Scanning Transmission X-ray Microscopy Research Articles

Formation of nanoparticles during accelerated UV degradation of fleece polyester textiles

Micro- and nanoplastics have emerged as critical pollutants in various ecosystems, posing potential environmental and human health risks. Washing of polyester textiles has been identified as one of the sources of nanoplastics. However, other stages of the textile life cycle may also release nanoparticles. This study aimed to examine nanoparticle release during UV degradation of polyester textiles under controlled and real-world conditions. Fleece polyester textiles were weathered under simulated sunlight for up to two months, either in air or submerged in water. We conducted bi-weekly SEM image analyses and quantified released nanoparticles using nanoparticle tracking analysis (NTA). At week 0, the fiber surface appeared smooth after prewashing. In the air group, nanoparticles appeared on the fiber surface after UV-exposure. In the group of textiles submerged in water, the surfaces developed more pits over time. The cumulative nanoparticle emission from the weathered textiles ranged from 1.4 × 1011 to 4.0 × 1011 particles per gram of fabric in the air group and from 1.6 × 1011 to 4.4 × 1011 particles per gram of fabric in the water group over two months. The predominant particle size fell into the 100 to 200 nm range. The estimated mass of the released nanoparticles was 0.06–0.26 g per gram of fabric, which is lower than the amount released during the washing of new textiles. Additionally, Scanning Transmission X-ray Microscopy (STXM) images indicated that the weathered nanoparticles underwent oxidation. Overall, the research offers valuable insights into nanoparticle formation and release from polyester textiles during UV degradation.

3D imaging of magnetic domains in Nd2Fe14B using scanning hard X-ray nanotomography.

Nanoscale structural and electronic heterogeneities are prevalent in condensed matter physics. Investigating these heterogeneities in 3D has become an important task for understanding material properties. To provide a tool to unravel the connection between nanoscale heterogeneity and macroscopic emergent properties in magnetic materials, scanning transmission X-ray microscopy (STXM) is combined with X-ray magnetic circular dichroism. A vector tomography algorithm has been developed to reconstruct the full 3D magnetic vector field without any prior noise assumptions or knowledge about the sample. Two tomographic scans around the vertical axis are acquired on single-crystalline Nd2Fe14B pillars tilted at two different angles, with 2D STXM projections recorded using a focused 120 nm X-ray beam with left and right circular polarization. Image alignment and iterative registration have been implemented based on the 2D STXM projections for the two tilts. Dichroic projections obtained from difference images are used for the tomographic reconstruction to obtain the 3D magnetization distribution at the nanoscale.

Morphological, Microstructural, and In Situ Chemical Characteristics of Siderite Produced by Iron-Reducing Bacteria.

Dissimilatory iron-reducing bacteria (DIRB) oxidize organic matter or hydrogen and reduce ferric iron to form Fe(II)-bearing minerals, such as magnetite and siderite. However, compared with magnetite, which was extensively studied, the mineralization process and mechanisms of siderite remain unclear. Here, with the combination of advanced electron microscopy and synchrotron-based scanning transmission X-ray microscopy (STXM) approaches, we studied in detail the morphological, structural, and chemical features of biogenic siderite via a growth experiment with Shewanella oneidensis MR-4. Results showed that along with the growth of cells, Fe(II) ions were increasingly released into solution and reacted with CO32- to form micrometer-sized siderite minerals with spindle, rod, peanut, dumbbell, and sphere shapes. They are composed of many single-crystal siderite plates that are fanned out from the center of the particles. Additionally, STXM revealed Fh and organic molecules inside siderite. This suggests that the siderite crystals might assemble around a Fh-organic molecule core and then continue to grow radially. This study illustrates the biomineralization and assembly of siderite by a successive multistep growth process induced by DIRB, also provides evidences that the distinctive shapes and the presence of organic molecules inside might be morphological and chemical features for biogenic siderite.

