High-resolution X-ray Powder Diffraction Research Articles

A new organic nonlinear optical material: L-asparagine cetrimonium bromide single crystal for photonic applications

Abstract The new organic nonlinear optical material, L-Asparagine Cetrimonium Bromide (LACB) was synthesized by using slow evaporation method at ambient conduction. The crystallographic data was analyzed by single crystal X-ray diffraction (XRD) and crystalline perfection was studied under high resolution powder X-ray diffraction technique. The functional groups were found out by FT-IR spectroscopy and various optical parameters were performed by using UV–Vis NIR spectroscopy. In fluorescence spectrum the sharp emission peak was observed at 529 nm it reveals the green emission. The second harmonic generation efficiency was determined by the Kurtz powder method using Nd-YAG laser. The laser induced damage threshold value was found to be higher than most of the reported organic single crystals. The dielectric permittivity and dielectric loss were analyzed as a function of frequency. The photoconductivity study implies that the grown crystal has positive photoconductive nature. Different mechanical properties were analyzed by Vickers microhardness test.

Fluorescent Zr(IV) Metal-Organic Frameworks Based on an Excited-State Intramolecular Proton Transfer-Type Ligand.

We report here the preparation of a series of Zr(IV) metal-organic frameworks (MOFs) of the MIL-140 structure type incorporating a ligand exhibiting an intense excited-state intramolecular proton transfer (ESIPT) fluorescence. These solids were obtained by systematically varying the substitution rate of 4,4'-biphenyldicarboxylate by 2,2'-bipyridine-3,3'-diol-5,5'-dicarboxylate, and they were thoroughly characterized by complementary techniques, including high-resolution powder X-ray diffraction, solid-state NMR spectroscopy, nitrogen sorption experiments, and time-resolved fluorescence. We show that the incorporation of the ESIPT-type ligand induces an increase of the hydrophilicity, leading ultimately to a higher sensitivity toward hydrolysis, a phenomenon rarely observed in this structure type, which is considered as one of the most stable among the Zr carboxylate MOFs. Eventually, optimization of the amount of fluorescent ligand within the structure allowed combining a decent microposity ( SBET > 750 m2·g-1) and a high stability even in boiling water, together with a high fluorescence quantum yield (>30%).

Reconciling Crystallographic and Physical Property Measurements on Thermoelectric Lead Sulfide.

For many decades the lead chalcogenides PbTe, PbSe, and PbS (and their solid solutions) have been preferred high-performance thermoelectric materials due to their exceptional electronic and thermal properties as well as great stability during operation. However, there is a lack of understanding about the fundamental relation between the reported high-defect crystal structure containing cation disorder and vacancies and the observed transport properties, which follow expectations for an ideal rock salt crystal structure. Here we have studied a series of undoped lead sulfide samples (Pb1- xS) with presumed small chemical variations. Crystallographic refinements of high-resolution synchrotron powder X-ray diffraction data give unphysically low lead occupancies (0.75-0.98), in contradiction with the measured charge carrier concentration, resistivity, mobility, and Seebeck coefficient, which show no signs of lead vacancies. A new Rietveld refinement model including preferred orientation parameters and anisotropic strain gives almost full lead occupancy and improved agreement factors. However, transmission electron microscopy analysis reveals that there is no preferred orientation in this system. Instead it is the diffuse scattering due to directional correlated disorder in the structure that necessitates the additional parameters when modeling Bragg intensities. The present approach is a general method for absorbing effects of direction-dependent correlations in advanced materials.

Solid solution formation in the metatorbernite-metazeunerite system (Cu(UO2)2(PO4)2- x(AsO4) x. nH2O) and their stability under conditions of variable temperature.

Mineral phases which can be thought of as members of a metatorbernite-metazeunerite solid solution (Cu(UO2)2(PO4)2- x(AsO4) x.8H2O have been identified in radioactive samples from spoil heaps at the uranium mine site in South Terras, Cornwall (grid reference SW935523). A complete solid solution (0 < x < 2) was synthesized by precipitation from solution using uranium (VI) nitrate and copper (II) chloride and phosphoric acid/arsenic acid in the appropriate molar proportions. Refined unit cell parameters determined by Pawley fitting of powder X-ray diffraction data showed a linear variation in the a unit cell parameter according to Vegard's Law, allowing the composition of the natural mineral phases found at South Terras to be determined from measurement of their unit cell parameters. High-resolution variable-temperature synchrotron powder X-ray diffraction studies were carried out at the Diamond Light Source on three members of this solid solution ( x = 0, 1, 2) and showed different structural behaviour as a function of composition and temperature. Metatorbenite ( x = 0) retains its tetragonal symmetry at low temperatures and dehydrates to an amorphous phase at 473 K, whereas metazeunrite ( x = 2) transforms to an orthorhombic phase at low temperatures, regains its tetragonal symmetry on heating to 323 K and undergoes a further transition to an, as yet, unidentified phase at 473 K. This article is part of the theme issue 'Fifty years of synchrotron science: achievements and opportunities'.

