Near-edge X-ray Absorption Fine Structure Spectroscopy Research Articles

Nanoscale mechanisms of carboxyl carbon preservation during Fe(II)-induced ferrihydrite transformation

The persistence of organic carbon (OC) in natural environments is widely attributed to OC associations with minerals such as iron (Fe) minerals. Carboxyl, a critical structure of OC, can form strong complexes with Fe minerals, but it is still largely unknown about the effects of carboxyl groups on the transformation of Fe oxides and the stabilization mechanisms of OC on Fe oxides at nanoscales. In this study, four carboxylic acids with varying numbers of carboxyl groups (2, 3, 4, and 27 carboxyls) and molecular weight (ranging from 100 to 2000 Da) were added during the coprecipitation of Fe oxides and OC. This approach was taken to systematically elucidate the nanoscale distribution and sequestration mechanisms of carboxyl-containing OC on Fe oxides over different aging periods. Results suggested that ferrihydrite transformed quickly into lepidocrocite, goethite, and magnetite with the presence of Fe(II). The transformation rate of lepidocrocite to goethite slowed with increasing carboxyl number in OC molecules for the low molecular weight carboxylic acids (100–300 Da), but the high molecular weight carboxylic acid (∼2000 Da) promoted ferrihydrite transformation into goethite. Meanwhile, the particle sizes of produced magnetite decreased with increasing carboxyl number in OC molecules. During the mineral transformation, the release of OC from Fe oxides to aqueous solution decreased with increasing numbers of carboxyl groups. Spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) coupled with electron-energy-loss spectroscopy (EELS) suggested that carboxyl-rich OC promoted the formation of abundant defective or porous structures in goethite, resulting in OC accumulation in the bulk areas of goethite, which provided an effective way to sequester OC. The aggregation of high molecular weight OC containing more carboxyl groups with magnetite nanoparticles also played an important role in the preservation of OC. Furthermore, Fourier-transform infrared spectroscopy (FTIR) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) indicated that OC may form bidentate binding with Fe oxides and the binding strength of Fe(III) and OC may change with varying numbers of carboxyl groups. Results in this study provided a comprehensive understanding of the dynamic interactions between OC with different numbers of carboxyl groups and Fe oxides, and shed insights into the nanoscale mechanisms of OC stabilization during Fe oxide transformation process.

Beagle: a near-edge X-ray absorption fine-structure spectroscopy data processing solution for beamline experiments at Pohang Accelerator Laboratory.

Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy is a powerful tool for identifying chemical bonding states at synchrotron radiation facilities. Advances in new materials require researchers in both academia and industry to measure tens to hundreds of samples during the available beam time on a synchrotron beamline, which is typically allocated to users. Automated measurement methods, along with analysis software, have been developed for beamlines. Automated measurements facilitate high-throughput experiments and accumulate vast amounts of measured spectral data. The analysis software supports various functions for analyzing the experimental data; however, these analysis methods are complicated, and learning them can be time-consuming. To process large amounts of spectral data, a new analysis software, dedicated to NEXAFS spectroscopy, that is easy to use and can provide results in a short time is desired. Herein, the development of Beagle is described, software calculating molecular orientation from NEXAFS spectroscopy data that can report results in a short time comparable with that required to measure one sample at the beamline. It was designed to progress in a single sequence from data loading to the printing of the results with a `click of a button'. The functions of the software include recognizing the dataset, correcting the background, normalizing the plot, calculating the electron yield and determining the molecular orientation. The analysis results can be saved as {\tt{.txt}} files (spectral data), {\tt{.pdf}} files (graphic images) and Origin files (spectral data and graphic images).

Isomer-specific photofragmentation of C3H3+ at the carbon K-edge.

Individual fingerprints of different isomers of C3H3+ cations have been identified by studying photoionization, photoexcitation, and photofragmentation of C3H3+ near the carbon K-edge. The experiment was performed employing the photon-ion merged-beams technique at the photon-ion spectrometer at PETRA III (PIPE). This technique is a variant of near-edge X-ray absorption fine-structure spectroscopy, which is particularly sensitive to the 1s → π* excitation. The C3H3+ primary ions were generated by an electron cyclotron resonance ion source. C3Hn2+ product ions with n = 0, 1, 2, and 3 were observed for photon energies in the range of 279.0 eV to 295.2 eV. The experimental spectra are interpreted with the aid of theoretical calculations within the framework of time-dependent density functional theory. To this end, absorption spectra have been calculated for three different constitutional isomers of C3H3+. We find that our experimental approach offers a new possibility to study at the same time details of the electronic structure and of the geometry of molecular ions such as C3H3+.

