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.

Electrolysis of water to generate hydrogen fuel is an attractive renewable energy storage technology. However, grid-scale freshwater electrolysis would put a heavy strain on vital water resources. Developing cheap electrocatalysts and electrodes that can sustain seawater splitting without chloride corrosion could address the water scarcity issue. Here we present a multilayer anode consisting of a nickel–iron hydroxide (NiFe) electrocatalyst layer uniformly coated on a nickel sulfide (NiSx) layer formed on porous Ni foam (NiFe/NiSx-Ni), affording superior catalytic activity and corrosion resistance in solar-driven alkaline seawater electrolysis operating at industrially required current densities (0.4 to 1 A/cm2) over 1,000 h. A continuous, highly oxygen evolution reaction-active NiFe electrocatalyst layer drawing anodic currents toward water oxidation and an in situ-generated polyatomic sulfate and carbonate-rich passivating layers formed in the anode are responsible for chloride repelling and superior corrosion resistance of the salty-water-splitting anode.

Crystalline mesoporous cobalt oxides with improved catalytic activity in CO oxidation were synthesized using an inverse surfactant micelle method. The prepared materials are monodispersed nanoparticle aggregates, and the mesopores are formed by connected intraparticle voids. Powder X-ray diffraction (PXRD), N2 sorption, field emission scanning electron microscope (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) revealed that both pore and nanoparticle sizes are enlarged with increasing thermal treatment temperatures (150–450 °C). Mesoporous cobalt oxide calcined at 350 °C exhibited the best oxidation activity and can achieve complete oxidization (100% conversion) of CO to CO2 at −60 °C under normal conditions (∼3–10 ppm of H2O) and at 80 °C under moisture rich conditions (∼3% H2O). The commercial Co3O4 reached 100% conversion at 220 °C under normal conditions. X-ray photoelectron spectroscopy (XPS), O2-temperature-programmed desorption (O2-TPD), H2-temperature-programmed reduction (H2-TPR), CO-TPD, and N2 sorption analyses indicated that the surface oxygen vacancy and large surface area promoted the lattice oxygen mobility of the catalysts and further enhanced their catalytic performance. The catalysts were deactivated by accumulation of water and formation of carbonates, but their activities can be easily restored by expelling water and carbonates at moderate temperature (200 °C).

Sodium is a promising anode material for batteries due to its low standard electrode potential, high abundance and low cost. In this work, we report a new rechargeable ~ 3.5 V sodium ion battery using Na anode, amorphous carbon-nanosphere cathode and a starting electrolyte comprised of AlCl 3 in SOCl 2 with uoride-based additives. The battery, exhibiting ultrahigh ~ 2800 mAh/g rst discharge capacity, could cycle with a high reversible capacity up to ~ 1000 mAh/g. Through battery cycling, the electrolyte evolved to contain NaCl, various sulfur and chlorine species that supported anode's Na/Na + redox and cathode's chloride/chlorine redox. Fluoride-rich additives were important in forming a solid-electrolyte interface, affording reversibility of the Na anode for a new class of high capacity secondary Na battery. Main TextDevising new battery concepts is important to meeting society's growing demand of energy storage.Different rechargeable batteries have been developed, including lithium ion batteries (LIBs), sodium ion batteries (SIBs) and aluminum ion batteries (AIBs) [1][2][3][4][5][6][7][8][9] . Prior to the invention of secondary LIBs, a primary Li-metal battery was developed in the 1970's using thionyl chloride (SOCl 2 ) as a catholyte, Li metal as anode and amorphous carbon as the positive electrode [10][11][12][13][14][15][16] . The Li-SOCl 2 battery was attractive due to its high energy density, but did not receive sustained interest due to the lack of rechargeability 17,18 . The battery discharges through Li anode oxidation and catholyte SOCl 2 reduction into sulfur (S), sulfur dioxide (SO 2 ), and chloride ion (Cl -) on the carbon electrode 19,20 . The Clions react with Li + stripped from