Structural and electronic properties of the overexpanded quaternary superconducting fulleride K0.25Rb0.25Cs2.5C60

The structural and magnetic properties of the overexpanded quaternary K0.25Rb0.25Cs2.5C60 fulleride are investigated. Rietveld analysis of the high-resolution synchrotron X-ray powder diffraction data shows that K0.25Rb0.25Cs2.5C60 adopts a cubic structure with face-centered (fcc) symmetry. Magnetization measurements at ambient pressure reveal that the material is a superconductor with a transition temperature, Tc, of 29.4 K. Temperature dependence of the magnetic susceptibility does not show a simple temperature-independent Pauli susceptibility term – instead, it shows a cusp at a certain temperature implying an insulator-to-metal crossover on cooling. Complementary high-pressure magnetization measurements to a pressure of 10.2 kbar show a non-monotonic response of Tc with a dome-shaped scaling with pressure and a maximum value of 32.4 K at 3.9 kbar. The experimental results are consistent with quaternary K0.25Rb0.25Cs2.5C60 following the established unconventional behavior of overexpanded fullerides. However, our results also unveil well-defined detrimental cation specific effects on the electronic properties associated with the introduction of increased disorder in the tetrahedral interstices of the fcc fulleride structure.

Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability.

The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA)2(MA) n-1Pb nI3 n+1 ( n = 1-5, PA = CH3(CH2)4NH3+, C5) and hexylamine (HA)2(MA) n-1Pb nI3 n+1 ( n = 1-4, HA = CH3(CH2)5NH3+, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

Mild Hydrothermal Crystallization of Heavy Rare-Earth Chromite RECrO3 (RE = Er, Tm, Yb, Lu) Perovskites and Magnetic Properties.

Crystallization of perovskite structure chromites (ACrO3) in aqueous conditions is difficult owing to the amphoteric nature of the Cr3+ in the alkaline-mediated reaction conditions. This is especially true for the small metal cations at the A-site with large distortion angle of CrO6 octahedral and small Goldschmidt tolerance factors. Here, we performed a progressive dehydration crystallization strategy to synthesize four RECrO3 with the smallest radii of rare earth elements (Er, Tm, Yb, Lu) in mild hydrothermal conditions. Profile refinement of the high-resolution powder X-ray diffraction results indicated slightly longer unit cell parameters of a and c in our samples with a higher distorted angle of CrO6 octahedral units along ⟨010⟩ direction. All of the samples show rounded rectangle plate morphology with uniform distribution of particle sizes. These four RECrO3 crystals can only form in a very narrow mineralization temperature range, i.e., 260-280 °C and 4.45-6.24 M of KOH. HRTEM results indicated that the normal crystallographic direction is ⟨001⟩, and the lattice of steps at the edge of elliptic rounded crystal is consistent with the bulk, which demonstrated single crystalline nature of the as-obtained crystals. Room-temperature Raman and FT-IR spectra reveal a continuous symmetry mode shift-dependent on the radii of A-site rare-earth cations. Temperature-dependent magnetization curves of RECrO3 show typical antiferromagnetism to paramagnetism transition with Néel temperature of 93, 90, 86, and 83 K for ErCrO3, TmCrO3, YbCrO3, and LuCrO3, respectively. Samples of YbCrO3 and LuCrO3 show clear magnetization reversal and exchange bias phenomena below their Néel points. This paper indicates that the coupling of magnetic exchange in perovskite structure oxides could be tailorable in mild hydrothermal condition, towards the exploration of new magnetic and other physical properties.

