Several studies report on the use of hematite-based nanorods (alpha-Fe2O3) for solar water splitting (SWS) applications, following various synthesis pathways with strong dispersion of the resulting photoelectrochemical (PEC) performances. Herein, we investigate the origin of strong PEC response variability in a set of Ti-doped alpha-Fe2O3 samples synthesized following, a priori, strictly the same conditions. Our findings reveal that alteration of Ti oxidation state in the TiCl3 precursor, induced most probably by aging, leads to a strong reduction of Fe3+ in the final Ti:alpha-Fe2O3 photoanode by a charge compensation process. While this adversely impacts PEC efficiency by altering the electronic structure, there are no detectable changes in the crystalline structure. Subtle chemical changes at the nanoscale were thus studied using a combination of transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM) and are demonstrated to be driving water splitting efficiency. The obtained results highlight the importance of a very detailed photoanode characterization, both structural and chemical, allowing us to understand and optimize their PEC activity.

Na-ion batteries have emerged as viable candidates for large-scale energy storage applica- tions due to resource abundance and cost advantages. The constraints imposed on their performance and durability, for instance, by complex phase transformations in positive electrode materials during electrochemical cycling, can be addressed and are thus not detrimental to their development. However, diffusion-limited Na-ion transport can drive spatially heterogeneous phase nucleation and propagation, leading to multiphase coexis- tence and locally non-uniform electrochemical activity, generating complex reaction path- ways that challenge both mechanistic understanding and predictive material optimization. These challenges can be addressed by investigating single-crystalline regions of materials, i.e. down to the scale of individual particles, although such analyses are often constrained by energetically and/or spatially sparse hyperspectral datasets. Here, we developed an AI-driven method to process hyperspectral data under sparse sampling conditions and generate multiphase maps with nanometer-scale resolution over a micrometer-scale field of view. We applied this processing on scanning transmission X-ray microscopy (STXM) data to determine the distribution and coexistence of phases in individual particles of NaxV2(PO4)2F3 cathode materials, at different states of charge. The methodology relies on a workflow which combines a Gaussian mixture variational autoencoder (GMVAE) algorithm with the Pearson corre- lation coefficient to identify the sodium content and map their spatial distribution. Our approach reveals nanoscale phase heterogeneity and evolution within individual particles, and improves the reliability of phase detection by identifying ambiguity zones, false assign- ments, and transition phases localized at grain boundaries.

Polarized x-rays allow for imaging birefringent or dichroic properties of materials with nanometric resolution. To disentangle these properties from the electronic density, either a polarization analyzer or several measurements with different polarizations (typically two or more) are needed. Here we demonstrate that ptychography can disentangle these from a single polarization measurement by using a multimodal analysis. This new method provides an alternative to obtain polarization-resolved images of a sample when manipulating the incident polarization is not possible or sufficient.

Magnetic skyrmions are chiral spin textures with rich physics and great potential for unconventional computing. Typically, skyrmions form in bulk crystals with reduced symmetry or ultrathin film multilayers involving heavy metals. Here, the formation of fractional Bloch skyrmion tubes at room temperature is demonstrated by 3D printing ferromagnetic double‐helix nanowires with two regions of opposite chirality. Using X‐ray microscopy and micromagnetic simulations, it is shown that the coexistence of vortex and anti‐parallel spin states induces the formation of fractional skyrmion tubes at zero magnetic fields, minimizing the energy cost of breaking the coupling between geometric and magnetic chirality. Control over zero‐field states is also demonstrated, including pure vortex, or mixed skyrmion‐vortex states, highlighting the magnetic reconfigurability of these 3D nanowires. This work shows how interfacing chiral geometries at the nanoscale can enable advanced forms of topological spintronics.

