The synthesis of structurally ordered non-noble intermetallic cobalt stannide (CoSn 2 )n anocrystals and their utilization for high-performance electrocatalytic overall watersplitting is presented. The structurally and electronically beneficial properties of the tetragonal CoSn 2 exhibit ac onsiderably low overpotential for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) on fluorinedoped tin oxide (FTO) and Ni foam (NF). Loss of Sn from the crystal lattices and oxidation of Co under strongly alkaline conditions furnishes highly disordered amorphous active CoO x (H), the catalytically active structure for OER. The Co 0 atoms in the CoSn 2 act as active sites for HER and the presence of Sn provides efficient electrical conductivity.T his intermetallic phase is an ovel type of cost-effective and competitive bifunctional electrocatalysts and predestinated for overall water-splitting devices:At wo-electrode electrolyzer with CoSn 2 on NF delivers ac ell voltage of merely 1.55 Va t 10 mA cm À2 maintaining long-term stability.Intermetallic nanocrystals are considered to be an important class of nanomaterials in the field of superconductivity, ferromagnetism, thermoelectricity,s hape-memory effects, and catalysis owing to their intriguing chemical and physical properties. [1] Recently,i ntermetallic compounds have gained enormous attention in heterogeneous catalysis by virtue of their unusual and attractive crystallographic and electronic properties. [2] It has been shown that the extent of atomic ordering and the relative concentration of both metals drastically influence the overall reactivity efficiency. The recent development of structurally ordered intermetallic materials based on noble metals (Pt, Pd) and early transition metals (Fe, Co,N i) have been successfully used for efficient oxygen reduction reaction (ORR) and HER. Intermetallic compounds containing non-noble metals (main group and transition metals) were also shown to be potential candidates for application in data storage,m agnetic materials,e lectronics,a nd sensors to electrodes in rechargeable batteries. [3] However,t he geometric and electronic influence of such materials for the energy conversion and storage applications are still scarcely investigated.As acentral part for asustainable realization of renewable energy conversion, the development of inexpensive materials for technologies capable of electrochemical water-splitting into hydrogen and oxygen in an economically viable way is highly desired. [4] Currently,n oble-metal-based materials (Pt, RuO 2, and IrO 2 )have been considered as the state-of-the-art electrocatalysts for HER and OER;however,relatively high costs and scarcity of the materials greatly stint their widespread industrial applications. [5] Recently,h igh-performance bifunctional OER and HER electrocatalysts based on nonnoble transition-metal oxides/hydroxides, [6] carbonate/ hydroxides, [7] chalcogenides, [8] phosphides, [9] borides, [10] phosphates, [11] and phosphite [12] functioning in ac ommon elect...
Core/shell and core/shell/shell particles comprised of the Prussian blue analogues K(j)Ni(k)[Cr(CN)(6)](l)·nH(2)O (A) and Rb(a)Co(b)[Fe(CN)(6)](c)·mH(2)O (B) have been prepared for the purpose of studying persistent photoinduced magnetization in the heterostructures. Synthetic procedures have been refined to allow controlled growth of relatively thick (50-100 nm) consecutive layers of the Prussian blue analogues while minimizing the mixing of materials at the interfaces. Through changes in the order in which the two components are added, particles with AB, ABA, BA, and BAB sequences have been prepared. The two Prussian blue analogues were chosen because B is photoswitchable, and A is ferromagnetic with a relatively high magnetic ordering temperature, ~70 K, although it is not known to exhibit photoinduced changes in its magnetic properties. Magnetization measurements on the heterostructured particles performed prior to irradiation show behavior characteristic of the individual components. On the other hand, after irradiation with visible light, the heterostructures undergo persistent photoinduced changes in magnetization associated with both the B and A analogues. The results suggest that structural changes in the photoactive B component distort the normally photoinactive A component, leading to a change in its magnetization.
Ceramic samples of MnW 1−x Mo x O 4 (x ≤ 0.3) solid solution were prepared by a solid-state route with the goal of increasing the magnitude of the spin-exchange couplings among the Mn 2+ ions in the spin spiral multiferroic MnWO 4 . Samples were characterized by X-ray diffraction, optical spectroscopy, magnetization, and dielectric permittivity measurements. It was observed that the Neél temperature T N , the spin spiral ordering temperature T M2 , and the ferroelectric phase-transition temperature T FE2 of MnWO 4 increased upon the nonmagnetic substitution of Mo 6+ for W 6+ . Like pure MnWO 4 , the ferroelectric critical temperature T FE2 (x) coincides with the magnetic ordering temperature T M2 (x). A density functional analysis of the spin-exchange interactions for a hypothetical MnMoO 4 that is isostructural with MnWO 4 suggests that Mo substitution increases the strength of the spin-exchange couplings among Mn 2+ in the vicinity of a Mo 6+ ion. Our study shows that the Mo-doped MnW 1−x Mo x O 4 (x ≤ 0.3) compounds are spin-frustrated materials that have higher magnetic and ferroelectric phase-transition temperatures than does pure MnWO 4 .
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