The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Atomic scale structure and bond stretching force constants in stoichiometric and off-stoichiometric kesterites.

The deviation from stoichiometry and the understanding of its consequences are key factors for the application of kesterites as solar cell absorbers. Therefore, this study investigates the local atomic structure of off-stoichiometric Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and Cu2ZnGeSe4 (CZGSe) by means of Extended X-ray Absorption Fine Structure Spectroscopy. Temperature dependent measurements yield the bond stretching force constants of all cation-anion bonds in stoichiometric CZTS and CZTSe and nearly stoichiometric CZGSe. Low temperature measurements allow high precision analysis of the influence of off-stoichiometry on the element specific average bond lengths and their variances. The overall comparison between the materials is in excellent agreement with measures like ionic/atomic radii and bond ionicities. Furthermore, the small uncertainties allow the identification of systematic trends in the Cu-Se and Zn-Se bond lengths of CZTSe and CZGSe. These trends are discussed in context of the types and concentrations of certain point defects, which gives insight into the possible local configurations and their influence on the average structural parameters. The findings complement the understanding of the effect of off-stoichiometry on the local structure of kesterites, which affects their electronic properties and thus their application for solar cells.

Guest Ion-Dependent Reaction Mechanisms of New Pseudocapacitive Mg3 V4 (PO4 )6 /Carbon Composite as Negative Electrode for Monovalent-Ion Batteries.

Polyanion-type phosphate materials, such as M3 V2 (PO4 )3 (M = Li/Na/K), are promising as insertion-type negative electrodes for monovalent-ion batteries including Li/Na/K-ion batteries (lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent-ion insertion. Here, triclinic Mg3 V4 (PO4 )6 /carbon composite (MgVP/C) with high thermal stability is synthesized via ball-milling and carbon-thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion-dependent reaction mechanisms of MgVP/C upon monovalent-ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg0 , V0 , and Li3 PO4 in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V3+ to V2+ . Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g-1 (30/19 Li+ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na+ /K+ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent-ion batteries with guest ion-dependent energy storage mechanisms.

Lattice assisted dielectric relaxation in four-layer Aurivillius Bi5FeTi3O15ceramic at low temperatures.

We have investigated magnetic, structural and dielectric properties of Bi5FeTi3O15(BFTO) in the temperature range 5K-300 K. Using diffraction, Raman spectroscopy and x-ray absorption fine structure measurements, iso-structural modifications are observed at low temperatures (≈100 K). The analysis of dielectric constant data revealed signatures of dielectric relaxation, concomitant with these structural modifications in BFTO at the same temperatures. Further, employing complementary experimental methods, it is shown that the distribution of Fe/Ti ions in BFTO is random. With the help of techniques that probe magnetism at various length and time scales, it is shown that the phase-pure BFTO is non-magnetic down to the lowest temperatures.

Giant zirconium-bisphosphonate nano-ribbons and their liquid crystalline phase behaviour in water.

In decimolar aqueous solutions, zirconium oxychloride octahydrate forms several micrometer long and approximately 15 nm wide thin ribbons through the reaction with excess amounts of the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid (HEDP, known as etidronic acid). Primarily deduced from SAXS, TEM, EXAFS and solid-state NMR analyses, a consistent structural model enables congruous explanations for the colloidal behaviour of the purified ribbons as well as of their reaction products with ammonia and amines, respectively. Properties of the lyotropic, liquid crystalline phases are discussed in the light of potential applications in aqueous coatings.

Elucidating the Mechanism of Li Insertion into Fe1-xS/Carbon via In Operando Synchrotron Studies.