Magnetic skyrmions are chiral spin textures with rich physics and great potential for unconventional computing. Typically, skyrmions form in bulk crystals with reduced symmetry or ultrathin film multilayers involving heavy metals. Here, we demonstrate the formation of fractional Bloch skyrmion tubes at room temperature by 3D printing ferromagnetic double-helix nanowires with two regions of opposite chirality. Using X-ray microscopy and micromagnetic simulations, we show that the coexistence of vortex and anti-parallel spin states induces the formation of fractional skyrmion tubes at zero magnetic fields, minimising the energy cost of breaking the coupling between geometric and magnetic chirality. We also demonstrate control over zero-field states, including pure vortex, or mixed skyrmion-vortex states, highlighting the magnetic reconfigurability of these 3D nanowires. This work shows how interfacing chiral geometries at the nanoscale can enable advanced forms of topological spintronics.

Over the past decade advances in instrumentation and software have enabled development of spectro-ptychography (SP) as a higher spatial resolution extension of scanning transmission X-ray microscopy (STXM). Direct comparisons are made of same-area chemical state imaging of Cu nanoparticles using STXM and SP in order to compare and contrast the two approaches. We show that SP gives very similar chemical state information as STXM with significantly better spatial resolution and much higher quality images and chemical maps, on account of finer pixels in the reconstructed images. When defocused spot sizes are used (i.e., 1-3 mu m, as opposed to full-focus 30-50 nm) SP data acquisition is faster and the radiation dose delivered to the sample is smaller than the corresponding STXM measurement. The limitations of SP are primarily related to the time and complexity of the ptychographic reconstruction. We argue that these documented advantages mean that SP rather than STXM should be used for more complex studies such as tomography and in situ studies, especially when radiation damage is a concern. The main point of this manuscript is to illustrate, with scientifically relevant samples, the significant advantages of SP relative to conventional STXM, with the goal of encouraging greater use of SP.

We report a scanning transmission X-ray microscopy (STXM) study of hematite nanorods, prototypical photoanode used in solar water splitting. Hematite nanorods were obtained by hydrothermal growth from aqueous solutions using FeCl3 as precursor. Potentials for onset of water splitting are smaller using this synthesis method, compared to values reported for hematite photoanodes obtained by epitaxial growth. STXM revealed the presence of a hexahydrate iron chloride phase at the surface of the nanorods, which is linked to the low onset potential values. We detail the quantification approach that revealed the specific microstructure of individual hematite nanorods.

Band engineering is employed thoroughly and targets technologicallyscalable photoanodes for solar water splitting applications. Complexand costly recipes are necessary, often for average performances.Here, we report simple photoanode growth and thermal annealing witheffective band engineering results. By comparing Ti-doped hematitephotoanodes annealed under nitrogen to photoanodes annealed in air,we found a strongly enhanced photocurrent of more than 200% in thefirst case. Using electrochemical impedance spectroscopy and synchrotronX-ray spectromicroscopy, we demonstrate that oxidized surface statesand increased density of charge carriers are responsible for the enhancedphotoelectrochemical (PEC) activity. Surface states are found to berelated to the formation of pseudo-brookite clusters by surface Tisegregation. Spectro-ptychography is used for the first time at theTi L-3 absorption edge to isolate Ti chemical coordinationarising from pseudo-brookite cluster contribution. Correlated withelectron microscopy investigation and density functional theory calculations,the synchrotron spectromicroscopy data unambiguously prove the originof enhanced PEC activity of N-2-annealed Ti-doped hematitenanorods. Finally, we present here a handy and cheap surface engineeringmethod beyond the known oxygen vacancy doping, allowing a net gainin the PEC activity for the hematite-based photoanodes.

