of a novel dimanganese-substituted Keggin polyoxotungstate , 2013 .

[15]  Scott G. Mitchell,et al.  A mixed-valence manganese cubane trapped by inequivalent trilacunary polyoxometalate ligands. , 2011, Angewandte Chemie.

[16]  N. Dalal,et al.  A planar {Mn19(OH)12}26+ unit incorporated in a 60-tungsto-6-silicate polyanion. , 2011, Angewandte Chemie.

[17]  X. Fang,et al.  {Mn14W48} aggregate: the perspective of isopolyanions as ligands. , 2011, Chemical communications.

[18]  R. Argazzi,et al.  Ruthenium polyoxometalate water splitting catalyst: very fast hole scavenging from photogenerated oxidants. , 2010, Chemical communications.

[19]  Fengyan Li,et al.  New assembly of transition metal complexes based on [GeW9O34]10− building blocks: Syntheses, crystal structures and magnetic properties , 2010 .

[20]  S. Dong,et al.  Nanocomposite multilayer film of preyssler-type polyoxometalates with fine tunable electrocatalytic activities , 2004 .

[21]  S. Dong,et al.  Fabrication of a Metalloporphyrin−Polyoxometalate Hybrid Film by a Layer-by-Layer Method and Its Catalysis for Hydrogen Evolution and Dioxygen Reduction , 2003 .

[22]  M. T. Pope,et al.  High-valent manganese in polyoxotungstates—II. Oxidation of the tetramanganese heteropolyanion [Mn4(H2O)2(PW9O34)2]10−☆ , 1996 .

[23]  M. Simões,et al.  Catalytic homogeneous oxidation of monoterpenes and cyclooctene with hydrogen peroxide in the presence of sandwich-type tungstophosphates [M4(H2O)2(PW9O34)2]n−, M = CoII, MnII and FeIII , 2017 .

[24]  Achim Müller,et al.  Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines , 1991 .