Contrast variation method applied to structural evaluation of catalysts by X-ray small-angle scattering.

In the process of developing carbon-supported metal catalysts, determining the catalyst particle-size distribution is an essential step, because this parameter is directly related to the catalytic activities. The particle-size distribution is most effectively determined by small-angle X-ray scattering (SAXS). When metal catalysts are supported by high-performance mesoporous carbon materials, however, their mesopores may lead to erroneous particle-size estimation if the sizes of the catalysts and mesopores are comparable. Here we propose a novel approach to particle-size determination by introducing contrast variation-SAXS (CV-SAXS). In CV-SAXS, a multi-component sample is immersed in an inert solvent with a density equal to that of one of the components, thereby rendering that particular component invisible to X-rays. We used a mixture of tetrabromoethane and dimethyl sulfoxide as a contrast-matching solvent for carbon. As a test sample, we prepared a mixture of a small amount of platinum (Pt) catalyst and a bulk of mesoporous carbon, and subjected it to SAXS measurement in the absence and presence of the solvent. In the absence of the solvent, the estimated Pt particle size was affected by the mesopores, but in the presence of the solvent, the Pt particle size was correctly estimated in spite of the low Pt content. The results demonstrate that the CV-SAXS technique is useful for correctly determining the particle-size distribution for low-Pt-content catalysts, for which demands are increasing to reduce the use of expensive Pt.

Investigating Degradation Mechanisms in PtCo Alloy Catalysts: The Role of Co Content and a Pt-Rich Shell Using Operando High-Energy Resolution Fluorescence Detection X-ray Absorption Spectroscopy.

Low Pt-based alloy catalysts are regarded as an efficient strategy in achieving high activity for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, the desired durability for the low Pt-based catalysts, such as the Pt1Co3 catalyst, has still been considered a great challenge for PEMFCs. In this study, we investigate sub-2.5 nm PtxCoy alloy catalysts with varying Co content and Pt1Co3@Pt core-shell (CS) nanostructure catalysts obtained through a simple displacement reaction. The Pt1Co3@Pt_H catalysts showed a high mass activity (MA) of 1.46 A/mgPt at 0.9 V and 14% MA loss after 10k accelerated degradation test (ADT) cycles, which suggested the improved stability compared with Pt1Co3 catalysts (52% MA loss). To clarify the degradation mechanism, operando high-energy resolution fluorescence detection X-ray absorption spectroscopy (XAS) was applied in addition to conventional advanced measurement techniques, including operando conventional XAS, to analyze the electronic state and structure changes during operation potentials. We found that introducing Co improves the catalysts' activity mainly from the strain effect, but an excessive amount of Co leads to increased Pt-oxidation, which accelerates the degradation of the catalysts. The Pt1Co3@Pt_H catalyst shows high tolerance to Pt-oxidation, benefiting both the stability and activity. Our findings demonstrate an in-depth understanding of the degradation mechanism and the importance of designing PtCo CS nanostructures with optimal Co content for enhanced performance in PEMFCs.

Protection Against Absorption Passivation on Platinum by a Nitrogen-Doped Carbon Shell for Enhanced Oxygen Reduction Reaction.

In polymer electrolyte type fuel cells, the platinum-based catalysts are applied for the oxygen reduction reaction. However, the specific adsorption from the sulfo group in perfluorosulfonic acid ionomers has been considered to passivate the active sites of the platinum. Herein, we present platinum catalysts covered by an ultrathin two-dimensional nitrogen-doped carbon shell (CNx) layer to protect the platinum from the specific adsorption of perfluorosulfonic acid ionomers. Such coated catalysts were obtained by the facile polydopamine coating method, which is available to tune the thickness of the carbon shell by tuning the polymerization time. The coated catalysts that possess a CNx with a thickness of 1.5 nm demonstrated superior ORR activity and comparable oxygen diffusivity when compared to the commercial Pt/C. These results were supported by the changes in the electronic statements observed in the X-ray photoelectron spectroscopy (XPS) and CO stripping analyses. Furthermore, the oxygen coverage, CO displacement charge, and operando X-ray absorption spectroscopy (XAS) tests were employed to identify the protection effect of CNx in coated catalysts compared with the Pt/C catalysts. In summary, the CNx could not only suppress the oxide species generation but also prevent the specific adsorption of the sulfo group in the ionomer.