A micro-chip based three-electrode electrochemical reactor enabling controlled, variable electrolyte flow, rapid electrolyte change and applied electrode potentials was used for in-situ soft X-ray spectro-ptychography of Cu particle catalysts under electrochemical CO2 reduction (CO2R) conditions. In comparison to scanning transmission X-ray microscopy (STXM), the spatial resolution was improved by a factor of three through measuring patterns of diffracted photons via spectro-ptychography. We present here a detailed study of how individual cubic Cu particles change morphology and oxidation state as a function of applied potential during CO2R. Quantitative chemical mapping by in-situ spectro-ptychography demonstrated that as-deposited, primarily mixed Cu(I) and Cu(0) particles were completely reduced to pure Cu(0) at an electrode potential of -0.2 VRHE, above the potential at which CO2R commences. At increasingly negative potentials, in the regime of CO2R, these Cu(0) particles underwent morphological changes, losing the initial cubic structure and forming irregular dendritic-like structures. This initial demonstration of in-situ soft X-ray spectro-ptychography sheds insight on the morphological and chemical structural changes of Cu particles in the CO2R regime and paves the way for more detailed in-situ studies of electrochemical materials and processes.

Spectro-ptychography offers improved spatial resolution and additional phase spectral information relative to that provided by scanning transmission X-ray microscopes. However, carrying out ptychography at the lower range of soft X-ray energies (e.g. below 200 eV to 600 eV) on samples with weakly scattering signals can be challenging. Here, results of soft X-ray spectro-ptychography at energies as low as 180 eV are presented, and its capabilities are illustrated with results from permalloy nanorods (Fe 2p), carbon nanotubes (C 1s) and boron nitride bamboo nanostructures (B 1s, N 1s). The optimization of low-energy X-ray spectro-ptychography is described and important challenges associated with measurement approaches, reconstruction algorithms and their effects on the reconstructed images are discussed. A method for evaluating the increase in radiation dose when using overlapping sampling is presented.

Chemical Looping Combustion is a promising midterm solution to mitigate CO2 emission, by carrying out indirect fuel combustion and allowing inherent separation of CO2. During the CLC process, an oxygen carrying material is subjected to successive oxidation‐reduction reactions at high temperature which induce significant material degradation. CuO/Al2O3 based materials have been widely considered as promising oxygen carriers (OC). However, the oxygen carrier ageing mechanisms (active phase migration and interactions with the support, phase transitions) are not well understood. Herein, an in‐depth overview of the material evolution is achieved by employing a multi‐scale characterization approach. At the μm‐scale, copper migration within the alumina support has been observed using Scanning Transmission X‐ray Microscopy (STXM) and Scanning Electron Microscopy (SEM). The spatial distribution of the Cu−Al species provides information on copper mobility and the different phases interactions. A comprehensive mechanism is proposed concerning the redox behaviour of the CuO/Al2O3 system, relating the diffusion of the Cu‐species, the active phase‐support interactions, and the role of copper in the Al2O3 support phase transition to the temperature and the number of redox cycles. Understanding the ageing process of CuO/Al2O3 materials paves a way to design more stable oxygen‐carriers.

Ptychography is a coherent diffraction imaging technique that measures diffraction patterns at many overlapping points on a sample and then uses an algorithm to reconstruct amplitude and phase images of the object and probe. Here, we report imaging, spectroscopy and linear dichroism ptychographic measurements at the carbon K-edge. This progress was achieved with a new generation of scientific Complementary Metal Oxide Semiconductor (sCMOS) X-ray cameras with an uncoated image sensor which has fast image transfer and high quantum efficiency at the carbon K-edge. Reconstructed amplitude and phase contrast images, C 1s spectral stacks, and X-ray linear dichroism of carbon nanotubes at the carbon K-edge were measured with ptychography. Ptychography and conventional Scanning Transmission X-ray Microscopy (STXM) are compared using results acquired from the same area. Relative to STXM, ptychography provides both improved spatial resolution and improved image quality. We used defocus ptychography, with an X-ray beam spot size of 1.0 micron, in order to reduce radiation damage and carbon deposition. Comparable spatial resolution was achieved to that of ptychography performed with a focused beam. Ptychography at the carbon K-edge offers unique opportunities to perform high resolution spectromicroscopy on organic materials important in medicine, biology, environmental science and energy materials.

