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Two highly active and stable Pd-based intermetallic nanocrystals with early d-metals Pd3Ti and Pd3Zr have been developed. The nanocrystals are synthesized by co-reduction of the respective salts of Pd and Ti/Zr. Hard X-ray photoemission Spectroscopy (HAXPES) analysis of the nanocrystals indicates that the electronic properties of Pd are modified significantly, as evident from the lowering of the d-band center of Pd. The intermetallic nanocrystals dispersed in Vulcan carbon, Pd3Ti/C and Pd3Zr/C, exhibit improved electrocatalytic activity towards methanol and ethanol oxidation in an alkaline medium (0.5 M KOH), compared to those of commercially available catalysts such as Pd/C, Pt/C, and Pt3Sn/C. In addition, Pd3Ti/C and Pd3Zr/C show significantly higher activity towards the oxidation of formic acid in an acidic medium (0.5 M H2SO4), compared to those of Pd/C and Pt/C. The modification of the d-band center of Pd as a result of the alloying of Pd with the early d-metals Ti and Zr may be responsible for the enhanced catalytic activity. [ABSTRACT FROM AUTHOR]

We report the effect of the synthesis route of starch-functionalized magnetite nanoparticles (NPs) on their adsorption properties of As(V) and As(III) from aqueous solutions. NP synthesis was achieved by two different routes implying the alkaline precipitation of either a mixed Fe2+/Fe3+ salt solution (MC samples) or a Fe2+ salt solution in oxidative conditions (MOP samples). Syntheses were carried out with starch to Fe mass ratio (R) ranging from 0 to 10. The crystallites of starch-free MC NPs (14 nm) are smaller than the corresponding MOP (67 nm), which leads to higher As(V) sorption capacity of 0.3 mmol gFe−1 to compare with respect to 0.1 mmol gFe−1 for MOP at pH = 6. MC and MOP starch-functionalized NPs exhibit higher sorption capacities than a pristine one and the difference in sorption capacities between MOP and MC samples decreases with increasing R values. Functionalization tends to reduce the size of the magnetite crystallites and to prevent their agglomeration. Size reduction is more pronounced for MOP samples (67 nm (R0) to 12 nm (R10)) than for MC samples (14 nm (R0) to 9 nm (R10)). Therefore, due to close crystallite size, both MC and MOP samples, when prepared at R = 10, display similar As(V) (respectively, As(III)) sorption capacities close to 1.3 mmol gFe−1 (respectively, 1.0 mmol gFe−1). Additionally, according to the effect of pH on arsenic trapping, the electrostatic interactions appear as a major factor controlling As(V) adsorption while surface complexation may control As(III) adsorption. [ABSTRACT FROM AUTHOR]

We develop an automatic peak fitting algorithm using the Bayesian information criterion (BIC) fitting method with confidence-interval estimation in spectral decomposition. First, spectral decomposition is carried out by adopting the Bayesian exchange Monte Carlo method for various artificial spectral data, and the confidence interval of fitting parameters is evaluated. From the results, an approximated model formula that expresses the confidence interval of parameters and the relationship between the peak-to-peak distance and the signal-to-noise ratio is derived. Next, for real spectral data, we compare the confidence interval of each peak parameter obtained using the Bayesian exchange Monte Carlo method with the confidence interval obtained from the BIC-fitting with the model selection function and the proposed approximated formula. We thus confirm that the parameter confidence intervals obtained using the two methods agree well. It is therefore possible to not only simply estimate the appropriate number of peaks by BIC-fitting but also obtain the confidence interval of fitting parameters. [ABSTRACT FROM AUTHOR]

We have developed hard X-ray photoelectron spectroscopy (HAXPES) under an applied magnetic field of 1 kOe to study the electronic and magnetic states related to the MgO/Fe interface-induced perpendicular magnetic anisotropy (PMA). In this work, we used MgO (2 nm)/Fe (1.5 and 20 nm)/MgO(001) structures to reveal the interface-induced electronic states of the Fe film. Perpendicular magnetization of the 1.5-nm-thick Fe film without extrinsic oxidation of the Fe film was detected by the Fe 2p core-level magnetic circular dichroism (MCD) in HAXPES under a magnetic field, and easy magnetization axis perpendicular to the film plane was confirmed by ex situ magnetic hysteresis measurements. The valence-band HAXPES spectrum of the 1.5-nm-thick Fe film revealed that the Fe 3d electronic states were strongly modified from the thick Fe film and a reference bulk Fe sample due to the lifting of degeneracy in the Fe 3d states near the MgO/Fe interface. We found that the tetragonal distortion of the Fe film by the MgO substrate also contributes to the lifting of degeneracy in the Fe 3d states and PMA, as well as the Fe 3d-O 2p hybridization at the MgO/Fe interface, by comparing the valence-band spectrum with density functional theory calculations for MgO/Fe multilayer structures. Thus, we can conclude that the Fe 3d-O 2p hybridization and tetragonal distortion of the Fe film play important roles in PMA at the MgO/Fe interface. HAXPES with in situ magnetization thus represents a powerful new method for studying spintronic structures. [ABSTRACT FROM AUTHOR]