The detailed understanding of kinetic and phase dynamics taking place in lithium-ion batteries (LIBs) is crucial for optimizing their properties. It was previously reported that Fe1-xS/C nanocomposites display a superior performance as anode materials in LIBs. However, the underlying lithium storage mechanism was not entirely understood during the 1st cycle. In this work, in operando synchrotron techniques are used to track lithium storage mechanisms during the 1st (de)-lithiation process in the Fe1-xS/C nanocomposite. The combination of in operando techniques enables the uncovering of the phase fraction alternations and crystal structural variations on different length-scales. Additionally, the investigation of kinetic processes, morphological changes, and internal resistance dynamics is discussed. These results reveal that the phase transition of Fe1-xS → Li2Fe1-xS2 → Fe0 + Li2S occurs during the 1st lithiation process. The redox reaction of Fe2+ + 2e- ⇌ Fe0 and the Fe K-edge X-ray absorption spectroscopy (XAS) transformation process are confirmed by in operando XAS. During the 1st de-lithiation process, Fe0 and Li2S convert to Li2-yFe1-xS2 and Li+ is extracted from Li2S to form Li2-yS. The phase transition from Li2S to Li2-yS is not detected in previous reports. After the 1st de-lithiation process, amorphous lithiated iron sulfide nanoparticles are embedded within the remaining Li2S matrix.

Investigation of the role and chemical form of iron in the ovarian carcinogenesis process.

BACKGROUND: Ovarian cancer is one of the most frequent types of gynaecological malignancy among women. Despite the advances in diagnostic techniques, ovarian tumours are still detected at a late stage, thus the survival rate is very low. Iron is an essential metal in the human body, yet its potential role in ovarian carcinogenesis is yet to be determined. The aim of this study was to check if iron oxidation state in tissue and cystic fluid can be treated as an indicator of the malignancy of the ovarian tumours. Another aspect of this study was to investigate the role of iron in carcinogenesis mechanism in ovarian tumour transformation. METHODS: Synchrotron radiation X-ray absorption near edge structure (SR-XANES) spectroscopy was used to analyze the human ovarian tumour tissues and cystic fluids of different types and grades of malignancy. Fresh, non-fixed, frozen samples were used to analyze the state of iron oxidation in all the biological materials. The samples were obtained from patients requiring surgical intervention. The High Energy X-ray Absorption Spectroscopy (XANES) measurements were performed at the beamline P65 at Petra III Extension, DESY - Deutsches Elektronen - Synchrotron. RESULTS: Fe XANES spectra were collected at selected points of a few different regions of the samples. For each specimen, an average of these points was probed. Having been measured, the spectra were compared with organic and inorganic reference materials. Also, the position of the absorption edge was calculated using the integration method. In all specimens, iron occurred in the oxidation states, Fe2+ and Fe3+, although the fraction of iron in the third oxidation state was substantial, especially in malignant cases. The results also show differences in the chemical form of iron in the tissue and cystic fluids of the same patient. CONCLUSIONS: The cryo-XANES measurement carried out for ovarian cancer tissues and cystic fluids showed changes in the chemical form of iron between non-malignant and malignant tumours. For both types of sample can be observed that they contain iron on second and iron on third oxidation state. Moreover, the tendency was observed that malignant tumours of the ovary contain a larger fraction of iron in the second oxidation state compared to non-malignant ones.

Mechanism Study of Carbon Coating Effects on Conversion-Type Anode Materials in Lithium-Ion Batteries: Case Study of ZnMn2O4 and ZnO-MnO Composites.

The carbon coating strategy is intensively used in the modification of conversion-type anode materials to improve their cycling stability and rate capability. Thus, it is necessary to elucidate the modification mechanism induced by carbon coating. For this purpose, bare ZnMn2O4, carbon-derivative-coated ZnMn2O4, and carbon-coated ZnO-MnO composite materials have been synthesized and investigated in-depth. Herein, high-temperature synchrotron radiation diffraction is used to monitor the phase transition from ZnMn2O4 to ZnO-MnO composite during the carbonization process. The electrochemical performance has been evaluated by cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The carbon- and carbon-derivative-coated samples display well-improved cycling stability in terms of suppressed electrode polarization, a moderate increase in resistance, and slight capacity variation. The influence of carbon coating on the intrinsic conversion process is investigated by ex situ X-ray absorption spectroscopy, which reveals the evolution of Zn and Mn oxidation states. This result confirms that the strong capacity variation of the bare ZnMn2O4 is induced not only by the reversible charge storage in the solid electrolyte interphase but also by the phase evolution of active materials. Carbon coating is an effective method to prevent the additional oxidation of MnO to Mn3O4, which leads to a stabilization of the main conversion reaction.