Direct cross-sectional imaging using X-ray Compton scattering: application to commercial batteries.

A synchrotron-based technique using Compton scattering imaging is presented. This technique has been applied to a coin battery (CR2023), and the cross-sectional image has been obtained in 34 ms without sample rotation. A three-dimensional image of the whole structure has been reconstructed from 74 cross-sectional images taken consecutively by scanning the incident, wide X-ray beam along one direction. This work demonstrates that quick cross-sectional imaging of regions of interest and three-dimensional image reconstruction without sample rotation are feasible using Compton scattering imaging.

Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials.

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials1,2. The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed3, because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects4. Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones.

Fermi surface in La-based cuprate superconductors from Compton scattering imaging.

Compton scattering provides invaluable information on the underlying Fermi surface (FS) and is a powerful tool complementary to angle-resolved photoemission spectroscopy and quantum oscillation measurements. Here we perform high-resolution Compton scattering measurements for La2-xSrxCuO4 with x = 0.08 (Tc = 20 K) at 300 K and 150 K, and image the momentum distribution function in the two-dimensional Brillouin zone. We find that the observed images cannot be reconciled with the conventional hole-like FS believed so far. Instead, our data imply that the FS is strongly deformed by the underlying nematicity in each CuO2 plane, but the bulk FSs recover the fourfold symmetry. We also find an unusually strong temperature dependence of the momentum distribution function, which may originate from the pseudogap formation in the presence of the reconstructed FSs due to the underlying nematicity. Additional measurements for x = 0.15 and 0.30 at 300 K suggest similar FS deformation with weaker nematicity, which nearly vanishes at x = 0.30.

Electron momentum density of hexagonal Zn studied by high-resolution Compton scattering.

High-resolution (0.12 a.u.) electron momentum density projections (Compton profiles) of a hexagonal Zn single crystal have been measured along five high-symmetry directions in reciprocal space. The experiment was performed with the use of 115.6 keV synchrotron radiation on the BL08W station at SPring-8. The quality of the measured Compton profiles is significantly better than that of previous medium- and high-resolution data. The experimental data were compared with the corresponding theoretical Korringa-Kohn-Rostoker (KKR) and density functional theory (DFT) calculations. Some minor and major differences between the two theoretical band-structure calculations have been observed. However, the good quality experimental results indicate their better agreement with DFT.

Compton profile of few-layer graphene investigated by electron energy-loss spectroscopy.

In this paper, acquisition of the valence Compton profile of few-layer graphene using electron energy-loss spectroscopy at large scattering angle is reported. The experimental Compton profile is compared with the corresponding theoretical profile, calculated using the full-potential linearized augmented plane wave method based on the local-density approximation. Good agreement exists between the theoretical calculation and experiment. The graphene profile indicates a substantially greater delocalization of the ground state charge density compared to that of graphite.

Temperature dependence of the hydrogen bond network in trimethylamine N-oxide and guanidine hydrochloride-water solutions.

We present an X-ray Compton scattering study on aqueous trimethylamine N-oxide (TMAO) and guanidine hydrochloride solutions (GdnHCl) as a function of temperature. Independent from the concentration of the solvent, Compton profiles almost resemble results for liquid water as a function of temperature. However, the number of hydrogen bonds per water molecule extracted from the Compton profiles suggests a decrease of hydrogen bonds with rising temperature for all studied samples, and the differences between water and the solutions are weak. Nevertheless, the data indicate a reduced bond weakening with rising TMAO concentration up to 5 M of 7.2% compared to 8% for pure water. In contrast, the addition of GdnHCl appears to behave differently for concentrations up to 3.1 M with a weaker impact on the temperature response of the hydrogen bond structure.

In operando quantitation of Li concentration for a commercial Li-ion rechargeable battery using high-energy X-ray Compton scattering.

