The valence states of Mn in mixed-valent layer and tunnel structure manganese dioxides (MnO2), usually referred to as phyllomanganates and tectomanganates, can be measured by X-ray absorption near-edge structure (XANES) spectroscopy with a precision and accuracy that are difficult to estimate owing to the paucity of well-characterized standards. A compilation of the Mn K -edge XANES spectra of most naturally occurring manganates, synthetic analogs of known structure and chemical composition, and pure-valence phase species is presented and made available as an open source. We intend this compilation to serve as a basis for the spectroscopic determination of the fractions of the Mn 2+, 3+, and 4+ valences in mixed-valent manganates and phase mixtures. The XANES derivatives of tectomanganates and phyllomanganates with no or little Mn3+ in the MnO2 layer exhibit intensities, shapes, and relative energy positions of the main features characteristics of a particular valence composition. For these compounds, valence fractions can be derived using linear combination fitting analysis. Best quantitative results are obtained when the unknown spectrum is fit to a weighted sum of all reference spectra in the database with the fractions of species constrained to be non-negative (Combo method). The accuracy of the average valence is estimated to 0.04 v.u. in the range of 3+ to 4+, and decreases when the proportion of divalent Mn is higher than 15%. The accuracy of the method is also lower in (layer Mn3+, Mn4+) manganates, because the XANES features are affected non-additively by the amount and distribution of the Jahn-Teller Mn3+ cations. The merit of the Combo method for the determination of manganese valence sums relative to the methods based on calibration curves is discussed.

http://xraysweb.lbl.gov/uxas/Publicatons/Papers/pdfs/MnXANES%20generic.pdf

Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy

Holey 2D nanosheets of low‐valent Mn2O3 can be synthesized by thermally induced phase transition of exfoliated layered MnO2 nanosheets. The heat treatment of layered MnO2 nanosheets at elevated temperatures leads not only to transitions to low‐valent manganese oxides but also to the creation of surface hole in the 2D nanosheet crystallites. Despite distinct phase transitions, highly anisotropic 2D morphology of the precursor MnO2 material remains intact upon the heat treatment whereas the diameter of surface hole becomes larger with increasing heating temperature. The obtained holey 2D Mn2O3 nanosheets show promising electrocatalyst performances for oxygen evolution reaction, which are much superior to that of nonporous Mn2O3 crystal. Among the present materials, the holey Mn2O3 nanosheet calcined at 500 °C displays the best electrocatalyst functionality with markedly decreased overpotential, indicating the importance of heating condition in optimizing the electrocatalytic activity. Of prime importance is that this material shows much better catalytic activity for Li–O2 batteries than does nonporous Mn2O3, underscoring the critical role of porous 2D morphology in this functionality. This study clearly demonstrates the unique advantage of holey 2D nanosheet morphology in exploring economically feasible transition metal oxide‐based electrocatalysts and electrodes for Li–O2 batteries.

Holey 2D Nanosheets of Low-Valent Manganese Oxides with an Excellent Oxygen Catalytic Activity and a High Functionality as a Catalyst for Li–O2 Batteries

In this report, a novel method is proposed to prepare MnO/reduced graphene oxide (rGO) composites via calcining the precursors (i.e. δ-MnO2/graphene oxide composites) at 500 °C in Ar using no external reducing gas, in which graphene oxide (GO) successfully serves as a reductant by releasing CO during its thermolysis for the first time. By controlling the initial ratios of GO to KMnO4, differently composed precursors can be obtained via the redox reaction between GO and KMnO4, then leading to the formation of composites with different MnO/rGO ratios and dispersion of MnO on the rGO surface (denoted as MGC1 and MGC2). When applied as an active material in lithium ion batteries, MGC1 shows excellent cycling performance and capacity retention. Under 100 and 200 mA g−1, MGC1 could deliver reversible capacities as high as 900 and 750 mA h g−1, respectively, after more than 100 cycles. Considering the simple operation and low energy consumption in the whole material synthesis processes, the present strategy is feasible and effective for practical application. Even more importantly, the reductibility of graphene oxide upon thermolysis is utilized for the first time, which is meaningful for its extension in synthesis of functional nanomaterials.