Evidence of continuous pottery production during the late Byzantine period in the Studenica Monastery, a UNESCO World Heritage Site

A collection of 63 pottery shards excavated at the Studenica Monastery, Serbia, originating from two distinct cultural strata (late 12th until the late 13th century, and the 14th and the first half of 15th century) was subject of this work. Mineralogical and chemical composition of body and glaze and production technology of investigated pottery were determined combining optical microscopy, inductively coupled plasma-optical emission and wavelength dispersive X-ray fluorescence spectrometry, Fourier transform infrared and micro-Raman spectroscopy, high-resolution synchrotron powder X-ray diffraction and multivariate statistical analysis. In addition, clay rod with traces of glaze from the kiln found within the Monastery complex was investigated. The firing temperature was estimated at 600–700 °C for the most of cookware and at 800–1000 °C for tableware. Pottery, made of non-calcareous clay, was covered with transparent lead based glaze and copper and iron were used as colorants. Combining results of all used techniques no significant differences in mineralogical and chemical composition among samples from two cultural strata were identified indicating continuous pottery production process from 13th until 15th century in Studenica.

Bulk properties of the van der Waals hard ferromagnet VI3

We present comprehensive measurements of the structural, magnetic and electronic properties of layered van-der-Waals ferromagnet VI$_3$ down to low temperatures. Despite belonging to a well studied family of transition metal trihalides, this material has received very little attention. We outline, from high-resolution powder x-ray diffraction measurements, a corrected room-temperature crystal structure to that previously proposed and uncover a structural transition at 79 K, also seen in the heat capacity. Magnetization measurements confirm VI$_3$ to be a hard ferromagnet (9.1 kOe coercive field at 2 K) with a high degree of anisotropy, and the pressure dependence of the magnetic properties provide evidence for the two-dimensional nature of the magnetic order. Optical and electrical transport measurements show this material to be an insulator with an optical band gap of 0.67 eV - the previous theoretical predictions of d-band metallicity then lead us to believe VI$_3$ to be a correlated Mott insulator. Our latest band structure calculations support this picture and show good agreement with the experimental data. We suggest VI$_3$ to host great potential in the thriving field of low-dimensional magnetism and functional materials, together with opportunities to study and make use of low-dimensional Mott physics.

Structural investigation of the Sm(Fe1−xRux)As(O0.85F0.15) system: a synchrotron x-ray powder diffraction study

The structural and microstructural properties of the Sm(Fe1−xRux)As(O0.85F0.15) system were investigated by means of high-resolution synchrotron x-ray powder diffraction between 10 and 300 K. The tetragonal to orthorhombic structural transition temperature decreases with the increase of the Ru content and the symmetry breaking is completely suppressed around x ∼ 0.38. By combining the present results with previous magnetic and resistivity measurements, a phase diagram for the Sm(Fe1−xRux)As(O0.85F0.15) system has been drawn.

Charge redistribution and the magnetoelastic transition across the first-order magnetic transition in (Mn,Fe) 2 (P,Si,B)

We used temperature dependent high-resolution x-ray powder diffraction and magnetization measurements to investigate structural, magnetic and electronic degrees of freedom across the ferromagnetic magneto-elastic phase transition in Mn1Fe1P0.6-wSi0.4Bw (w = 0, 0.02, 0.04, 0.06, 0.08). The magnetic transition was gradually tuned from a strong first-order (w = 0) towards a second-order magnetic transition by substituting P by B. Increasing the B content leads to a systematic increase in the magnetic transition temperature and a decrease in thermal hysteresis, which completely vanishes for w = 0.08. Furthermore, the largest changes in lattice parameter across the magnetic transition occur for w = 0, which systematically becomes smaller approaching the samples with w = 0.08. Electron density plots show a strong directional preference of the electronic distribution on the Fe site, which indicates the forming of bonds between Fe atoms and Fe and P/Si in the paramagnetic phase. On the other hand, the Mn-site shows no preferred directions resembling the behaviour of a free electron gas. Due to the low B concentrations (w = 0 - 0.08), distortions of the lattice are limited. However, even small amounts of B strongly disturb the overall topology of the electron density across the unit cell. Samples containing B show a strongly reduced variation in the electron density compared to the parent compound without B.