Synchrotron X-ray spectromicroscopy analysis of wear tested graphene-containing alumina coatings

Thermally sprayed Al2O3 coatings containing graphene nano platelets (GNP) have been shown to exhibit improved wear resistance. To understand the positive influence of GNP on wear properties, scanning transmission X-ray microscopy (STXM) analyses were performed to determine the structural and chemical changes that occur on the GNP and alumina matrix after wear tests. STXM results acquired at the C K-edge showed that the GNP are aligned parallel to the specimen surface in the as-sprayed coatings. GNP flakes are also observed at the tribo-surface of the wear tested sample. The results obtained at the Al K-edge show that the aluminum oxide below the wear track becomes amorphous during the wear test and carbon is dissolved in it. Wear tests performed on thermally sprayed pure alumina samples (without GNP) and on sintered bulk alumina prove that neither the presence of GNP nor the porosity in the coating are responsible for the amorphization of the alumina matrix. The results discussed in this work advance the fundamental understanding of graphene-containing composites, which is considered very important to exploit the unique advantages of graphene in technological applications.

Deep understanding of LiCoO2 electrode degradation for optimized recycling strategies

Empowered by a synergistic combination approach of Scanning Transmission X-ray Microscopy (STXM) imaging and X-ray Absorption Near Edge Structure (XANES) spectroscopy, a quantitative analysis on the composition and spatial distribution of the cathode in a failed 18650 LiCoO2 (LCO) battery was conducted. Distinct compositional differences between the central and peripheral cathode regions in the failed LCO battery were discerned by utilizing bulk XANES in Total Electron Yield (TEY) and Fluorescence Yield (FY) modes. The central region shows more severe degradation in terms of LCO reduction and excess cathode-electrolyte interface (CEI) buildup. Meanwhile, the STXM technique precisely imaged a specific region of interest in the center of the cathode, covering C, O, and F K-edges, and Co L2,3-edge, to deeply investigate the degradation. Quantitative chemical mapping with spatially resolved XANES spectroscopy, facilitate an in-depth understating of the interfacial reactions on battery electrodes and battery failure fundamentals.

Aqueous inks for ecofriendly processing of organic solar cells: Investigation of morphological changes

Aqueous dispersions of organic semiconducting nanoparticles (NPs) are particularly attractive as inks for the environmentally friendly preparation of organic solar cells. The internal morphology of the NPs, which depends on their elaboration process, is a key parameter, which has a significant influence on the final morphology of the active layer and therefore its effectiveness. In the present study, core-shell (PF2:PC71BM) NPs were prepared by miniemulsion. Their internal morphology including the composition of the two phases was characterized by scanning transmission X-ray microscopy (STXM) showing a core composed of 77% PC71BM and a shell composed of 75% PF2. It was found that thermal annealing promotes PC71BM diffusion from the core to the shell, increasing its proportion in the shell from 25% to 42%. This annealing, when applied after NPs deposition by spincoating, allows partial coalescence of the NPs, reducing the roughness of the active layer, and increases electron mobility, thus demonstrating the formation of PC71BM percolation paths for electron transport. A PCE of 1.6% could thus be obtained after 10 min of thermal annealing at 100°C. At higher temperature, Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) analyses demonstrate the modification of the PF2 structuration from randomly oriented lamella after deposition to edge-on orientation after annealing, leading to an unfavorable decrease of the hole mobility in the direction perpendicular to the substrate, while increasing the hole mobility in the substrate plane. This study demonstrates the need to systematically characterize the internal morphology of NPs in order to rationalize the morphology of the active layer and optimize its properties.

Are the Fe-rich-clay veins in the igneous rock of the Kansas (USA) Precambrian crust of magmatic origin?