We introduce a spectrum-adapted expectation-maximization (EM) algorithm for high-throughput analysis of a large number of spectral datasets by considering the weight of the intensity corresponding to the measurement energy steps. Proposed method was applied to synthetic data in order to evaluate the performance of the analysis accuracy and calculation time. Moreover, the proposed method was performed to the spectral data collected from graphene and MoS2 field-effect transistors devices. The calculation completed in less than 13.4 s per set and successfully detected systematic peak shifts of the C 1s in graphene and S 2p in MoS2 peaks. This result suggests that the proposed method can support the investigation of peak shift with two advantages: (1) a large amount of data can be processed at high speed; and (2) stable and automatic calculation can be easily performed. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles were synthesized by laser pyrolysis, their surface and electronic properties were modified by gold and/or nitrogen. These materials were characterized by different techniques like X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Time resolved conductivity (TRMC) was used to study the charge separation of electron/hole pairs. Altogether (XPS, EPR, TRMC), the physicochemical characterizations are well correlated with chemical photoactivity of the different samples. Their photocatalytic activity was evaluated for the degradation of linear carboxylic acids (C2-C3) under UV and visible illumination. The decomposition rate of acids was measured, it shows that the modification with gold increases the photoactivity while the presence of nitrogen slows down the process. Such observations are in good agreement with evolution of TRMC signals. A degradation pathway has been determined by identification of intermediate products by chromatography and EPR, results show different intermediate species. In particular EPR confirms the presence of NO2−paramagnetic centers and shows two novel N centered paramagnetic centers. A decrease of the degradation rate is observed with increase of carboxylic acid chain length. [ABSTRACT FROM AUTHOR]

We report the photoluminescence (PL) and cathodoluminescence (CL) properties of face-capped [Mo6Xi8La6]2−(X = Cl, Br, I; L = organic or inorganic ligands) cluster units. We show that the emission of Mo6metal atom clusters depends not only on the nature of X and L ligands bound to the cluster and counter-cations, but also on the excitation source. Seven members of the AxMo6Xi8La6series (A = Cs+, (n-C4H9)4N+, NH4+) were selected to evaluate the influence of counter-cations and ligands on de-excitation mechanisms responsible for multicomponent emission of cluster units. This study evaluates the ageing of each member of the series, which is crucial for further energy conversion applications (photovoltaic, lighting, water splitting, etc.). [ABSTRACT FROM AUTHOR]

Controlling the chemistry on the surface of new carbon materials is a key factor to widen the range of their applicability. In this paper we show a grafting methodology of polyalkylamines to the surface of carbon nanomaterials, in particular, carbon nanotubes and a carbon black. The aim of this work is to reach large degrees of covalent functionalization with hyperbranched polyethyleneimines (HBPEIs) and to efficiently preserve the strong chelating properties of the HBPEIs when they are fixed to the surface of these carbon materials. This functionalization opens new possibilities of using these carbon nanotubes-based hybrids. The results show that the HBPEIs are covalently attached to the carbon materials, forming hybrids. These hybrids emerge from the reaction of amine functions of the HBPEIs with carbonyls and carboxylic anhydrides of the carbon surface which become imine and imide bonds. Thus, due to the nature of these bonds, the pre-oxidized samples with relevant number of C=O groups showed an increase in the degree of functionalization with the HBPEIs. Furthermore, both the acid-base properties and the coordination capacity for metal ions of the hybrids are equivalent to that of the free HBPEIs in solution. This means that the chemical characteristics of the HBPEIs have been efficiently transferred to the hybrids. To reach this conclusion we have developed a novel procedure to assess the acid-base and the coordination properties of the hybrids (solids) by means of potentiometric titration. The good agreement of the values obtained for the hybrids and for the free HBPEIs in aqueous solution supports the reliability of the procedure. Moreover, the high capacity of the hybrids to capture Ni2+by complexation opens new possibilities of using these hybrids to capture high-value metal ions such as Pd2+and Pt2+. Hyperbranched polyethylenimines are covalently fixed to the surface of carbon materials, so the chemical characteristics of the amines are transferred to the hybrid materials. [ABSTRACT FROM AUTHOR]

