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.
[Abstract] Multiferroics, defined for those multifunctional materials in which two or more kinds of fundamental ferroicities coexist, have become one of the hottest topics of condensed matter physics and materials science in recent years. The coexistence of several order parameters in multiferroics brings out novel physical phenomena and offers possibilities for new device functions. The revival of research activities on multiferroics is evidenced by some novel discoveries and concepts, both experimentally and theoretically. In this review article, we outline some of the progressive milestones in this stimulating field, specially for those single phase multiferroics where magnetism and ferroelectricity coexist. Firstly, we will highlight the physical concepts of multiferroicity and the current challenges to integrate the magnetism and ferroelectricity into a single-phase system. Subsequently, we will summarize various strategies used to combine the two types of orders. Special attentions to three novel a) E-mail: liujm@nju.edu.cn b) E-mail: renzh@bc.edu Multiferroics 2 mechanisms for multiferroicity generation: (1) the ferroelectricity induced by the spin orders such as spiral and E-phase antiferromagnetic spin orders, which break the spatial inversion symmetry, (2) the ferroelectricity originating from the charge ordered states, and (3) the ferrotoroidic system, will be paid. Then, we will address the elementary excitations such as electromagnons, and application potentials of multiferroics. Finally, open questions and opportunities will be prospected.
The dimensionless thermoelectric figure of merit ͑ZT͒ of the n-type silicon germanium ͑SiGe͒ bulk alloy at high temperature has remained at about one for a few decades. Here we report that by using a nanostructure approach, a peak ZT of about 1.3 at 900°C in an n-type nanostructured SiGe bulk alloy has been achieved. The enhancement of ZT comes mainly from a significant reduction in the thermal conductivity caused by the enhanced phonon scattering off the increased density of nanograin boundaries. The enhanced ZT will make such materials attractive in many applications such as solar, thermal, and waste heat conversion into electricity.
Perovskite-type polycrystalline BiFeO 3 ͑BFO͒ nanowires ͑ϳ50 nm in diameter and ϳ5 m in length͒ were synthesized using the anodized alumina template technique. An energy band gap of ϳ2.5 eV was determined from the UV-visible diffuse reflectance spectrum, and its photocatalytic ability to produce O 2 was revealed under UV irradiation. Weak ferromagnetism at room temperature and superparamagnetism at low temperature were observed for the BFO nanowires, different from the antiferromagnetic order in bulk BFO, reflecting the significant size effects on the magnetic ordering of BFO.
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).
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