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.

Monitoring the Synthesis of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron-Based XRD and Sxas

The synthesis of Ni-poor (NCM111, LiNi1/3Co1/3Mn1/3O2) and Ni-rich (NCM811 LiNi0.8Co0.1Mn0.1O2) lithium transition metal oxides (space group R-3m ) from hydroxide precursors (Ni1/3Co1/3Mn1/3(OH)2, Ni0.8Co0.1Mn0.1(OH)2) are investigated with in situ synchrotron powder diffraction (SXPD) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The development of the layered structure of these two cathode materials proceeds via two utterly different reaction mechanisms. While the synthesis of NCM811 involves a rock salt-type intermediate phase, NCM111 reveals a layered structure throughout the entire synthesis. Moreover, the necessity and the impact of a pre-annealing step and a high-temperature holding step are discussed.

Studying Surface Chemistry of Mixed Conducting Perovskite Oxide Electrodes with Synchrotron-Based Soft X-rays.

A fundamental understanding of the electrochemical reactions and surface chemistry at the solid-gas interface in situ and operando is critical for electrode materials applied in electrochemical and catalytic applications. Here, the surface reactions and surface composition of a model of mixed ionic and electronic conducting (MIEC) perovskite oxide, (La0.8Sr0.2)0.95Cr0.5Fe0.5O3-δ (LSCrF8255), were investigated in situ using synchrotron-based near-ambient pressure (AP) X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure spectroscopy (NEXAFS). The measurements were conducted with a surface temperature of 500 °C under 1 mbar of dry oxygen and water vapor, to reflect the implementation of the materials for oxygen reduction/evolution and H2O electrolysis in the applications such as solid oxide fuel cell (SOFC) and electrolyzers. Our direct experimental results demonstrate that, rather than the transition metal (TM) cations, the surface lattice oxygen is the significant redox active species under both dry oxygen and water vapor environments. It was proven that the electron holes formed in dry oxygen have a strong oxygen character. Meanwhile, a relatively higher concentration of surface oxygen vacancies was observed on the sample measured in water vapor. We further showed that in water vapor, the adsorption and dissociation of H2O onto the perovskite surface were through forming hydroxyl groups. In addition, the concentration of Sr surface species was found to increase over time in dry oxygen due to Sr surface segregation, with the presence of oxygen holes on the surface serving as an additional driving force. Comparatively, less Sr contents were observed on the sample in water vapor, which could be due to the volatility of Sr(OH)2. A secondary phase was also observed, which exhibited an enrichment in B-site cations, particularly in Fe and relatively in Cr, and a deficiency in A-site cation, notably in La and relatively in Sr. The findings and methodology of this study allow for the quantification of surface defect chemistry and surface composition evolution, providing crucial understanding and design guidelines in the electrocatalytic activity and durability of electrodes for efficient conversions of energy and fuels.

Correlation of the electronic structure and Li‐ion mobility with modulus and hardness in LiNi0.6Co0.2Mn0.2O2 cathodes by combined near edge X‐ray absorption finestructure spectroscopy, atomic force microscopy, and nanoindentation

AbstractThe electrochemical performance of cathode materials in Li‐ion batteries is reflected in macroscopic observables such as the capacity, the voltage, and the state of charge (SOC). However, the physical origin of performance parameters are atomistic processes that scale up to a macroscopic picture. Thus, revealing the function and failure of electrochemical devices requires a multiscale (and ‐time) approach using spectroscopic and microscopic techniques. In this work, we combine near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS) to determine the chemical binding state of transition metals in LiNi0.6Co0.2Mn0.2O2 (NCM622), electrochemical strain microscopy to understand the Li‐ion mobility in such materials, and nanoindentation to relate the mechanical properties exhibited by the material to the chemical state and ion mobility. Strikingly, a clear correlation between the chemical binding, the mechanical properties, and the Li‐ion mobility is found. Thereby, the significant relation of chemo‐mechanical properties of NCM622 on a local and global scale is clearly demonstrated.

