X-ray Absorption Spectroscopy In Transmission Mode Research Articles

Structure Determination of Phosphoric Acid and Phosphate Ions in Aqueous Solution Using EXAFS Spectroscopy and Large Angle X-ray Scattering.

The structures of hydrated phosphoric acid and phosphate ions (H2PO4-, HPO42-, and PO43-) in aqueous solution have been determined by P K-edge EXAFS and large angle X-ray scattering (LAXS). The P-O bond distance in all phosphate species studied is close to 1.53 Å. The P-(O)···Oaq distances have been refined to ca. 3.6 Å from the LAXS data giving a P-O···Oaq bond angle close to tetrahedral, suggesting that each oxygen or OH group of phosphoric acid and dihydrogen phosphate, on average, hydrogen bind three water molecules. The (P-)O(-H)···Oaq and (P-)O···(H-)Oaq hydrogen bonds in hydrated phosphoric acid and the H2PO4- ion are shorter than the hydrogen bonds in neat water. This supports previous infrared spectroscopic studies claiming that the hydrogen bonds in hydrated phosphoric acid and phosphate ions are stronger than the hydrogen bonds in neat water. Phosphoric acid and phosphate ions can therefore be regarded as structure making solutes. This is the first study applying transmission mode X-ray absorption spectroscopy (XAS) data collection on the P K-edge. It shows that XAS spectra collected in transmission mode have a much better S/N ratio than data collected in fluorescence mode, allowing accurate determination of P-O bond distances. Furthermore, P K-edge EXAFS data collected in fluorescence mode display a higher amplitude at high k than expected due to increasing radiated volume of the sample with increasing energy as the total absorption decreases sharply with increasing energy of the X-rays. As a result, the fluorescence signal becomes nonproportional to the intensity of the X-ray beam over the EXAFS spectrum. This results in an increasing amplitude of the EXAFS function with increasing energy of the X-ray beam resulting in too small Debye-Waller coefficients.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions.

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

軟 X 線透過吸収法：分子間相互作用解析のための化学シフトと測定技術

Recent technical developments of X-ray absorption spectroscopy (XAS) enable us to measure in situ/operando transmission spectra of liquid samples in the soft X-ray region. We have discussed how various inter-molecular interactions around the core-excited atom are analyzed from the chemical shifts in XAS for the chemical state analysis of interacting molecular systems. We have newly developed liquid flow cells for XAS in transmission mode, where liquid samples are sandwiched between two 100 nm thick Si3N4 (or SiC) membranes in vacuum or in helium atmosphere. In order to get reliable XAS spectra, our XAS system makes it possible to optimize the absorbance by simply controlling the liquid sample thickness from 20 nm to 2000 nm, and also makes it possible to find the region of uniform thickness by scanning the beam position on sandwiched liquid samples.

X-Ray absorption spectroscopy of transition metal–magnesium hydride thin films

Mixed metal thin films containing magnesium and a first-row transition element exhibit very large changes in both reflectance and transmittance on exposure to hydrogen gas. Changes in electronic structure and coordination of the magnesium and transition metal atoms during hydrogen absorption were studied using dynamic in situ transmission mode X-ray absorption spectroscopy. Mg K-edge and Ni, Co, and Ti L-edge spectra reflect both reversible and irreversible changes in the metal environments. A significant shift in the nickel L absorption edge shows it to be an active participant in hydride formation. The effect on cobalt and titanium is much less dramatic, suggesting that these metals act primarily as catalysts for formation of magnesium hydride.