The morphologically and compositionally controlled synthesis of coordination polymers and spinel oxides is highly desirable for realizing new advanced nanomaterial functionalities. Here we develop a novel and scalable strategy, containing a "copolymer-co-morphology" conception, to shape-controlled synthesis of various types of Prussian blue analogues (PBAs). Three series of PBAs MyFe1-y[Co(CN)6]0.67·nH2O (MyFe1-y-Co, M = Co, Mn and Zn) with well-controlled morphology have been successfully prepared through this strategy. Using MnyFe1-y-Co PBAs as the model, by increasing the relative content of Mn, flexible modulation of the morphology could be easily realized. In addition, a series of porous MnxFe1.8-xCo1.2O4 nano-dices with well-inherited morphologies and defined cation distribution could be obtained through a simple thermal treatment of the PBAs. All these results demonstrate the good universality of this novel strategy. When evaluated as an electrocatalyst, the octahedral-site Mn(III)/Mn(IV) content in MnxFe1.8-xCo1.2O4, mainly determined by sensitive (57)Fe Mössbauer in combination with X-ray photoelectron spectroscopic techniques, was discovered to be directly correlated with the oxygen reduction/evolution reaction (ORR/OER) activity.
The theory of both transmission and grazing incidence Mössbauer spectroscopy is re-analyzed. Starting with the nuclear susceptibility tensor a common concise first order perturbation formulation is given by introducing the forward scattering amplitude into an anisotropic optical scheme. Formulae of Blume and Kistner as well as those of Andreeva are re-derived for the forward scattering and grazing incidence geometries, respectively. Limitations of several previously intuitively introduced approximations are pointed out. The grazing incidence integral propagation matrices are written in a form built up from 2 × 2 matrix exponentials which is particularly suitable for numerical calculations and practical fitting of both energy domain (conventional source experiment) and time domain (synchrotron radiation experiment) Mössbauer spectra.
Using the general approach of Lax for multiple scattering of waves a 2 × 2 covariant expression for the reflectivity of polarized slow neutrons of a magnetic layer structure of arbitrary complexity is given including polarization effects of the external magnetic field. The present formalism is identical to the earlier published one for the (nuclear) resonant x-ray (Mössbauer) reflectivity and properly takes the effect of the external magnetic field of arbitrary direction on the neutron beam into account. The form of the reflectivity matrix allows for an efficient numerical calculation.
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