Reactivity of Solid Rubrene with Potassium: Competition between Intercalation and Molecular Decomposition

We present the synthesis and characterization of the K+-intercalated rubrene (C42H28) phase, K2Rubrene (K2R), and identify the coexistence of amorphous and crystalline materials in samples where the crystalline component is phase-pure. We suggest this is characteristic of many intercalated alkali metal-polyaromatic hydrocarbon (PAH) systems, including those for which superconductivity has been claimed. The systematic investigation of K-rubrene solid-state reactions using both K and KH sources reveals a complex competition between K intercalation and the decomposition of rubrene, producing three K-intercalated compounds, namely, K2R, K(RR*), and K xR' (where R* and R' are rubrene decomposition derivatives C42H26 and C30H20, respectively). K2R is obtained as the major phase over a wide composition range and is accompanied by the formation of amorphous byproducts from the decomposition of rubrene. K(RR*) is synthesized as a single phase, and K xR' is obtained only as a secondary phase to the majority K2R phase. The crystal structure of K2R was determined using high-resolution powder X-ray diffraction, revealing that the structural rearrangement from pristine rubrene creates two large voids per rubrene within the molecular layers in which K+ is incorporated. K+ cations accommodated within the large voids interact strongly with the neighboring rubrene via η6, η3, and η2 binding modes to the tetracene cores and the phenyl groups. This contrasts with other intercalated PAHs, where only a single void per PAH is created and the intercalated K+ weakly interacts with the host. The decomposition products of rubrene are also examined using solution NMR, highlighting the role of the breaking of C-Cphenyl bonds. For the crystalline decomposition derivative products K(RR*) and K xR', a lack of definitive structural information with regard to R* and R' prevents the crystal structures from being determined. The study illustrates the complexity in accessing solvent-free alkali metal salts of reduced PAH of the type claimed to afford superconductivity.

Combining a nine-crystal multi-analyser stage with a two-dimensional detector for high-resolution powder X-ray diffraction

The high-resolution powder diffraction beamline at ESRF (ID22), built with a dual-undulator source on the 6 GeV storage ring, combines a wide continuous range of incident energy (6–80 keV) with high brightness, offering the possibility to carry out high-flux high-resolution powder diffraction measurements. In routine operation, a bank of nine scintillation detectors is scanned vertically to measure the diffracted intensity versus 2θ, each detector being preceded by an Si 111 analyser crystal. Although the current detector system has operated successfully for the past 20 years, recent developments in detector technology could be exploited to improve the overall performance. With this in mind, as a test, a two-dimensional Pilatus3 X CdTe 300 K-W pixel detector has been mounted on the arm of the diffractometer, replacing the nine scintillator detectors. At each nominal 2θ value, a two-dimensional image is recorded showing nine distinct regions corresponding to the diffraction signals passing via each of the analyser crystals. This arrangement offers new flexibility in terms of data handling and processing, with the possibility to optimize both peak shape and statistics, to remove parasitic effects, and to gain spatial resolution information. Combining the high efficiency of a hybrid photon-counting area detector with the high angular resolution given by analyser crystals is an effective approach to improving the overall performance of high-resolution powder diffraction.

Position and oxidation state of tin in Sn-bearing tetrahedrites Cu12-xSnxSb4S13

We have explored the homogeneity range of Cu12-xSnxSb4S13 tetrahedrites, the peculiarities of their crystal structure, and the oxidation state of tin in them. Phase analysis and crystal structure refinement based on high-resolution powder X-ray diffraction have shown that tin-bearing tetrahedrites exist to the maximum of 0.75÷0.8 tin atoms per formula, with the cubic unit cell parameter increasing from 10.331 to 10.391 Å. The analysis of atomic parameters have proved that tin substitutes for copper only on the Cu(1) site, which is characterized by a regular tetrahedral coordination. The substitution site is further confirmed by 119Sn Mössbauer spectroscopy, showing the low quadrupole splitting, Δ = 0.14–0.16 mm s−1, evidencing the highly-symmetric tetrahedral coordination of tin. Also, the +4 oxidation state of tin directly follows from the isomer shifts values, δ = 1.50–1.52 mm s−1.

Crystal Chemistry of Three Volcanic K-rich Nepheline Samples From Oldoinyo Lengai, Tanzania and Mount Nyiragongo, Eastern Congo, Africa