Compton scattering is one of the most promising probes for quantitating Li under in operando conditions, since high-energy X-rays, which have high penetration power, are used as the incident beam and the Compton-scattered energy spectrum has specific line-shapes for each element. An in operando quantitation method to determine the Li composition in electrodes has been developed by using line-shape (S-parameter) analysis of the Compton-scattered energy spectrum. In this study, S-parameter analysis has been applied to a commercial coin cell Li-ion rechargeable battery and the variation of the S-parameters during the charge/discharge cycle at the positive and negative electrodes has been obtained. By using calibration curves for Li composition in the electrodes, the change in Li composition of the positive and negative electrodes has been determined using the S-parameters simultaneously.

Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering.

Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delithiation processes is thus of great fundamental and practical interest for understanding the workings of battery materials. We show that inelastic scattering spectroscopy using high-energy x-ray photons (Compton scattering) can yield faithful momentum space images of the redox orbitals by considering lithium iron phosphate (LiFePO4 or LFP) as an exemplar cathode battery material. Our analysis reveals a new link between voltage and the localization of transition metal 3d orbitals and provides insight into the puzzling mechanism of potential shift and how it is connected to the modification of the bond between the transition metal and oxygen atoms. Our study thus opens a novel spectroscopic pathway for improving the performance of battery materials.

A flow cell for measuring X-ray Compton scattering of liquid at temperatures up to 623 K and pressures up to 20 MPa.

A flow-type cell was developed for measuring Compton scattering spectra of heat-sensitive aqueous solution. Compton scattering spectra of water and ethanol were measured in the region from ambient conditions to 623 K and 20 MPa. Compton profiles derived from measurement with the flow-type cell were comparable with those in the literature. Results obtained from the flow-type cell showed that delocalization of electronic charge density of water and ethanol at high temperatures occurred. Delocalization of the electronic charge density of ethanol was greater than that of water at high temperature, which is consistent with the prior works that use proton NMR chemical shifts to describe hydrogen bonding.

Densitometry and temperature measurement of combustion gas by X-ray Compton scattering.

Measurement of combustion gas by high-energy X-ray Compton scattering is reported. The intensity of Compton-scattered X-rays has shown a position dependence across the flame of the combustion gas, allowing us to estimate the temperature distribution of the combustion flame. The energy spectra of Compton-scattered X-rays have revealed a significant difference across the combustion reaction zone, which enables us to detect the combustion reaction. These results demonstrate that high-energy X-ray Compton scattering can be employed as an in situ technique to probe inside a combustion reaction.

A Monte Carlo study of high-energy photon transport in matter: application for multiple scattering investigation in Compton spectroscopy.

The first results of multiple scattering simulations of polarized high-energy X-rays for Compton experiments using a new Monte Carlo program, MUSCAT, are presented. The program is developed to follow the restrictions of real experimental geometries. The new simulation algorithm uses not only well known photon splitting and interaction forcing methods but it is also upgraded with the new propagation separation method and highly vectorized. In this paper, a detailed description of the new simulation algorithm is given. The code is verified by comparison with the previous experimental and simulation results by the ESRF group and new restricted geometry experiments carried out at SPring-8.

Compton scattering imaging of a working battery using synchrotron high-energy X-rays.

Results of studies on Compton scattering imaging using synchrotron high-energy X-rays are reported. The technique is applied to a discharging coin cell, and the intensity of Compton scattered X-rays from the inside of the cell has been measured as a function of position and time. The position-time intensity map captures the migration of lithium ions in the positive electrode and reveals the structural change due to the volume expansion of the electrode. This experiment is a critical step in developing synchrotron-based Compton scattering imaging for electrochemical cells at a product level.

Understanding spin structure in metallacrown single-molecule magnets using magnetic compton scattering.