The North American Mid-Continent rift (MCR) is a 1.1 Ga aborted rift, which has recently become an area of intense focus for energy resource exploration following the report of H2 emissions. To document the nature of the producing rocks, we conducted a multi-scale study on preserved drill-core samples from the DR1-A well located in the same area as the H2-producing wells in Kansas. We showed that this well reaches an unmapped part of the MRS composed of fayalite-bearing monzo-diorites in which we identified atypical veins of iddingsite, a complex mixing of Fe-rich phyllosilicates. Combining scanning and transmission electron microscopy (SEM and TEM) with scanning transmission X-ray microscopy (STXM) allowed us to differentiate at least two types of sub-micro-meter Fe-rich veins. A central reduced vein cutting the fayalite, other mafic minerals, the plagioclase, and to a lesser extent the alkali feldspar, contains a complex mix of serpentine, chlorite, and mica. Furthermore, a border vein, with a higher degree of Fe-oxidation, is found to be contained only within the fayalite. This external vein mainly contains iron and silicon, together with a few percent of potassium and calcium, and can be divided into two sub-veins composed of Fe3+-rich interstratified chlorite-smectite and Fe3+-rich serpentine in direct contact with the fayalite. Textures and microstructures of these phyllosilicates suggest that they have crystallized from a late magmatic and differentiated fluid, which precipitation produced the central vein together with the exsolution of an H2O-enriched fluid phase. This exsolved fluid, chemically far from equilibrium with the fayalite, appears to have induced a deuteric alteration of the fayalite, leading to the crystallization of the external veins enriched in ferric iron. These observations bring new perspectives on the history of formation of iron-rich clay minerals, which may, somehow, be related to H2 production.

Electrochemical and scanning transmission X-ray microscopy studies of MnO2 and Mn3O4 for supercapacitor cathodes: Influence of fabrication method and electrochemical activation on charge storage

This investigation is motivated by increasing interest in Mn3O4 as a promising alternative to MnO2 for supercapacitors with high active mass and the need for better understanding of charging and electrode activation mechanisms. High energy ball milling (HEBM) of chemically precipitated MnO2 and Mn3O4 in the presence of quercetin resulted in significant capacitance increase. The use of Mn2+ salts for Mn3O4 synthesis facilitated the application of quercetin as a new chelating capping agent for synthesis of Mn3O4, which showed higher capacitance, compared to HEBM Mn3O4. The capacitance of Mn3O4 prepared using quercetin was 6.0F cm−2 (149.50 F g−1) for cyclic voltammetry at 2 mVs−1 and 8.03 F cm−2 (200.93 F g−1) for chronopotentiometry at 3 mA cm−2, which is on-par with the capacitance of MnO2. The time-consuming activation procedure, which limits Mn3O4 applications, was significantly accelerated for HEBM Mn3O4 and practically eliminated for Mn3O4 prepared using quercetin as a capping agent. Soft X-ray scanning transmission X-ray microscopy (STXM), an advanced synchrotron based analytical microscopy, was used at the O 1s and Mn 2p edges to identify and quantitatively map the Mn oxidation states present in Mn3O4 materials. Variable and fixed sweep rate electrochemical cycling procedures were used for the analysis of oxidation state of Mn and charging mechanism using STXM analysis coupled with electrochemical testing. The combination of STXM and electrochemistry provided valuable insights into the activation kinetics and charging mechanism. The STXM results showed that the tested materials contained mixtures of Mn2+, Mn3+ and Mn4+ oxides. A small amount of MnO phase in the tested samples indicated partial reduction. The higher content of MnO2 phase in the tested Mn3O4 prepared using quercetin as a capping agent, compared to HEBM Mn3O4, correlated with higher capacitance and the ability to eliminate the activation procedure.

Coherent Magnons with Giant Nonreciprocity at Nanoscale Wavelengths.