An evidence of local structural disorder across spin-reorientation transition in DyFeO3: an extended x-ray absorption fine structure (EXAFS) study.

The present work is aimed at exploring the local atomic structure modifications related to the spin reorientation transition (SRT) in DyFeO3 orthoferrite exploiting x-ray absorption fine structure (XAFS) spectroscopy. For this purpose we studied by XAFS the evolution of the local atomic structure around Fe and Dy as function of temperature (10-300 K) in a DyFeO3 sample having the SRT around 50-100 K. For sake of comparison we studied a YFeO3 sample having no SRT. The analysis of the extended region has revealed an anomalous trend of Fe-O nearest neighbour distribution in DFO revealing (i) a weak but significant compression with increasing temperature above the SRT and (ii) a peculiar behavior of mean square relative displacement (MSRD) [[Formula: see text]] of Fe-O bonds showing an additional static contribution in the low temperature region, below the SRT. These effects are absent in the YFO sample supporting these anomalies related to the SRT. Interestingly the analysis of Dy L 3-edge data also reveal anomalies in the Dy-O neighbour distribution associated to the SRT, pointing out a role of magnetic Re ions across [Formula: see text]. These results point out micro-structural modification at both Fe and Dy sites associated to the magnetic transitions in DFO, it can be stated in general terms that such local distortions across [Formula: see text] and magnetic Re3+ may be present in other orthoferrites exhibiting multiferroic nature.

In Operando Synchrotron Diffraction and in Operando X-ray Absorption Spectroscopy Investigations of Orthorhombic V2O5 Nanowires as Cathode Materials for Mg-Ion Batteries.

Orthorhombic V2O5 nanowires were successfully synthesized via a hydrothermal method. A cell-configuration system was built utilizing V2O5 as the cathode and 1 M Mg(ClO4)2 electrolyte within acetonitrile, together with Mg xMo6S8 ( x ≈ 2) as the anode to investigate the structural evolution and oxidation state and local structural changes of V2O5. The V2O5 nanowires deliver an initial discharge/charge capacity of 103 mAh g-1/110 mAh g-1 and the highest discharge capacity of 130 mAh g-1 in the sixth cycle at C/20 rate in the cell-configuration system. In operando synchrotron diffraction and in operando X-ray absorption spectroscopy together with ex situ Raman and X-ray photoelectron spectroscopy reveal the reversibility of magnesium insertion/extraction and provide information on the crystal structure evolution and changes of the oxidation states during cycling.

A call for a round robin study of XAFS stability and platform dependence at synchrotron beamlines on well defined samples.

Round robin studies have been used across fields of science for quality control testing and to investigate laboratory dependencies and cross-platform inconsistencies as well as to drive forward the improvement of understanding of experimental systems, systematic effects and theoretical limitations. Here, following the Q2XAFS Workshop and Satellite to IUCr Congress 2017 on `Data Acquisition, Treatment, Storage - quality assurance in XAFS spectroscopy', a mechanism is suggested for a suitable study across XAFS (X-ray absorption fine-structure) beamlines and facilities, to enable each beamline to cross-calibrate, provide representative test data, and to enable collaborative cross-facility activities to be more productive.

Kinetic alteration of the 6Mg(NH2)2-9LiH-LiBH4 system by co-adding YCl3 and Li3N.