Natural nepheline (Nph) samples are intermediate members of solid solutions that extend from the pure Na end-member Na[AlSiO4] to the pure K end-member K[AlSiO4] (= kalsilite, Kls). We examined two volcanic nepheline (ideally, K2Na6[Al8Si8O32] or Nph0.75Kls0.25) samples from Oldoinyo Lengai, Tanzania (samples 1 and 2) and a third sample 3 from Mount Nyiragongo, Eastern Congo. The crystal structure of these three samples was obtained using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data and Rietveld structure refinements in space group P63. Satellite reflections were not observed in these samples. The EPMA composition of sample 1 is {K1.50Na0.19Ca0.070.23}Σ2(Na)6[Si8.35Al7.48Fe0.18]Σ16.00O32. The A site contains 0.23 vacancies () with some Na and Ca atoms, whereas the B site is completely filled with only Na atoms. From the EPMA formula, K(sof) = 0.844 and Na(sof) = 1.0. The refinement unit-cell parameters are a = 10.00247(1), c = 8.38396(1) A, V = 726.431(1) A3; K(sof) = 0.779(2) and Na(sof) = 0.988(2). The composition of sample 2 is {K1.670.33}Σ2(Na5.76K0.174Ca0.06)Σ6[Si8.44Al7.37Fe0.20]Σ16.01O32, so K(sof) = 0.835 and Na(sof) = 1.030. Sample 2 has a = 10.01769(2), c = 8.39586(2) A, V = 729.678(1) A3, K(sof) = 0.812(2), and Na(sof) = 0.995(2). Sample 3 is a three-phase (3a, 3b, 3c) intergrowth with an average formula of {K1.770.23}2(Na4.30K1.51Ca0.19)Σ6[Si8.13Al7.76Fe0.11]Σ16.00O32, K(sof) = 0.887, and Na(sof) = 1.208. A large amount of K and Ca atoms occur in the B site. Based on the weight percentages and sofs of the three phases, the Rietveld refinement gives an average K(sof) = 0.859 and Na(sof) = 1.145. The average distances indicate a high degree of Al-Si disorder in samples 1, 2, and phase 3b. These African samples extend natural nepheline solid solutions to about Nph0.55Kls0.45. The average distance increases linearly with Na(sof) and V across nepheline solid solutions because K atoms enter the Na site. K-rich nepheline seems to always contain vacancies in the A site.

Interstitial nitrides revisited – A simple synthesis of MxMo3N (M = Fe, Co, Ni)

The efficient synthesis of polycrystalline filled beta-Mn structured Ni2Mo3N, and the eta-carbides Fe3Mo3N and Co3Mo3N, by a single heating of metal powders at 975 °C under a hydrogen-nitrogen mixture is reported. Rietveld analysis of high-resolution X-ray powder diffraction data shows that the reduction-nitridation of NiMoO4 produces Ni2Mo3N and nickel; Ni3Mo3N is not obtained in this way and its existence is disproved.

Nitro-functionalized Bis(pyrazolate) Metal-Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions.

The metal-organic frameworks (MOFs) M(BPZNO2 ) (M=Co, Cu, Zn; H2 BPZNO2 =3-nitro-4,4'-bipyrazole) were prepared through solvothermal routes and were fully investigated in the solid state. They showed good thermal stability both under a N2 atmosphere and in air, with decomposition temperatures peaking up to 663 K for Zn(BPZNO2 ). Their crystal structure is characterized by 3D networks with square (M=Co, Zn) or rhombic (M=Cu) channels decorated by polar NO2 groups. As revealed by N2 adsorption at 77 K, they are micro-mesoporous materials with BET specific surface areas ranging from 400 to 900 m2 g-1 . Remarkably, under the mild conditions of 298 K and 1.2 bar, Zn(BPZNO2 ) adsorbs 21.8 wt % CO2 (4.95 mmol g-1 ). It shows a Henry CO2 /N2 selectivity of 15 and an ideal adsorbed solution theory (IAST) selectivity of 12 at p=1 bar. As a CO2 adsorbent, this compound is the best-performing MOF to date among those bearing a nitro group as a unique chemical tag. High-resolution powder X-ray diffraction at 298 K and different CO2 loadings revealed, for the first time in a NO2 -functionalized MOF, the insurgence of primary host-guest interactions involving the C(3)-NO2 moiety of the framework and the oxygen atoms of carbon dioxide, as confirmed by Grand Canonical Monte Carlo simulations. This interaction mode is markedly different from that observed in NH2 -functionalized MOFs, for which the carbon atom of CO2 is involved.

Combining a nine-crystal multianalyser stage with a Pilatus3 X CdTe detector for high-resolution X-ray powder diffraction at ESRF-ID22

Combining a nine-crystal multianalyser stage with a Pilatus3 X CdTe detector for high-resolution X-ray powder diffraction at ESRF-ID22

Doped Sr2FeIrO6-Phase Separation and a Jeff ≠ 0 State for Ir5.