The 3d-4f mixed metallacrowns frequently show single-molecule magnetic behavior. We have used magnetic Compton scattering to characterize the spin structure and orbital interactions in three isostructural metallacrowns: Gd2Mn4, Dy2Mn4, and Y2Mn4. These data allow the direct determination of the spin only contribution to the overall magnetic moment. We find that the lanthanide 4f spin in Gd2Mn4 and Dy2Mn4 is aligned parallel to the Mn 3d spin. For Y2Mn4 (manganese-only spin) we find evidence for spin delocalization into the O 2p orbitals. Comparing the magnetic Compton scattering data with SQUID studies that measure the total magnetic moment suggests that Gd2Mn4 and Y2Mn4 have only a small orbital contribution to the moment. In contrast, the total magnetic moment for Dy2Mn4 MCs is much larger than the spin-only moment, demonstrating a significant orbital contribution to the overall magnetic moment. Overall, these data provide direct insight into the correlation of molecular design with molecular magnetic properties.

A planar parabolic refractive nickel lens for high-energy X-rays.

A compound refractive lens made of nickel and designed for focusing high-energy synchrotron X-rays is presented. The lens consists of 600 parabolic grooves and focuses X-rays in one plane only (planar lens). The lenses made and investigated by us earlier exhibited low transmission and irregularities in the focused beam profile. Since then, improvements in lens manufacturing technology have been made. The present lens gives an almost Gaussian profile and produces four times higher intensity at its maximum compared with the intensity of primary X-ray beams of 174 keV.

Estimating the burden of acute gastroenteritis and foodborne illness caused by Campylobacter, Salmonella, and Vibrio parahaemolyticus by using population-based telephone survey data, Miyagi Prefecture, Japan, 2005 to 2006.

Most cases of acute gastroenteritis and foodborne disease are not ascertained by public health surveillance because the ill person does not always seek medical care and submit a stool sample for testing, and the laboratory does not always test for or identify the causative organism. We estimated the total burden of acute gastroenteritis in Miyagi Prefecture, Japan, using data from two 2-week cross-sectional, population-based telephone surveys conducted in 2006 and 2007. To estimate the number of acute gastroenteritis illnesses caused by Campylobacter, Salmonella, and Vibrio parahaemolyticus in Miyagi Prefecture, we determined the number of cases for each pathogen from active laboratory-based surveillance during 2005 to 2006 and adjusted for seeking of medical care and submission of stool specimens by using data from the population-based telephone surveys. Monte Carlo simulation was used to incorporate uncertainty. The prevalence of acute gastroenteritis in the preceding 4 weeks was 3.3% (70 of 2,126) and 3.5% (74 of 2,121) in the winter and summer months, yielding an estimated 44,200 episodes of acute gastroenteritis each year in this region. Among people with acute gastroenteritis, the physician consultation rate was 32.0%, and 10.9% of persons who sought care submitted a stool sample. The estimated numbers of Campylobacter-, Salmonella-, and V. parahaemolyticus -associated episodes of acute gastroenteritis were 1,512, 209, and 100 per 100,000 population per year, respectively, in this region. These estimates are significantly higher than the number of reported cases in surveillance in this region. Cases ascertained from active surveillance were also underrepresented in the present passive surveillance, suggesting that complementary surveillance systems, such as laboratory-based active surveillance in sentinel sites, are needed to monitor food safety in Japan.

Evidence of instantaneous electron correlation from Compton profiles of crystalline silicon.

The combination of new experimental and theoretical techniques provides evidence of instantaneous electron correlation effects in directional Compton profiles of crystalline silicon, which cannot be reproduced when reference is made to a density matrix obtained from a single-determinantal wavefunction. These effects are instead accounted for by a recently implemented post-Hartree-Fock periodic scheme, which gives results in quite good agreement with the high-quality experimental data.

The role of single element errors in planar parabolic compound refractive lenses.

The propagation of X-rays through a compound refractive lens (CRL) with imperfect CRL elements is investigated. The trajectories of random rays within the geometrical optics regime are calculated in one plane using Monte Carlo methods. Three different lenses were simulated: Be, Al and Ni lenses designed for photon energies of 20 keV, 60 keV and 175 keV, respectively. The results show that while transverse displacements of single elements in a CRL do not influence imaging resolution, rotational errors can be important. Systematic calculations of aberrations owing to the deviation of the element's surface from a perfect parabolic shape are also presented.