Synthesis and comprehensive synchrotron-based structural analysis of Si-doped nanodiamond composite films deposited on cemented carbide

Si-doped nanodiamond composite (NDC) films were deposited on unheated WC − Co substrates by coaxial arc plasma deposition for advanced cutting tools applications. The nanoindentation test revealed changes in films hardness and Young's modulus attributed to various Si doping concentrations (0, 1, 5, and 20 at.%) and the catalytic effects of Co diffused from the substrate surface into the films. To reveal the physical origin behind these changes, the films' structure was examined by synchrotron-based Auger electron spectroscopy (AES), soft X-ray photoemission spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). The AES and XPS analysis showed a consistent correlation between nanoindentation measurements and the estimated C sp3 fraction in the films. The NEXAFS spectra revealed intense C − C σ* resonance, consistent with the measured film hardness. The 1 at.% Si-doped film, deposited with an undoped NDC buffer layer to mitigate the Co catalytic effects, exhibited the highest hardness of 60 GPa, the largest C sp3 fraction, and the most intense CC σ* peak. Si doping resulted in the formation of C − Si sp3 bonds at the expense of C sp2 bonds, increasing the fraction of C sp3 bonds and enhancing film hardness. The synchrotron-based analysis effectively revealed the electronic states of NDC hard coatings, particularly after the removal of surface contaminants through mechanical polishing.

Versatile tabletop setup for picosecond time-resolved resonant soft-x-ray scattering and spectroscopy.

We present a laser-driven, bright, and broadband (50 to 1500eV) soft-x-ray plasma source with <10ps pulse duration. This source is employed in two complementary, laboratory-scale beamlines for time-resolved, magnetic resonant scattering and spectroscopy, as well as near-edge x-ray absorption fine-structure (NEXAFS) spectroscopy. In both beamlines, dedicated reflection zone plates (RZPs) are used as single optical elements to capture, disperse, and focus the soft x rays, reaching resolving powers up to E/ΔE > 1000, with hybrid RZPs at the NEXAFS beamline retaining a consistent E/ΔE > 500 throughout the full spectral range, allowing for time-efficient data acquisition. We demonstrate the versatility and performance of our setup by a selection of soft-x-ray spectroscopy and scattering experiments, which so far have not been possible on a laboratory scale. Excellent data quality, combined with experimental flexibility, renders our approach a true alternative to large-scale facilities, such as synchrotron-radiation sources and free-electron lasers.

Response of size-dependent chemical composition of dissolved organic and inorganic species to land use types in tropical coastal headstreams

Land-use types dramatically affect the source, composition, behavior and fate of headstream chemical species. However, the influence of land-use types on the size-dependent composition of dissolved organic matter (DOM) and dissolved inorganic matter (DIM) is still unclear. Here, we evaluated the size-dependent concentration, composition and relationship of chemical species from 9 coastal headstreams (i.e. forested, agricultural and wetland headstreams) using multiple spectroscopic techniques including absorbance, excitation-emission matrix, near-edge X-ray absorption fine structure spectroscopy (NEXAFS), X-ray diffraction (XRD), scanning electron microscopy combined with energy dispersive spectroscopy (SEM-EDS) and synchrotron-based micro-X-ray fluorescence (μ-XRF). Results showed that 68.57%-85.78% of dissolved organic carbon (DOC) with abundant humic/fulvic-like substances were distributed in the <1 kDa fraction in all samples, with a higher percentage in wetland samples. Agricultural land-use increased the export of aluminosilicate minerals in >1 kDa fractions and terrestrial fulvic/humic-like substances from land to stream. Forested streams showed high DOC in the 1 kDa-0.2 μm fraction, predominance of autochthonous DOM rich in amides, amines, carboxyl and O-alkyl groups, and abundance whitlockite and ferromanganese oxides. Wetland streams were characterized by abundant halite, sylvite, and microbially-transformed humic-like DOM rich in aromatic and phenolic groups. Morphology and correlation analysis implied DIM was closely combined with fluorescent DOM (FDOM) and colored DOM (CDOM), resulting in more irregular organo-inorganic complexes in forested and agricultural streams, and more halite and sylvite crystal blocks encapsulating by smooth and close organic–inorganic complexes in wetland streams. Redundancy analysis (RDA) analysis suggested that land-use types (17.20%) and molecular weight (14.29%) were the prominent factors impacting the composition and relationship of DOM and DIM. Land-use types altered the sources and transport patterns of chemical species in headstreams, influencing their size-dependent compositions and associated biogeochemical processes. Such information is imperative for monitoring and developing land-use policies in coastal regions undergoing intense anthropogenic alterations.