Nonreciprocal wave propagation arises in systems with broken time-reversal symmetry and is key to the functionality of devices, such as isolators or circulators, in microwave, photonic, and acoustic applications. In magnetic systems, collective wave excitations known as magnon quasiparticles have so far yielded moderate nonreciprocities, mainly observed by means of incoherent thermal magnon spectra, while their occurrence as coherent spin waves (magnon ensembles with identical phase) is yet to be demonstrated. Here, we report the direct observation of strongly nonreciprocal propagating coherent spin waves in a patterned element of a ferromagnetic bilayer stack with antiparallel magnetic orientations. We use time-resolved scanning transmission X-ray microscopy (TR-STXM) to directly image the layer-collective dynamics of spin waves with wavelengths ranging from 5 μm down to 100 nm emergent at frequencies between 500 MHz and 5 GHz. The experimentally observed nonreciprocity factor of these counter-propagating waves is greater than 10 with respect to both group velocities and specific wavelengths. Our experimental findings are supported by the results from an analytic theory, and their peculiarities are further discussed in terms of caustic spin-wave focusing.

Autotrophic biofilms sustained by deeply sourced groundwater host diverse bacteria implicated in sulfur and hydrogen metabolism

BackgroundBiofilms in sulfide-rich springs present intricate microbial communities that play pivotal roles in biogeochemical cycling. We studied chemoautotrophically based biofilms that host diverse CPR bacteria and grow in sulfide-rich springs to investigate microbial controls on biogeochemical cycling.ResultsSulfide springs biofilms were investigated using bulk geochemical analysis, genome-resolved metagenomics, and scanning transmission X-ray microscopy (STXM) at room temperature and 87 K. Chemolithotrophic sulfur-oxidizing bacteria, including Thiothrix and Beggiatoa, dominate the biofilms, which also contain CPR Gracilibacteria, Absconditabacteria, Saccharibacteria, Peregrinibacteria, Berkelbacteria, Microgenomates, and Parcubacteria. STXM imaging revealed ultra-small cells near the surfaces of filamentous bacteria that may be CPR bacterial episymbionts. STXM and NEXAFS spectroscopy at carbon K and sulfur L2,3 edges show that filamentous bacteria contain protein-encapsulated spherical elemental sulfur granules, indicating that they are sulfur oxidizers, likely Thiothrix. Berkelbacteria and Moranbacteria in the same biofilm sample are predicted to have a novel electron bifurcating group 3b [NiFe]-hydrogenase, putatively a sulfhydrogenase, potentially linked to sulfur metabolism via redox cofactors. This complex could potentially contribute to symbioses, for example, with sulfur-oxidizing bacteria such as Thiothrix that is based on cryptic sulfur cycling. One Doudnabacteria genome encodes adjacent sulfur dioxygenase and rhodanese genes that may convert thiosulfate to sulfite. We find similar conserved genomic architecture associated with CPR bacteria from other sulfur-rich subsurface ecosystems.ConclusionsOur combined metagenomic, geochemical, spectromicroscopic, and structural bioinformatics analyses of biofilms growing in sulfide-rich springs revealed consortia that contain CPR bacteria and sulfur-oxidizing Proteobacteria, including Thiothrix, and bacteria from a new family within Beggiatoales. We infer roles for CPR bacteria in sulfur and hydrogen cycling.8FE2mu4H1cxgQVBqjGxsC2Video

Beyond Constant Current: Origin of Pulse-Induced Activation in Phase-Transforming Battery Electrodes.

Mechanistic understanding of phase transformation dynamics during battery charging and discharging is crucial toward rationally improving intercalation electrodes. Most studies focus on constant-current conditions. However, in real battery operation, such as in electric vehicles during discharge, the current is rarely constant. In this work we study current pulsing in LiXFePO4 (LFP), a model and technologically important phase-transforming electrode. A current-pulse activation effect has been observed in LFP, which decreases the overpotential by up to ∼70% after a short, high-rate pulse. This effect persists for hours or even days. Using scanning transmission X-ray microscopy and operando X-ray diffraction, we link this long-lived activation effect to a pulse-induced electrode homogenization on both the intra- and interparticle length scales, i.e., within and between particles. Many-particle phase-field simulations explain how such pulse-induced homogeneity contributes to the decreased electrode overpotential. Specifically, we correlate the extent and duration of this activation to lithium surface diffusivity and the magnitude of the current pulse. This work directly links the transient electrode-level electrochemistry to the underlying phase transformation and explains the critical effect of current pulses on phase separation, with significant implication on both battery round-trip efficiency and cycle life. More broadly, the mechanisms revealed here likely extend to other phase-separating electrodes, such as graphite.