High-resolution synchrotron X-ray and neutron powder diffraction data demonstrate that, in contrast to recent reports, Sr2FeIrO6 adopts an I1̅ symmetry double perovskite structure with an a-b-c- tilting distortion. This distorted structure does not tolerate cation substitution, with low levels of A-site (Ca, Ba, La) or Fe-site (Ga) substitution leading to separation into two phases: a stoichiometric I1̅ phase and a cation-substituted, P21/ n symmetry, a-a-c+ distorted double perovskite phase. Magnetization, neutron diffraction, and 57Fe Mössbauer data show that, in common with Sr2FeIrO6, the cation substituted Sr2- xA xFe1- yGa yIrO6 phases undergo transitions to type-II antiferromagnetically ordered states at TN ∼ 120 K. However, in contrast to stoichiometric Sr2FeIrO6, cation substituted samples exhibit a further magnetic transition at TA ∼ 220 K, which corresponds to the ordering of Jeff ≠ 0 Ir5+ centers in the cation-substituted, P21/ n symmetry, double perovskite phases.

Hazardous Metal Cations Recovery Using Electrochemical Intercalation in the Chevrel Phases: A Combined Synchrotron X-Ray Powder Diffraction/Electrochemistry Study

Industrial activities generate effluents containing metallic cations noxious for the environment, humans and wild life, motivating intensive research as those cations are considered as micro contaminants according to European standards [1]. It is important to detect and separate these cations in order to reduce pollution and also to collect the matter due to metals cost and ore depletion. Chalcogenide molybdenum clusters known as Chevrel phases [2] exhibit outstanding physical (superconductivity, thermoelectricity) [3] and chemical (cations intercalation, catalysis) [4] properties. The vacancies in the Chevrel Phases structure enable reversible redox reactions Mo6X8 + x Mn+ + x ne- ó MxMo6X8 [5] (X= S, Se) that lead to a room temperature ionic mobility exploited for selective recovery of metallic cations [6]; to amperometric detection heavy metals [7] and as electrode for magnesium battery [8]. Electrochemistry studies have been conducted on Mo6X8 in Cd2+, Ni2+, Co2+ and Zn2+ single-cationic solutions. Those cations were chosen so as to recreate effluents resulting from battery recycling. Multi-cationic electrolytes (namely Cd2+/Ni2+, Ni2+/Co2+, Cd2+/Co2+, Cd2+/Zn2+, Ni2+/Zn2+, Ni2+/Co2+/Cd2+, Ni2+/Co2+/Zn2+, Ni2+/Cd2+/Zn2+) were investigated with the aim to examine if selectivity occurs. Chronoamperometry and Chronopotentiometry were performed to obtain the fully intercalated phases. For few cationic solutions, further in-situ experiments were done at the ID22 beamline (European Synchrotron Radiation Facility) coupling electrochemistry and high resolution X-ray powder diffraction (XPRD). Complementary ex-situ XRPD experiments on CdxMo6S8 end NiyMo6S8 were also carried out. It has been shown by in-situ experiments that Cd2+ is preferentially intercalated in presence of other cations due to its higher mobility in the channels of the host lattice. We also gathered information such as accurate cell parameters, intercalation kinetics and relative proportions of phases during the entire electrochemical processes. Ex-situ experiments performed in capillary at the ESRF allowed to determine a ternary phase never reported in the literature for the intercalation of Cd2+ into Mo6S8. [1]http://eur-lex.europa.eu/legal-content/FR/ALL/?uri=CELEX:32008L0105http://eur-lex.europa.eu/legal-content/FR/ALL/?uri=CELEX:3200L0105, Directive 2008/105/CE, European Parliament and Union European Council (2008) [2] R. Chevrel, et al., Material Research Bulletin, 9, 1487-1498 (1974) [3] O. Fischer et al., J. of Physic, C, 7 (1974) [4] K.F. Mc Carty, et al., J. Catal., 93, 375 (1985), [5] R. Schöllhorn, et al., Material Research Bulletin, 12, 781 (1977) [6] S. Seghir, et al., Electrochemistry Communications, 10, 1505-1508 (2008) [7] S. Boursicot et al., Electrochemica Acta, 10.1016/j.electacta.2017.10.039 (2017) [8] D. Aurbach et al., Chem. Mater., 14, 2767-2733 (2002)