A Unique Mechanochemical Redox Reaction Yielding Nanostructured Double Perovskite Sr2FeMoO6 With an Extraordinarily High Degree of Anti-Site Disorder.

Strontium ferromolybdate, Sr2FeMoO6, is an important member of the family of double perovskites with the possible technological applications in the field of spintronics and solid oxide fuel cells. Its preparation via a multi-step ceramic route or various wet chemistry-based routes is notoriously difficult. The present work demonstrates that Sr2FeMoO6 can be mechanosynthesized at ambient temperature in air directly from its precursors (SrO, α-Fe, MoO3) in the form of nanostructured powders, without the need for solvents and/or calcination under controlled oxygen fugacity. The mechanically induced evolution of the Sr2FeMoO6 phase and the far-from-equilibrium structural state of the reaction product are systematically monitored with XRD and a variety of spectroscopic techniques including Raman spectroscopy, 57Fe Mössbauer spectroscopy, and X-ray photoelectron spectroscopy. The unique extensive oxidation of iron species (Fe0 → Fe3+) with simultaneous reduction of Mo cations (Mo6+ → Mo5+), occuring during the mechanosynthesis of Sr2FeMoO6, is attributed to the mechanically triggered formation of tiny metallic iron nanoparticles in superparamagnetic state with a large reaction surface and a high oxidation affinity, whose steady presence in the reaction mixture of the milled educts initiates/promotes the swift redox reaction. High-resolution transmission electron microscopy observations reveal that the mechanosynthesized Sr2FeMoO6, even after its moderate thermal treatment at 923 K for 30 min in air, exhibits the nanostructured nature with the average particle size of 21(4) nm. At the short-range scale, the nanostructure of the as-prepared Sr2FeMoO6 is characterized by both, the strongly distorted geometry of the constituent FeO6 octahedra and the extraordinarily high degree of anti-site disorder. The degree of anti-site disorder ASD = 0.5, derived independently from the present experimental XRD, Mössbauer, and SQUID magnetization data, corresponds to the completely random distribution of Fe3+ and Mo5+ cations over the sites of octahedral coordination provided by the double perovskite structure. Moreover, the fully anti-site disordered Sr2FeMoO6 nanoparticles exhibit superparamagnetism with the blocking temperature T B = 240 K and the deteriorated effective magnetic moment µ = 0.055 µ B per formula unit.

Ionic conductivity and structure of M1-xPbxF2 (M = Ca, Sr, Ba) solid solutions prepared by ball milling.

Nanocrystalline M1-xPbxF2 (M = Ca, Sr, Ba) solid solutions were prepared by ball milling mixtures of binary parent materials. The structure of the obtained materials was investigated by 19F MAS NMR spectroscopy and XRPD, and their ionic conductivity by impedance spectroscopy. It was found that fluorite-structured solid solutions over the whole range of compositions can be prepared by ball milling for all three systems, closing the broad miscibility gap of the CaF2-PbF2 system. The fluoride ion conductivity increased with increasing Pb content of the solid solutions, with Ba0.10Pb0.90F2 showing the highest conductivity of all samples prepared, being 1.5 orders of magnitude smaller than the one of PbSnF4. Ca1-xPbxF2 showed a fluoride ion conductivity increase which can be assigned to geometric frustration induced disorder. Ball milling of pure PbF2 revealed an increase of the fluoride ion conductivity by 2.5 orders of magnitude in the case of PbF2 containing a large amount of ß-PbF2 compared to microcrystalline ß-PbF2. Its fluoride ion conductivity is also 2.5 orders of magnitude larger than the fluoride ion conductivity of ball milled PbF2 consisting of a small amount of ß-PbF2 but a large amount of α-PbF2 pointing to differently conducting and structured grain boundaries of α-PbF2 and ß-PbF2.

Using light, X-rays and electrons for evaluation of the nanostructure of layered materials.

As a case study for the evaluation of the nanostructure of layered materials, we report on results of the comprehensive characterization of high-energy ball-milled layered molybdenum disulfide (2H-MoS2) on different length scales. Analysis of X-ray powder diffraction patterns (XRPDs) including the Debye background at low scattering angles caused by uncorrelated single or few-layer MoS2 slabs (full scattering model), yield much more precise data about the average stacking degree than routine XRPD evaluation, and an estimation of the amount of single layer material is possible. Reflections with super Lorentzian line shape can be satisfactorily modeled assuming different stacking sequences induced by the mechanical forces exerted during the high-energy ball-mill process. An advanced analysis of UV-Vis spectra to determine layer number and lateral crystallite size, which was recently developed for liquid exfoliation materials, is used for the first time, and the results demonstrate the universal applicability of the approach. The data obtained with this analysis support the main findings of evaluation of the XRPD data. Both methods clearly evidence that increasing the duration of high-energy ball-mill treatment leads to an increase of material with decreasing average stacking and a reduction of the lateral size of the slabs. Finally, high-resolution transmission electron microscopy enabled identification of defects which can hardly be detected in XRPDs or in UV-Vis spectra.

Tuning Antisite Defect Density in Perovskite-BaLiF3 via Cycling between Ball Milling and Heating.

The defect density of a material is central to its properties. Here, we show, employing EXAFS measurements and MD simulation, how the Ba-Li antisite defect density of perovskite-structured BaLiF3 nanoparticles can be tuned. In particular, we show that ball milling reduces the defect content. Conversely, thermal annealing increases the defect density. The work represents a first step toward tailoring the properties of a material via defect tuning postsynthesis.

Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF2, by ball milling it with BaF2, to create nanostructured Ba1-xCaxF2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including "simulating synthesis", we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba1-xCaxF2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015 , 521 , 303 ] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated "snake-like" ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013 , 138 , 12A538 ]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the "snake" arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization.

Mechanochemical reactions and syntheses of oxides.

Technological and scientific challenges coupled with environmental considerations have prompted a search for simple and energy-efficient syntheses and processing routes of materials. This tutorial review provides an overview of recent research efforts in non-conventional reactions and syntheses of oxides induced by mechanical action. It starts with a brief account of the history of mechanochemistry. Ensuing discussions will review the progress in homogeneous and heterogeneous mechanochemical reactions in oxides of various structures. The review demonstrates that the event of mechanically induced reactions provides novel opportunities for the non-thermal manipulation of materials and for the tailoring of their properties.

Mechanosynthesized nanocrystalline BaLiF(3): The impact of grain boundaries and structural disorder on ionic transport.

The mechanosynthesis of highly pure nanocrystalline BaLiF(3) is reported. The product with mean crystallite diameter of about 30 nm was prepared by joint high-energy ball-milling of the two binary fluorides LiF and BaF(2) at ambient temperature. Compared to coarse-grained BaLiF(3) with µm-sized crystallites, which is available via conventional solid-state synthesis at much higher temperatures, the mechanosynthesized product exhibits a drastic increase of ionic conductivity by several orders of magnitude. This is presumably due to structural disorder introduced during milling and to the presence of a large volume fraction of interfacial regions in the nanocrystalline form of BaLiF(3) providing fast diffusion pathways for the charge carriers. Starting from mechanosynthesized nanocrystalline BaLiF(3) it is possible to tune the transport parameters in a well defined way by subsequent annealing. Changes of the electrical response of mechanosynthesized BaLiF(3) during annealing are studied in situ by impedance spectroscopy. The results are compared with those of a structurally well-ordered single crystal which clearly shows extrinsic and intrinsic regions of ionic conduction.