Surface characterization of covalently functionalized carbon-based nanomaterials using comprehensive XP and NEXAFS spectroscopies

Reliable and straightforward characterization and analysis of carbon-based nanomaterials on the atomic level is essential to exploring their potential for application. Here we use a combination of highly surface sensitive x-ray photoelectron (XP) spectroscopy and near edge x-ray absorption fine structure spectroscopy (NEXAFS) to study and quantify the covalent functionalization of nanographene and single-walled carbon nanotubes with nitrene [2 + 1]-cycloaddition. With this comprehensive analytical approach, we demonstrate that the π-conjugated system of functionalized carbon-based nanomaterials is preserved according to NEXAFS analysis, which is challenging to prove with XP spectroscopy investigation alone. Using this combination of analytical approaches, we show significant similarities after functionalization for various carbon-based nanomaterials. Both analytical methods are strongly suited to study possible post-modification reactions of functionalized carbon-based nanomaterials.

Field-induced modification of the electronic structure in BTBT-based organic thin films observed by NEXAFS spectroscopy

We present an in operando near-edge x-ray absorption fine structure (NEXAFS) study on p-type [11-(benzo[b]benzo[4,5]thieno[2,3-d]thiophen-2-yl)dodecyl)] BTBT-based self-assembled monolayer (BTBT-SAM) films. As a 2D-model system, the BTBT-SAM offers direct insight into the active organic semiconductor layer without interfering bulk materials. This allows for the observation of polaronic states caused by charged species at the dielectric/organic interface. Linear NEXAFS dichroism is employed to derive the molecular orientation of the BTBT subunit. Field-induced modifications in the unoccupied molecular orbitals are observed in the NEXAFS spectra. The spectral changes in the on- and off-states are discussed in the context of polaron formation due to charge accumulation induced by the applied electric field.

Silicon as a potential limiting factor for phosphorus availability in paddy soils

Rice cultivation requires high amounts of phosphorus (P). However, significant amounts of P fertilizer additions may be retained by iron (Fe) oxides and are thus unavailable for plants. At the same time, rice cultivation has a high demand for silicic acid (Si), reducing Si availability after short duration of rice cultivation. By studying a paddy chronosequence with rice cultivation up to 2000 years, we show that Si limitation, observed as early as a few decades of rice cultivation, is limiting P availability along the paddy soils chronosequence. Using near edge X-ray absorption fine structure spectroscopy (NEXAFS) in a scanning transmission (soft) X-ray microscope (STXM) we show release of available P was linked to a Si-induced change in speciation of Fe-phases in soil particles and competition of Si with P for binding sites. Hence, low Si availability is limiting P availability in paddy soils. We propose that proper management of Si availability is a promising tool to improve the P supply of paddy plants.

Insights into the Redox Behavior of Pr0.5Ba0.5MnO3−δ-Derived Perovskites for CO2 Valorization Technologies

In situ temperature-programmed (TP) analyses in a multianalytical approach including X-ray diffractometry (XRD), temperature-programmed reduction (TPR), thermogravimetry (TGA), near-edge X-ray absorption fine structure spectroscopy (NEXAFS) are used to study the relationship between redox properties and structural changes in Pr0.5Ba0.5MnO3−δ (m-PBM), PrBaMn2O5+δ (r-PBM), and PrBaMn2O6−δ (o-PBM) when exposed to reduction/oxidation cycles. TP-XRD analysis shows that under reducing conditions, between 300 and 850 °C, the biphase perovskite m-PBM turns into the monolayered perovskite r-PBM. Stabilization of the latter phase at room temperature requires early oxidation in air at a high temperature (850 °C) to avoid segregation, resulting in the formation of the oxidized layered phase (o-PBM). The o-PBM layered perovskite is characterized by the H2-TPR profile, showing two reduction peaks at temperatures below 500 °C. TP-NEXAFS characterization reveals the copresence of Mn(IV) (60%), Mn(III) (30%), and Mn(II) (10%) and helps to interpret the reduction profile: Mn(IV) converts to Mn(III) at ∼300 °C (I pk), Mn(III) to Mn(II) at ∼450 °C (II pk). The TGA characterization confirms the reversibility of the o-PBM ↔ r-PBM process at 800 °C; in addition, it shows that the r-PBM can be oxidized almost completely (∼99%) also by CO2 without accumulation of carbonates. This study sheds light on the peculiar redox behavior of PBM-based materials and paves the way for their application as oxygen carriers and catalytic promoters in different CO2 enhancement technologies. Here, we discuss the results obtained to develop versatile and redox-resistant electrodes for solid oxide electrochemical cell/solid oxide fuel cell applications.