The extracellular ionic microenvironment has a close relationship to biological activities such as by cellular respiration, cancer development, and immune response. A system composed of ion-sensitive field-effect transistors (ISFET), cells, and program-controlled fluidics has enabled the acquisition of real-time information about the integrity of the cell membrane via pH measurement. Here we aimed to extend this system toward floating cells such as T lymphocytes for investigating complement activation and pharmacokinetics through alternations in the plasma membrane integrity. We functionalized the surface of tantalum oxide gate insulator of ISFET with oleyl-tethered phosphonic acid for interacting with the plasma membranes of floating cells without affecting the cell signaling. The surface modification was characterized by X-ray photoelectron spectroscopy and water contact angle measurements. The Nernst response of −37.8 mV/pH was obtained for the surface-modified ISFET at 37 °C. The oleyl group-functionalized gate insulator successfully captured Jurkat T cells in a fluidic condition without acute cytotoxicity. The system was able to record the time course of pH changes at the cells/ISFET interface during the process of instant addition and withdrawal of ammonium chloride. Further, the plasma membrane injury of floating cells after exposure by detergent Triton™ X-100 was successfully determined using the modified ISFET with enhanced sensitivity as compared with conventional hemolysis assays. [ABSTRACT FROM PUBLISHER]

Abstract Charging effect frequently occurs when characterizing nonconductive materials using electrons as probes and/or signals and can impede the acquisition of useful information about the material under investigation. It is not adequate to investigate it merely by experiments, but theoretical investigations, for which the Monte Carlo method is a suitable tool, are also necessary. In this paper we review Monte Carlo simulations and selected experiments, intending to provide general insight into the charging effects induced by electron beam irradiation. We will introduce categories of the charging effect, the theoretical framework that is adopted in Monte Carlo modeling of the charging effect and present some typical simulation results. At last, with the knowledge on charging effect imparted by the above contents, we will discuss the measures that can be used for minimizing it. [ABSTRACT FROM AUTHOR]

We report spin-resolved hard X-ray photoelectron spectroscopy (spin-HAXPES) for a buried Fe thin film in the valence band region. For the spin-HAXPES experiments, we developed an ultracompact built-in Mott-type spin-filter in a sample carrier, which enabled us to use the merit of two-dimensional (2D) multi-channel detector in a recent photoelectron analyser without modifying an apparatus for HAXPES. The effective Sherman function and the single-channel figure of merit (FOM) of the spin-filter were assessed to be -0.07 and 2.0 × 10 -4 , respectively. By utilizing the 2D detector of the photoelectron analyser, the effective FOM increased by a factor of ~4 × 10 4 compared to the case when only 1 channel of the 2D detector was used. We have applied spin-HAXPES to MgO(2 nm)/Fe(50 nm)/MgO(001) structures. The spin-HAXPES experiments revealed the majority and minority spin electronic states and the spin polarisation of the buried Fe thin film. Due to the large photoionization cross-section of the 4 s orbital of Fe in HAXPES, the spin-resolved spectra mainly reflected the Fe 3 d and 4 s states. The observed spin-HAXPES and spin polarisation spectral shapes agreed well with the calculated spin-resolved cross-section weighted densities of states and spin polarisation spectra. In contrast, a small discrepancy in the energy scale was recognised due to the electron correlation effects. These results suggest that the electron correlation effects are important in the electronic structure of bulk Fe, and spin-HAXPES is useful for detecting genuine spin-resolved valence band electronic structures of buried magnetic materials., Competing Interests: No potential conflict of interest was reported by the author(s)., (© 2021 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

In the present paper we discuss correlations between crystal structure and magnetic properties of epitaxial ε-Fe 2 O 3 films grown on GaN. The large magnetocrystalline anisotropy and room temperature multiferroic properties of this exotic iron oxide polymorph, make it a perspective material for the development of low power consumption magnetic media storage devices. Extending our recent progress in PLD growth of ε-Fe 2 O 3 on the surface of technologically important nitride semiconductors, we apply reciprocal space tomography by electron and x-ray diffraction to investigate the break of crystallographic symmetry occurring at the oxide-nitride interface resulting in the appearance of anisotropic crystallographic disorder in the sub-100 nm ε-Fe 2 O 3 films. The orthorhombic-on-hexagonal nucleation scenario is shown responsible for the development of a peculiar columnar structure observed in ε-Fe 2 O 3 by means of HRTEM and AFM. The complementary information on the direct and reciprocal space structure of the columnar ε-Fe 2 O 3 films is obtained by various techniques and correlated to their magnetic properties. The peculiar temperature dependence of magnetization studied by the small-field magnetization derivative method and by neutron diffraction reveals the existence of a magnetic softening below 150 K, similar to the one observed earlier solely in nanoparticles. The magnetization reversal in ε-Fe 2 O 3 films probed by X-ray magnetic circular dichroism is found different from the behavior of the bulk averaged magnetization measured by conventional magnetometry. The presented results fill the gap between the numerous studies performed on randomly oriented ε-Fe 2 O 3 nanoparticles and much less frequent investigations of epitaxial epsilon ferrite films with lattice orientation fixed by the substrate., Competing Interests: The authors declare no conflict of interest., (© 2021 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