An innovative in situ AFM system for a soft X-ray spectromicroscopy synchrotron beamline.

Multimodal imaging and spectroscopy like concurrent scanning transmission X-ray microscopy (STXM) and X-ray fluorescence (XRF) are highly desirable as they allow retrieving complementary information. This paper reports on the design, development, integration and field testing of a novel in situ atomic force microscopy (AFM) instrument for operation under high vacuum in a synchrotron soft X-ray microscopy STXM-XRF end-station. A combination of μXRF and AFM is demonstrated for the first time in the soft X-ray regime, with an outlook for the full XRF-STXM-AFM combination.

Characterization of hydrated magnesium carbonate materials with synchrotron radiation-based scanning transmission X-ray spectromicroscopy

Soft X-ray spectromicroscopy reveals the evolution of different phases in the formation of green alternative cements.

Nanoscale in-Situ Characterization of Polymer Electrolyte Membrane Fuel Cell Catalyst Layers for Improved Water Management

Polymer electrolyte membrane fuel cells (PEMFCs) facilitate a sustainable energy infrastructure by offering emission-free electricity generation using renewably sourced hydrogen gas. The electrochemical reactions in a fuel cell occur at platinum-loaded catalyst layers (CLs), which are susceptible to degradation. Obstructing catalyst sites (triple phase boundaries1) with reaction by-products, such as water2,3, is the primary degradation mechanism in PEMFCs. Although various CL designs have been tested for improved electrochemical performance, in situ nanoscale visualization of platinum degradation and water accumulation in the CL at controlled temperature and relative humidity (RH) values are required to understand fundamental water mechanics through platinum and carbon nanostructures.In this work, we employed scanning transmission X-ray microscopy (STXM) and X-ray absorption fine structure spectroscopy (XANES) to evaluate the effect of temperature on pristine and broken-in fuel cell CLs. We developed a novel CL in-situ sample cell to enable nanostructured characterization of catalyst layers using STXM in a controlled temperature environment. Carbon 1s, Fluorine 1s, and Oxygen 1s spectral edges were probed utilizing near-edge X-ray absorption fine structure spectroscopy (NEXAFS) to reveal chemical degradation mechanisms and differentiate material structure. Through our custom in-situ cell, we demonstrate that the chemical composition and water accumulation throughout the PEMFC CLs at low, intermediate, and high operating temperatures (25°C, 40°C, and 60°C, respectively) can be quantified, along with thermal expansion analyses of the CL and ionomer membrane. Moreover, we reveal realistic structural and chemical characteristics of nanoscale catalysts by distinguishing regions of Nafion® Ionomer, catalyst carbon support, and platinum throughout the PEMFC’s membrane electrode assembly at industrially relevant fuel cell temperatures. The insights from this work will inform strategies to mitigate water flooding from a nanoscale perspective in addition to the novel in-situ spectromicroscopy characterization of current CL features.1. Fouzaï, I., Gentil, S., Bassetto, V. C., Silva, W. O., Maher, R., & Girault, H. H. (2021). 9(18), 11096-11123.2. Li, H., Tang, Y., Wang, Z., Shi, Z., Wu, S., Song, D., ... & Mazza, A. (2008). 178(1), 103-117.3. Kumsa, D. W., Bhadra, N., Hudak, E. M., Kelley, S. C., Untereker, D. F., & Mortimer, J. T. (2016). 13(5), 052001.