Surface reconstructions on Mn3O4(001) films

The structural complexity of surfaces of spinel-like oxides together with the existence of competing phases of different or mixed valencies have limited surface structure determinations so far. Only recently, the concept of subsurface cation vacancies (SCVs) could be demonstrated for an ${\mathrm{Fe}}_{3}{\mathrm{O}}_{4}$ single crystal surface. Here, we present the appearance of SCVs for ultrathin and thin films of ${\mathrm{Mn}}_{3}{\mathrm{O}}_{4}$(001) depending on film thickness. The structures of films grown by molecular beam epitaxy have been investigated using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and near-edge x-ray absorption fine structure spectroscopy (NEXAFS). For coverage up to 4 (Mn ions)/(Ag atom) of ${\mathrm{Mn}}_{3}{\mathrm{O}}_{4}$ and an annealing temperature of 640 K, a $p(2\ifmmode\times\else\texttimes\fi{}1)$ reconstruction has been observed in STM and LEED. Using NEXAFS, the identity of the manganese oxide has been narrowed down to the spinel ${\mathrm{Mn}}_{3}{\mathrm{O}}_{4}$ and its related vacancy compound $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Mn}}_{2}{\mathrm{O}}_{3}$. Thus the $p(2\ifmmode\times\else\texttimes\fi{}1)$ reconstruction corresponds to an ${\mathrm{Mn}}_{3}{\mathrm{O}}_{4}$(001) surface with $\mathrm{Mn}{\mathrm{O}}_{2}$ termination. For a lower annealing temperature of 450 K or thicker films [5 and 10 (Mn ions)/(Ag atom) ], additional $p(4\ifmmode\times\else\texttimes\fi{}2)$ and $c(4\ifmmode\times\else\texttimes\fi{}4)$ reconstructions have been observed. These extra reconstructions stem from lateral shifts of top-sublayer ions induced by SCVs.

Micro-spectroscopic and freezing characterization of ice-nucleating particles collected in the marine boundary layer in the eastern North Atlantic

Abstract. Formation of atmospheric ice plays a crucial role in the microphysical evolution of mixed-phase and cirrus clouds and thus climate. How aerosol particles impact ice crystal formation by acting as ice-nucleating particles (INPs) is a subject of intense research activities. To improve understanding of atmospheric INPs, we examined daytime and nighttime particles collected during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) field campaign conducted in summer 2017. Collected particles, representative of a remote marine environment, were investigated for their propensity to serve as INPs in the immersion freezing (IMF) and deposition ice nucleation (DIN) modes. The particle population was characterized by chemical imaging techniques such as computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX) and scanning transmission X-ray microscopy with near-edge X-ray absorption fine-structure spectroscopy (STXM/NEXAFS). Four major particle-type classes were identified where internally mixed inorganic–organic particles make up the majority of the analyzed particles. Following ice nucleation experiments, individual INPs were identified and characterized by SEM/EDX. The identified INP types belong to the major particle-type classes consisting of fresh sea salt with organics or processed sea salt containing dust and sulfur with organics. Ice nucleation experiments show IMF events at temperatures as low as 231 K, including the subsaturated regime. DIN events were observed at lower temperatures of 210 to 231 K. IMF and DIN observations were analyzed with regard to activated INP fraction, ice-nucleation active site (INAS) densities, and a water activity-based immersion freezing model (ABIFM) yielding heterogeneous ice nucleation rate coefficients. Observed IMF and DIN events of ice formation and corresponding derived freezing rates demonstrate that the marine boundary layer aerosol particles can serve as INPs under typical mixed-phase and cirrus cloud conditions. The derived IMF and DIN parameterizations allow for implementation in cloud and climate models to evaluate predictive effects of atmospheric ice crystal formation.