Two highly active and stable Pd-based intermetallic nanocrystals with early d-metals Pd 3 Ti and Pd 3 Zr have been developed. The nanocrystals are synthesized by co-reduction of the respective salts of Pd and Ti/Zr. Hard X-ray photoemission Spectroscopy (HAXPES) analysis of the nanocrystals indicates that the electronic properties of Pd are modified significantly, as evident from the lowering of the d-band center of Pd. The intermetallic nanocrystals dispersed in Vulcan carbon, Pd 3 Ti/C and Pd 3 Zr/C, exhibit improved electrocatalytic activity towards methanol and ethanol oxidation in an alkaline medium (0.5 M KOH), compared to those of commercially available catalysts such as Pd/C, Pt/C, and Pt 3 Sn/C. In addition, Pd 3 Ti/C and Pd 3 Zr/C show significantly higher activity towards the oxidation of formic acid in an acidic medium (0.5 M H 2 SO 4 ), compared to those of Pd/C and Pt/C. The modification of the d-band center of Pd as a result of the alloying of Pd with the early d-metals Ti and Zr may be responsible for the enhanced catalytic activity., Competing Interests: No potential conflict of interest was reported by the authors., (© 2020 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

Charge trap in amorphous perfluoro-polymer electret is studied, focusing on electron trap site and trap energy. Low-energy inverse photoelectron spectroscopy is adopted to measure solid-state electron affinity (EA) of cyclic transparent optical polymer (CYTOP). EA of CYTOP CTL-S is discovered by compensating the unwanted charge-up effect. Negatively-charged electret materials (polyethylene, ethylene-tetra-fluoro-ethylene, poly-tetra-fluoro-ethylene, and CYTOP) are analyzed by quantum mechanical calculation. Density functional theory with long-range correction is adopted to analyze orbital energies of single molecular systems. Intramolecular distribution of trapped electron and EA are investigated. Calculated electron affinities of CYTOP polymers with different end group are qualitatively in accordance with trapped charge stability measured with thermal stimulated discharge, signifying that electron affinities obtained with the present simulation can be used as an index of amorphous polymer electret.

Photovoltaic generation has stepped up within the last decade from outsider status to one of the important contributors of the ongoing energy transition, with about 1.7% of world electricity provided by solar cells. Progress in materials and production processes has played an important part in this development. Yet, there are many challenges before photovoltaics could provide clean, abundant, and cheap energy. Here, we review this research direction, with a focus on the results obtained within a Japan-French cooperation program, NextPV, working on promising solar cell technologies. The cooperation was focused on efficient photovoltaic devices, such as multijunction, ultrathin, intermediate band, and hot-carrier solar cells, and on printable solar cell materials such as colloidal quantum dots.

Alloy nanoparticles (NPs) can offer a wide range of opportunities for various applications due to their composition and structure dependent properties such as multifunctionality, electronic heterogeneity, site-specific response, and multiple plasmon resonance bands. In this work, the fabrication of self-assembled Pd x Ag 1-x NPs alloy nanostructures with distinct size, density, shape, and composition is demonstrated via the solid-state dewetting of sputtered Pd/Ag thin films on c-plane sapphire. The initial stage of bilayer dewetting exhibits the nucleation of voids, followed by the expansion of voids and cluster breakdown and finally shape transformation along with the temperature control. Bilayer composition shows a substantial influence on the dewetting such that the overall dewetting is enhanced along with the increased Ag composition, i.e. Pd 0.25 Ag 0.75  > Pd 0.5 Ag 0.5  > Pd 0.75 Ag 0.25 . On the other hand, the size and density of NPs can be efficiently controlled by varying the initial thickness of bilayers. Reflectance peaks in UV and near-infrared (NIR) regions and a wide absorption band in the visible region arisen from the surface plasmon resonance are observed in reflectance spectra. The peak intensity depends on the composition of Pd x Ag 1-x NPs and the NIR peaks gradually blue-shift with the size decrement.