Analysis of Electrode Materials for Li-Ion Batteries by Synchrotron Soft X-Ray Microspectroscopy

The development of clean energy devices such as Li-ion batteries is attracting attention in order to realize a low-carbon society. In addition to development of materials for Li-ion batteries, advanced analytical methods are also being developed to obtain the guideline of new materials and improve battery performance. We have been working on electronic structure analysis of transition metals and oxygen using synchrotron soft X-ray absorption and emission spectroscopy including ex-situ measurements and operando measurements. [1-3] We have also reported on synchrotron radiation micro-photoemission spectroscopy of all-solid-state Li-ion batteries using an operando measurement system. [4,5]In this presentation, we report analysis of each facet of a single crystalline LiCoO2 particle by resonant photoemission microspectroscopy. Resonant photoemission spectroscopy is element-selective method for obtaining valence band spectra using excitation energies around the absorption edge of target elements. Co 2p-3d absorption (L 2,3 absorption edge) of LiCoO2 was used to study the Co 3d orbitals near the Fermi level in detail. [6] Next, we report on the absorption spectroscopy of LiCoO2 using scanning transmission X-ray microscopy (STXM). The spatial resolution of about 100 nm can be used to analyze the chemical state distribution for each particle or within each particle. [7]References Electrochem. Commun. 50 (2015) 93-96.Phys. Chem. Chem. Phys. 21 (2019) 26351–26357.Phys. Chem. Chem. Phys. 24 (2022) 19177-19183.J. Electron Spectrsc. Relat. Phenom., 233 (2019) 64-68.Sci. Rep., 9 (2019) 12452.CrystEngComm, 25 (2023)183-188.Sci. Rep., 13 (2023) 4639.

In-Situ Scanning Transmission X-Ray Microscopy Studies of MnO2-Based Supercapacitor Electrodes

Supercapacitors (SCs) as energy storage devices provide higher energy density than conventional capacitors and higher power density than batteries1. Understanding how charge is efficiently stored in the electrodes or across the electrolyte/electrode interface is key to developing advanced SC electrodes. Scanning transmission x-ray microscopy (STXM) studies2 have been used to investigate MnO2 based supercapacitor electrodes using a novel three-electrode based in-situ flow electrochemical device (Fig. 1)3, 4. Near-edge X-ray absorption fine structure (NEXAFS) spectra of MnO2 films in-situ deposited and subjected to several different electrochemical processes were measured with high spatial resolution at the Mn L3 and O K edges (Fig. 2) at both working electrode (WE) and counter electrode (CE) regions. In this work, the redox state changes associated with pseudocapacitance during charging/discharging processes in a potential window of -0.5 VAu to +0.9 VAu (+0.1 VRHE to +1.5 VRHE) have been investigated. The spectroscopic data and quantitative chemical mapping by in-situ STXM measurements demonstrated that an as-electrodeposited MnO2 film was reduced to both Mn3+ and Mn2+ oxidation states through a reversable Mn4+ ↔ Mn3+/Mn2+ redox reaction. A significant change from a quasi-uniform MnO2 film to a dendritc MnO2 structure was observed during discharging at +1.5 VRHE (Fig. 3, Fig. 4) corresponding to redeposition of Mn2+ dissolved into electrolyte during the reduction process5. In-situ STXM measurements at the CE showed there is deposition of MnO2 during the reduction reaction (charging process) at +0.1 VRHE. Mn L3 features of Mn2+ appeared in the electrolyte region during the reduction process and disappeared during the oxidation process, confirming the dissolution/redeposition mechanism. We have developed a novel and versatile platform for in situ studies of electrochemical processes, including supercapacitors, batteries, and electro-catalysts3, 4. References A. G. Olabi, Q. Abbas, A. Al Makky, and M. A. Abdelkareem, Energy, 248 123617 (2022). K. V. Kaznatcheev, C. Karunakaran, U. D. Lanke, S. G. Urquhart, M. Obst, and A. P. Hitchcock, Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 582 (1), 96-99 (2007). A. P. Hitchcock, C. Zhang, H. Eraky, L. Shahcheraghi, F. Ismail, and D. Higgins, Microscopy and Microanalysis, 27 (S2), 59-60 (2021). C. Zhang, N. Mille, H. Eraky, S. Stanescu, S. Swaraj, R. Belkhou, D. Higgins, and A. Hitchcock, (2023). T.-H. Wu, Y.-Q. Lin, Z. D. Althouse, and N. Liu, ACS Applied Energy Materials, 4 (11), 12267-12274 (2021). Figure 1