Spectroscopic investigations and density functional theory calculations reveal differences in retention mechanisms of lead and copper on chemically-modified phytolith-rich biochars

A better understanding of different retention mechanisms of potentially toxic elements (PTEs) by biochars during the remediation of contaminated sites is critically needed. In this study, different spectroscopic techniques including synchrotron-based micro-X-ray fluorescence (μ-XRF), X-ray absorption fine structure (XAFS), and near-edge XAFS spectroscopy (NEXAFS), were used to investigate the spatial distributions and retention mechanisms of lead (Pb) and copper (Cu) on phytolith-rich coconut-fiber biochar (CFB), and ammonia, nitric acid and hydrogen peroxide modified CFB (MCFB) (i.e., ACFB, NCFB and HCFB). The μ-XRF analyses indicated that sorption sites on ACFB and NCFB were more efficient compared to those on CFB and HCFB to bind Pb/Cu. XAFS analyses revealed that the percentage of Pb species as Pb(C2H3O2)2 increased from 22.2% (Pb-loaded CFBs) to 47.4% and 41.9% on Pb-loaded NCFBs and HCFBs, while the percentage of Cu(OH)2 and Cu(C2H3O2)2 increased from 5.8% to 32.8% (Cu-loaded CFBs) to 41.5% and 43.4% (Cu-loaded NCFBs), and 27.1% and 35.1% (Cu-loaded HCFBs), respectively. Due to their similar atomic structures of Pb/Cu, Pb(C2H3O2)2/Pb-loaded montmorillonite and Cu(C2H3O2)2/Cu(OH)2 were identified as the predominant Pb/Cu species observed in Pb- and Cu-loaded MCFBs. The NEXAFS analyses of carbon confirmed that increasing amounts of carboxylic groups were formed on HCFB and NCFB by oxidizing carbon-containing functional groups, which could provide additional active binding sites for Pb/Cu retention. Results from the X-ray photoelectron spectroscopy analyses of nitrogen showed that azido-groups of ACFB played major roles in Pb/Cu retention, while amide-groups and pyridine-groups of NCFB primarily participated in Pb/Cu retention. Overall, density functional theory calculations suggested that silicate and the synergistic effect of hydroxyl and carboxylic-groups on MCFBs were highly efficient in Pb retention, while azido-groups and/or carboxylic-groups played major roles in Cu retention. These results provide novel insights into the PTE retention mechanisms of MCFBs.

Electronic structure of multi-layered graphene oxide membrane moderately reduced in vacuum

Graphene oxide (GO) has recently attracted more attention for its own physical and chemical properties regardless of being initially seen only as an ideal candidate for the production process of single/few graphene layers. One of the most interesting forms of this material is a multilayer structure, sometimes called graphene paper, with a thickness approaching a value up to a few micrometers. We present and discuss the results of investigation on electronic structure of such a thick material produced by the improved Hummer's method and deposited on a metallic mesh. The samples were investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) around the carbon absorption edge. The NEXAFS results are supplemented with the output of the X-ray photoelectron spectroscopy (XPS) analysis for C1s and O1s lines and with the micro-Raman spectroscopy. There are still some discrepancies concerning the electronic structure of graphene oxide (GO), especially, when many individual GO sheets are stacked together as in the case under consideration. The samples were heavily functionalized by oxidation (the presence of carbonyl, epoxy, and hydroxyl groups). There are indications that the prepared samples tended towards the turbostratic form of stacking when annealed in vacuum at moderate temperatures between 100 °C and 500 °C. These changes were observed in both π* and σ* resonance areas. Surprisingly, the features of the NEXAFS spectrum of both the annealed and non-annealed samples resemble reasonably the theoretically determined structure of the density of states (DOS) of monocrystalline carbon. It could suggest a strong “graphitisation” process already in the sample preparation phase. The observed increase in the sample amenability to the environmental water with annealing temperature is discussed briefly. The results also deliver a clear support for the claims of room-temperature metastability of multilayer GO.

Reversible and Irreversible Redox Processes in Li-Rich Layered Oxides

Reversible and irreversible charge exchange reactions of Li- and Mn-rich layered oxides (Li1.15Ni0.2Co0.1Mn0.55O2, LLO) are investigated with bulk and surface-sensitive near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the Ni L2,3, Co L2,3, Mn L2,3, and O K edges; mass spectrometry (MS); and operando synchrotron X-ray powder diffraction (SXPD). The present work shows the relation between O–O formation in the bulk and Ni, Co, and Mn reduction/oxidation processes, which in turn deliver outstanding capacities of Li-rich layered oxides (LLO). Moreover, the reversibility of charge compensation reactions is discussed and differences between O–O formation and oxygen release, both occurring mainly upon the first charge (so-called activation), are identified.

On the Origin of Reversible and Irreversible Reactions in LiNixCo(1−x)/2Mn(1−x)/2O2

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO2, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNixCo(1−x)/2Mn(1−x)/2O2 (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g−1), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes.