The construction of nanoporous membranes is of great technological importance for various applications, including catalyst supports, filters for biomolecule purification, environmental remediation and seawater desalination. A major challenge is the scalable fabrication of membranes with the desirable combination of good thermal stability, high selectivity and excellent recyclability. Here we present a self-assembly method for constructing thermally stable, free-standing nanowire membranes that exhibit controlled wetting behaviour ranging from superhydrophilic to superhydrophobic. These membranes can selectively absorb oils up to 20 times the material's weight in preference to water, through a combination of superhydrophobicity and capillary action. Moreover, the nanowires that form the membrane structure can be re-suspended in solutions and subsequently re-form the original paper-like morphology over many cycles. Our results suggest an innovative material that should find practical applications in the removal of organics, particularly in the field of oil spill cleanup.

Manganese oxides of various structures (α-, β-, and δ-MnO2 and amorphous) were synthesized by facile methods. The electrocatalytic properties of these materials were systematically investigated for catalyzing both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in alkaline media. Extensive characterization was correlated with the activity study by investigating the crystal structures (XRD, HRTEM), morphologies (SEM), porosities (BET), surfaces (XPS, O2-TPD/MS), and electrochemical properties (Tafel analysis, Koutechy-Levich plots, and constant-current electrolysis). These combined results show that the electrocatalytic activities are strongly dependent on the crystallographic structures, and follow an order of α-MnO2 > AMO > β-MnO2 > δ-MnO2. Both OER studies and ORR studies reveal similar structure-determined activity trends in alkaline media. In the OER studies, α-MnO2 displays an overpotential of 490 mV compared to 380 mV shown by an Ir/C catalyst in reaching 10 mA cm(-2). Meanwhile, α-MnO2 also exhibits stability for 3 h when supplying a constant current density of 5 mA cm(-2). This was further improved by adding Ni(2+) dopants (ca. 8 h). The superior OER activity was attributed to several factors, including abundant di-μ-oxo bridges existing in α-MnO2 as the protonation sites, analogous to the OEC in PS-II of the natural water oxidation system; the mixed valencies (AOS = 3.7); and the lowest charge transfer resistances (91.8 Ω, η = 430 mV) as revealed from in situ electrochemical impedance spectroscopy (EIS). In the ORR studies, when reaching 3 mA cm(-2), α-MnO2 shows 760 mV close to 860 mV for the best ORR catalyst (20% Pt/C). The outstanding ORR activity was due to the strongest O2 adsorption capability of α-MnO2 suggested by temperature-programmed desorption. As a result, this discovery of the structure-related electrocatalytic activities could provide guidance in the further development of easily prepared, scalable, and low-cost catalysts based on metal oxides and their derivatives.

A thermally stable 3 x 3 octahedral molecular sieve corresponding to natural todorokite (OMS-1) has been synthesized by autoclaving layer-structure manganese oxides, which are prepared by reactions of MnO(4)(-) and Mn(2+) under markedly alkaline conditions. The nature and thermal stability of products depend strongly on preparation parameters, such as the MnO(4)(-)/Mn(2+) ratio, pH, aging, and autoclave conditions. The purest and the most thermally stable todorokite is obtained at a ratio of 0.30 to 0.40. Autoclave treatments at about 150 degrees to 180 degrees C for more than 2 days yield OMS-1, which is as thermally stable (500 degrees C) as natural todorokite minerals. Adsorption data give a tunnel size of 6.9 angstroms and an increase of cyclohexane or carbon tetrachloride uptake with dehydration temperature up to 500 degrees C. At 600 degrees C, the tunnel structure collapses. Both Lewis and Brönsted acid sites have been observed in OMS-1. Particular applications of these materials include adsorption, electrochemical sensors, and oxidation catalysis.

Hexagonal and cubic phases of manganese oxide mesoporous structures (MOMS) have been prepared by means of the oxidation of Mn(OH) 2 . The hexagonal MOMS materials form a hexagonal array of pores with an open porous structure, thick walls (1.7 nanometers), and exceptional thermal stability (1000°C). The walls of the mesopores are composed of microcrystallites of dense phases of Mn 2 O 3 and Mn 3 O 4 , with MnO 6 octahedra as the primary building blocks. The calcined hexagonal MOMS have an electrical conductivity of 8.13 × 10 −6 per ohm·centimeter, an average manganese oxidation state of 3.55, and a band gap of 2.46 electron volts. Catalytic oxidations of cyclohexane and n -hexane in aqueous solutions in a batch reactor show conversions of ∼10 and ∼8 percent, respectively. Characterization and catalytic data suggest that MOMS systems show significant enhancement in thermal stability with respect to octahedral molecular sieve materials.

This review concerns the synthesis, characterization, and applications of porous manganese oxides during the last two years. The synthesis of porous tunnel structures, layered structures, and related materials is discussed. Both microporous and mesoporous systems materials are covered here. Characterization discussed here focuses around structural studies. The focus of the application sections include electrochemical and catalytic studies.