The 6Mg(NH2)2-9LiH-LiBH4 composite system has a maximum reversible hydrogen content of 4.2 wt% and a predicted dehydrogenation temperature of about 64 °C at 1 bar of H2. However, the existence of severe kinetic barriers precludes the occurrence of de/re-hydrogenation processes at such a low temperature (H. Cao, G. Wu, Y. Zhang, Z. Xiong, J. Qiu and P. Chen, J. Mater. Chem. A, 2014, 2, 15816-15822). In this work, Li3N and YCl3 have been chosen as co-additives for this system. These additives increase the hydrogen storage capacity and hasten the de/re-hydrogenation kinetics: a hydrogen uptake of 4.2 wt% of H2 was achieved in only 8 min under isothermal conditions at 180 °C and 85 bar of H2 pressure. The re-hydrogenation temperature, necessary for a complete absorption process, can be lowered below 90 °C by increasing the H2 pressure above 185 bar. Moreover, the results indicate that the hydrogenation capacity and absorption kinetics can be maintained roughly constant over several cycles. Low operating temperatures, together with fast absorption kinetics and good reversibility, make this system a promising on-board hydrogen storage material. The reasons for the improved de/re-hydrogenation properties are thoroughly investigated and discussed.

Design considerations for a new beamline for standard EXAFS at a high-energy low-emittance storage ring.

P65 is a new EXAFS beamline to be built at the PETRA III storage ring at DESY in Hamburg. It will mainly be used for standard EXAFS applications with a relatively large beam and moderate flux density. While the beamline optics will be similar to many other standard EXAFS beamlines, the insertion device at such a large high-energy storage ring with low emittance like PETRA III will need special attention. This paper discusses the main design considerations for the construction of such a beamline at a 6 GeV storage ring with an emittance of 1 nm rad.

A fast energy-dispersive multi-element detector for X-ray absorption spectroscopy.

In this paper results are presented from fluorescence-yield X-ray absorption fine-structure spectroscopy measurements with a new seven-cell silicon drift detector (SDD) module. The complete module, including an integrated circuit for the detector readout, was developed and realised at DESY utilizing a monolithic seven-cell SDD. The new detector module is optimized for applications like XAFS which require an energy resolution of approximately 250-300 eV (FWHM Mn Kalpha) at high count rates. Measurements during the commissioning phase proved the excellent performance for this type of application.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Compost-based permeable reactive barriers for the source treatment of arsenic contaminations in aquifers: column studies and solid-phase investigations.

The bulk of arsenic (As) at contaminated sites is frequently associated with iron (hydr)oxides. Various studies ascribe increasing dissolved As concentrations to the transformation of iron (hydr)oxides into iron sulfides, which is initiated by dissolved sulfide. We investigated whetherthis processes can be utilized as a source treatment approach using compost-based permeable reactive barriers (PRB), which promote microbial sulfate reduction. Arsenic-bearing aquifer sedimentfrom a contaminated industrial site showed a decrease in As content of <10% after 420 days of percolation with sulfide-free artificial groundwater. In contrast, water that had previously passed through organic matter and exhibited sulfide concentrations of 10-30 mg/L decreased As content in the sediment by 87% within 360 days. X-ray diffraction showed no arsenic sulfides, but XANES spectra (X-ray absorption near edge structure) and associated linear combinations revealed that adsorbed arsenate of the original sediment was in part reduced to arsenite and indicated the formation of minor amounts of a substance that contains As and sulfur. The speciation of dissolved As changed from initially As(V)-dominated to As(III)-dominated after sulfide flushing was started, which increases the mobility of As. Because sulfide can be supplied not only by compost-based PRBs but also by direct injection, sulfide flushing has a wide range of application for the source treatment of arsenic.

A new X-ray spectrometer with large focusing crystal analyzer.

A new focusing spectrometer employing Johann geometry has been built and permanently installed at the wiggler beamline W1 at the Hamburger Synchrotron Strahlungslabor (HASYLAB) am Deutschen Elektronen Synchrotron (DESY). It is now available for user operation. The design of the spectrometer is optimized for the use of a large source spot size at the DORIS storage ring as well as for simple operation and robustness under user-mode conditions. Nevertheless, the ideal source for enlarging the number of possible applications in the future would be an undulator at one of the PETRA III beamlines. In the following the spectrometer design is described and boundary conditions such as the available energy range for future experiments are discussed. Two benchmark experiments, resonant inelastic X-ray scattering (RIXS) and X-ray absorption fluorescence spectroscopy (XAFS), on samples with complicated matrices demonstrate the performance of the new instrument.