X-Ray Absorption Spectroscopy Studies of Ti-Mn Redox Flow Battery to Clarify the Redox Reaction

Redox flow battery (RFB) is a promising candidate of large-scale stationary energy storage which is necessary to utilize renewable energy. For RFBs, the capability to easily increase the capacity by enlarging the electrolyte tank, high charge-discharge cycle performance, and wide flexibility to high- and low-frequency fluctuations are highly advantageous.Nowadays vanadium RFBs are used for practical use, but the material cost of vanadium is problematic to further spread them. An alternative candidate for commercial use is titanium-manganese (Ti-Mn) RFBs [1] whose material cost should be lower. On the other hand, the stability of the electrolyte for positive electrode (catholyte) need to be improved, because precipitates are created by a charge disproportionation reaction of Mn ions in the charged catholyte [2]. The formation of precipitates decreases the energy density and degrades the cyclability. To improve the characteristics, the chemical state and redox reaction of the electrolytes of Ti-Mn RFBs should be clarified by precise analyses.We performed synchrotron radiation X-ray absorption spectroscopy (XAS) for the electrolytes of a Ti-Mn RFB to directly observe the redox reaction [3]. In this study, the same Ti-Mn RFB electrolyte was used for both positive and negative electrodes. The Ti K-edge XAS of the electrolyte for negative electrode (anolyte) revealed gradual reduction reaction of Ti from Ti4+ on the charge process. The Ti L 2,3-edge XAS spectrum for the anolyte at state of charge (SOC) of 80% was mostly attributed to Ti3+ state. The results for Ti are consistent with electrochemical views in previous reports [2]. The Mn K-edge XAS of the catholyte gradually shifted to higher energy-side up to SOC of 50%, indicating a slight oxidation reaction of Mn from Mn2+. However, the Mn L 2,3-edge XAS spectrum for the catholyte solution at SOC of 80% was of Mn2+ state that was not changed from the initial state. Instead, scanning transmission X-ray microscopy (STXM; XAS mapping with a high spatial resolution) at the Mn L 3-edge unveiled that the precipitates mostly consist of Mn4+. Thus, the charge disproportionation reaction of 2Mn3+ -> Mn2+ (solution) + Mn4+ (precipitates) in the charged catholyte was confirmed. In the presentation, the electronic-structure change of the Ti and Mn ions in both catholyte and anolyte will be discussed in detail.

In Situ Transmission Electron Microscopy and Soft X-Ray Spectro-Microscopy to Understand Electrochemical Processes

Electrochemical CO2 conversion offers a route to use renewable sources of electricity to convert CO2 into valuable carbon-based fuels and chemicals, including carbon monoxide, ethanol and ethylene. For electrochemical CO2 conversion technologies to become a viable component of future sustainable energy infrastructures, improved performance materials (catalysts, electrodes, membrane electrode assemblies) are needed to achieve high conversion rates, selectivity and single-pass utilization of CO2. This talk will focus on the development of techniques to characterize the properties of electrochemical CO2 conversion materials under reaction conditions. These in-situ methods are producing results which will guide the design of next generation materials and reactors. The talk will focus primarily on in situ transmission electron microscopy (TEM) and related spectroscopic techniques (energy dispersive X-ray analysis and selected area electron diffraction), along with synchrotron-based methods including in-situ soft X-ray scanning transmission X-ray microscopy (STXM).

