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Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

To achieve an ultrahigh resolution of a beamline for soft X-rays at the Taiwan Photon Source (TPS), the profile of a highly precise grating is required at various curvatures. The slope error could be decreased to 0.1 µrad (rms) at a thermal load with a specially designed bender having 25 actuators. In the meantime, a long-trace profiler (LTP) was developed in situ to monitor the grating profile under a thermal load; it consists of a moving optical head, an air-bearing slide, an adjustable stand, and a glass viewport on the vacuum chamber. In the design of this system, a test chamber with an interior mirror was designed to simulate the chamber in the beamline. To prevent an error induced from a commercial viewport, a precision glass viewport (150CF, flatness 1/150 λ rms at 632.8 nm) was designed. The error induced from the slope error of the glass surface and the vacuum deformation was also simulated. The performance of the optical head of the LTP in situ (ISLTP) has been tested in the metrology laboratory. The sources of error of this LTP including the linearity and the glass viewport were corrected after the measurement. For the beamline measurement, an optical head was mounted outside the vacuum chamber; the measuring beam passed through the glass viewport to measure the grating profile in vacuum. The measurement of the LTP after correction of the above errors yielded a precision about 0.2 µrad (rms). In a preliminary test, an ISLTP was used to measure the grating profile at soft X-ray beamline TPS45A. The measured profile was for the bending mechanism to optimize the slope profile. From the measured energy spectrum, the slope error of the grating was estimated with software for optical simulation to be about 0.3 µrad (rms), consistent with our estimate of the ISLTP. In the future, it will be used to monitor the thermal bump under a large thermal load. In addition, an ISLTP was used to monitor the properties of optical elements—the twist and radius in the beamline during the installation phase. [ABSTRACT FROM AUTHOR]

Effects of electronic and atomic structures of V-doped 2D layered SnS 2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS 2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS 2 is ≈4 + but also the charge transfer (CT) from V to ligands, supported by V L α,β resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS 2 . Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS 2 compare to pristine SnS 2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS 2 ., (© 2021 Wiley-VCH GmbH.)

Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO 4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core-shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core-shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p-V 3d hybridization and reduce the crystal field energy 10 Dq ∼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron-hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron-hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core-shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.

This work elucidates the effects of high-temperature annealing on the microscopic and electronic structure of multiwalled carbon nanotubes (MWCNTs) using high-resolution transmission electron microscopy, micro-Raman spectroscopy, X-ray diffraction, X-ray absorption near-edge structure (XANES) and valence-band photoemission spectroscopy (VBPES), respectively. The field emission and magnetization behaviors are also presented. The results of annealing are as follows: (1) MWCNTs tend to align in the form of small fringes along their length, promote graphitization and be stable in air, (2) XANES indicates an enhancement in oxygen content on the sample, implying that it can be adopted for sensing and storing oxygen gas, (3) the electron field emission current density (J) is enhanced and the turn-on electric field (E(TOE)) reduced, suggesting potential use in field emission displays and as electron sources in microwave tube amplifiers and (4) as-grown MWCNTs with embedded iron nanoparticles exhibits significantly higher coercivity approximately 750 Oe than its bulk counterpart (Fe(bulk) approximately 0.9 Oe), suggesting its potential use as low-dimensional high-density magnetic recording media.