X-ray absorption and optical luminescence can both provide valuable but very different information on the chemical and physical properties of materials. Although it is known that the spectral characteristics of many materials are highly heterogeneous on the micro- and/or nanoscale, no methodology has so far been shown to be capable of spatially resolving both full X-ray absorption and X-ray excited optical luminescence (XEOL) spectra on the nanoscale in a correlative manner. For this purpose, the scanning transmission X-ray microscope at the HERMES beamline of the SOLEIL synchrotron was equipped with an optical detection system capable of recording high-resolution XEOL spectra using a 40 nm soft X-ray probe. The functionality of the system was demonstrated by analyzing ZnO powder dispersions - showing simultaneously the X-ray linear dichroism and XEOL behavior of individual submicrometric ZnO crystallites.

X-ray linear dichroism (XLD) is a fundamental property of many ordered materials that can for instance provide information on the origin of magnetic properties and the existence of differently ordered domains. Conventionally, measurements of XLD are performed on single crystals, crystalline thin films, or highly ordered nanostructure arrays. Here, it is demonstrated how quantitative measurements of XLD can be performed on powders, relying on the random orientation of many particles instead of the controlled orientation of a single ordered structure. The technique is based on a scanning X-ray transmission microscope operated in the soft X-ray regime. The use of a Fresnel zone plate allows X-ray absorption features to be probed at ∼40 nm lateral resolution – a scale small enough to probe the individual crystallites in most powders. Quantitative XLD parameters were then retrieved by determining the intensity distributions of certain diagnostic dichroic absorption features, estimating the angle between their transition dipole moments, and fitting the distributions with four-parameter dichroic models. Analysis of several differently produced ZnO powders shows that the experimentally obtained distributions indeed follow the theoretical model for XLD. Making use of Monte Carlo simulations to estimate uncertainties in the calculated dichroic model parameters, it was established that longer X-ray exposure times lead to a decrease in the amplitude of the XLD effect of ZnO.

We present and fully characterize a flow cell dedicated to imaging in liquid at the nanoscale. Its use as a routine sample environment for soft X-ray spectromicroscopy is demonstrated, in particular through the spectral analysis of inorganic particles in water. The care taken in delineating the fluidic pathways and the precision associated with pressure actuation ensure the efficiency of fluid renewal under the beam, which in turn guarantees a successful utilization of this microfluidic tool for in situ kinetic studies. The assembly of the described flow cell necessitates no sophisticated microfabrication and can be easily implemented in any laboratory. Furthermore, the design principles we relied on are transposable to all microscopies involving strongly absorbed radiation (e.g. X-ray, electron), as well as to all kinds of X-ray diffraction/scattering techniques.

The availability of intense soft x-ray beams with tunable energy and polarization has pushed the development of highly sensitive, element-specific, and noninvasive microscopy techniques to investigate condensed matter with high spatial and temporal resolution. The short wavelengths of soft x-rays promise to reach spatial resolutions in the deep single-digit nanometer regime, providing unprecedented access to magnetic phenomena at fundamental length scales. Despite considerable efforts in soft x-ray microscopy techniques, a two-dimensional resolution of 10 nm has not yet been surpassed in direct imaging. Here, we report on a significant step beyond this long-standing limit by combining newly developed soft x-ray Fresnel zone plate lenses with advanced precision in scanning control and careful optical design. With this approach, we achieve an image resolution of 7 nm. By combining this highly precise microscopy technique with the x-ray magnetic circular dichroism effect, we reveal dimensionality effects in an ensemble of interacting magnetic nanoparticles. Such effects are topical in current nanomagnetism research and highlight the opportunities of high-resolution soft x-ray microscopy in magnetism research and beyond.

The performance of hematite and Ti-substituted hematite nanorods as photoanodes for solar water splitting was quantitatively evaluated from the photoelectrochemical point of view. The nanostructure, morphology and chemical/electronic structure were characterized using various complementary methods, including X-ray diffraction, electron microscopy, X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy. The presence of both reductive and oxidative surface states was evidenced and their impact on the photoelectrochemical efficiency was characterized. We show that both electronic conduction enhancement provided by the Ti substitution and charge transfer promoted by oxidative surface states improve the solar water splitting performance.