/pdf/synthesis-and-lithium-storage-properties-of-mno-reduced-1n6sieoeml.pdf

Synthesis and lithium-storage properties of MnO/reduced graphene oxide composites derived from graphene oxide plus the transformation of Mn(VI) to Mn(II) by the reducing power of graphene oxide

Electrodeposition of poly(3,4-ethylenedioxythiophene)/reduced graphene oxide/manganese dioxide for simultaneous detection of uric acid, dopamine and ascorbic acid

Keggin-type molecular clusters formed from the partial hydrolysis of aluminum in aqueous solutions have the capacity to adsorb a variety of inorganic and organic contaminants. The adsorptive capability of Keggin-type polyaluminum species, such as Al13 and Al30, lead to their wide usage as precursors for heterogeneous catalysts and clarifying agents for water purification applications, but a molecular-level understanding of adsorption process is lacking. Two model Al30 clusters, whose surface has been modified with chelated metals (Al(3+) and Zn(2+)) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Al32IDA [(Al(IDA)H2O)2(Al30O8(OH)60(H2O)22)](2,6-NDS)4(SO4)2Cl4(H2O)40, IDA = iminodiacetic acid, 2,6-NDS = 2,6 napthalene disulfonate) crystallize in the triclinic space group, P1 with a = 13.952(2) A, b = 16.319(3) A, c = 23.056(4) A, α = 93.31(1)°, β = 105.27(1)°, and γ = 105.52(1)°. Zn2Al32 [(Zn(NTA)H2O)2(Al(NTA)(OH)2)2(Al30(OH)60(O)8(H2O)20](2,6-NDS)5(H2O)64, (NTA = nitrilotriacetic acid), also crystallizes in P1 with unit cell parameter refined as a = 16.733(7) A, b = 18.034(10) A, c = 21.925(11) A, α = 82.82(2)°, β = 70.96(2)°, and γ = 65.36(2)°. The chelated metal centers adsorb to the surface of the Al30 clusters through hydroxyl bridges located at the central belt region of the molecule. The observed binding sites for the metal centers mirror the reactivity predicted by previously reported molecular dynamic simulations and can be identified by the acidity and hydration factor of the water group that participates in the adsorption process.

Surface modification of Al30 Keggin-type polyaluminum molecular clusters.

Manganese oxide nanocrystals are combined with aluminum oxide nanocrystals to improve their crystallinity via calcination without a significant increase of crystal size. A nanocomposite, consisting of two metal oxides, can be synthesized by the reaction between permanganate anions and aluminum oxyhydroxide keggin cations. The as-prepared manganese oxide–aluminum oxide nanocomposite is X-ray amorphous whereas heat-treatment gives rise to the crystallization of an α-MnO2 phase at 600 °C and Mn3O4/Mn2O3 and γ-Al2O3 phases at 800 °C. Electron microscopy and N2 adsorption-desorption-isotherm analysis clearly demonstrate that the as-prepared nanocomposite is composed of a porous assembly of monodisperse primary particles with a size of ∼20 nm and a surface area of >410 m2 g−1. Of particular interest is that the small particle size of the as-prepared nanocomposite is well-maintained up to 600 °C, a result of the prevention of the growth of manganate grains through nanoscale mixing with alumina grains. The calcined nanocomposite shows very-high catalytic activity for the oxidation of cyclohexene with an extremely high conversion efficiency of >95% within 15 min. The present results show that the improvement of the crystallinity without significant crystal growth is very crucial for optimizing the catalytic activity of manganese oxide nanocrystals.

A Composite Formation Route to Well-Crystalline Manganese Oxide Nanocrystals: High Catalytic Activity of Manganate–Alumina Nanocomposites

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A Composite Formation Route to Well-Crystalline Manganese Oxide Nanocrystals: High Catalytic Activity of Manganate–Alumina Nanocomposites