Revealing the Impact of Cell Conditioning on PEMWE Catalyst Layer Morphology

Polymer electrolyte membrane (PEM) water electrolysis is a promising green hydrogen generation technology to mitigate the effects of anthropogenic climate change. To achieve stable cell voltages, a conditioning procedure is typically required, where current or voltage cycling is applied until stable performance is achieved. Previous studies have demonstrated that a decrease in voltage occurs within the first few hours of operation [1], but this conditioning period has not been extensively studied for PEM electrolyzers, despite a variety of standard conditioning protocols available for PEM fuel cells in the literature. Previous works additionally suggest that changes in performance may be induced due to structural changes in the anode catalyst layer (CL) caused by large gas bubble evolution during the first few hours of operation [2]. However, to establish and optimize a conditioning procedure for PEMWEs, the specific structural changes caused by conditioning on the anode CL must be elucidated and correlated with the electrochemical performance parameters.In this work, we applied scanning transmission X-ray microscopy (STXM) to PEMWE catalyst layers to reveal pore and ionomer distributions in pristine and conditioned commercial CL samples. Prior to imaging, CL samples were embedded in epoxy and cut to 50 nm thick slices using an ultramicrotome. Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, Carbon 1s and Fluorine 1s absorption edges were probed to reveal pore and ionomer distributions, respectively. After image acquisition, the image stacks were processed to obtain the ionomer and epoxy spectra to enable spectral fitting and thresholding. Through this analysis, we quantified various morphological properties of catalyst layers (including CL thickness, porosity, pore size distribution, agglomerate distribution, and ionomer content) and compared these properties to those of pristine CLs to explain changes in cell performance. The insights gained from this work will aid in the development of efficient conditioning protocols and identify optimal post-conditioned anode CL morphology to inform the design of next-generation catalyst materials. A. Weiß et al., J Electrochem Soc, 166, F487–F497 (2019).O. Panchenko et al., Mater Today Energy, 16, 100394 (2020).

(Invited) Leveraging Imaging Techniques to Accelerate the Advancement of Polymer Electrolyte Membrane Water Electrolyzers

Polymer electrolyte membrane water electrolyzers (PEMWEs) are critically needed to meaningfully incorporate clean renewable energy into our energy, transportation, and manufacturing sectors, for without this energy conversion mechanism, the intermittency of renewable energy will always pose a prohibitive cost barrier to practical use. However, in addition to overcoming the intermittency issue of renewable energy, energy storage also has the power to transform current energy infrastructure, particularly when plagued by older systems that lack modularity and flexibility. For example, electricity grids are often constrained to move electricity in and out of a jurisdiction with careful predictions based on past use and future needs. This comes at a cost when electricity must be sold at a loss to prevent a catastrophic surplus of electricity in the grid. While the potential for PEMWEs is tremendous, we must reduce their capital and operating costs in order to reach widespread adoption. In recent years, important work in the field has contributed to advancing PEMWEs in a variety of areas from new materials to flow field design; however, experimental validation, particularly spatially resolved, is necessary to take a fully informed approach to tailoring these materials and architectures.In this talk, I will discuss how we use X-ray and neutron imaging, both ex situ and operando, to provide high spatial and temporal resolution experimental performance and materials characterization for PEMWEs to inform our design process for new materials fabrication, new architectures, and operating parameters. We obtained nano-scale, 3D imaging of PEMWE catalyst layers to inform the stochastic simulations used to uncover the influence of pore size and ionomer distributions on electrical and ionic conductivities. We also used operando X-ray imaging to elucidate the influence of catalyst layer and porous transport layer interfacial conditions on liquid and gas transport behaviour. By applying neutron imaging, we elucidated the impact of temperature on the distribution heterogeneity of liquid water reactant at the catalyst layer. I will also discuss how we are using soft X-rays to perform synchrotron-based scanning transmission X-ray microscopy with absorption spectroscopy to uncover heterogeneity across performance and material characteristics for the PEMWE. Through these highly resolved techniques (in terms of time and space), we aim to advance our predictive models for designing next generation materials, interfaces, and flow configurations for high performance water electrolyzers.