X-ray Absorption Fine Structure Spectroscopy Research Articles

Modification of Visible-Light-Responsive Pb2Ti2O5.4F1.2with Metal Oxide Cocatalysts to Improve Photocatalytic O2Evolution toward Z-scheme Overall Water Splitting.

The development of a highly active photocatalyst for visible-light water splitting requires a high-quality semiconductor material and a cocatalyst, which promote the migration of photogenerated charge carriers and surface redox reactions. In this work, cocatalyst loading on an oxyfluoride photocatalystPb2Ti2O5.4F1.2was applied to improve the water oxidation activity. Among the metal oxides examined, RuO2was found to be the most suitable, and the O2evolution activity depended on the preparation conditions of Ru/Pb2Ti2O5.4F1.2. The highest activity was obtained with RuCl3-impregnatedPb2Ti2O5.4F1.2, heated under a flow of H2at 523 K. The H2-heated Ru/Pb2Ti2O5.4F1.2showed an O2evolution rate ~13 times higher than the analogues without the H2treatment (e.g., RuO2/Pb2Ti2O5.4F1.2). Physicochemical analyses by means of X-ray absorption fine-structure spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and time-resolved-microwave-conductivity measurement indicated that the optimized photocatalyst contained partially-reduced RuO2species having ~5 nm in size, which effectively trapped the photogenerated charge carriers and promoted the oxidation of water into O2. The optimized Ru/Pb2Ti2O5.4F1.2was workable as an O2-evolving photocatalyst in Z-scheme overall water splitting, in combination of Ru-loaded, Rh-doped SrTiO3photocatalyst.

Tuning the metal-insulator transition temperature by the controlled generation of oxygen vacancies on La0.7Ca0.3MnO3-x epitaxial thin films

This report presents a study on the effect of the controlled generation of oxygen vacancies on the electronic transport properties of La0.7Ca0.3MnO3-x epitaxial thin films. Oxygen defects cause significant changes in the crystalline structure of mixed-valence manganites and lower the Mn valence, resulting in a shift of the metal-insulator transition to lower temperatures due to modifications in the angles and lengths of Mn-O bonds. Experiments using Polarized Extended X-Ray Absorption Fine Structure Spectroscopy have provided strong evidence that oxygen vacancies are mainly formed in the basal plane of the MnO6 octahedra. The accurate control of oxygen vacancies generation opens possibilities for managing and enhancing the magneto-electronic properties of epitaxial manganite thin films with potential in industrial applications.

Demonstration of Sensitivity of the Total-Electron-Yield Extended X-ray Absorption Fine Structure Method on Plastic Deformation of the Surface Layer

X-ray Absorption Fine Structure Spectroscopy (XAFS) has proven instrumental for the study of atomic-scale structures across diverse materials. This study conducts a meticulous comparative analysis between total electron yield (TEY) and absorption coefficients at the K absorption edge of polycrystalline Fe and Zr60Cu20Fe20 alloy. Our findings not only highlight differences between TEY and transmission XAFS measurements but also demonstrate the capabilities and limitations inherent in these measurement modes within the context of XAFS. This article provides an experimental exploration of widely used X-ray absorption spectroscopy methods, shedding light on the nuances of TEY and transmission XAFS. Through presenting experimental results, we aim to offer insights crucial to the material science community, guiding experimentalists in optimizing measurements while raising awareness about potential misinterpretations.

Compressed sensing for rapid tabletop X-ray absorption spectroscopy

X-ray Absorption Fine Structure (XAFS) spectroscopy is an analytical technique of chemical insight. Improvements to this technique are continuously carried out for reduction of the acquisition time and increasing the resolution, especially for studying operando processes. The accurate reconstruction of XAFS signals requires that the collected data are noise-free to extract elemental structure information in post-processing. A novel approach to rapid sampling (encoded measurement) is validated conceptually. The technique relies on sparse signal recovery, i.e. using compressed sensing to reconstruct under-sampled signals. The proof of concept is demonstrated by using a python code to reconstruct under-sampled XAFS spectra. A case study of transition metal samples and their oxides is considered for this purpose. The results demonstrate a robust recovery of chemical information from a 30% sampled signal for the near-edge region analysis and from a 45% sampled signal for extended-edge region analysis. The application of this procedure is important for demonstrating the feasibility of tabletop operation using laboratory X-ray sources which are not continuously tunable.

Structural analysis of pharmaceutical tablets using two-dimensional X-ray absorption fine-structure spectroscopy and its combination with X-ray computed tomography

The pharmaceutical properties of a solid formulations depend on their structure. To obtain structural information, such as the density, porosity, crystal forms of drugs, and the three-dimensional distribution of the drug and excipient particles within the formulations, is useful for formulation design and development. In this research, two-dimensional X-ray absorption fine-structure spectroscopy (2D-XAFS) and its combination with X-ray computed tomography (CT) were used for internal-structure analysis of tablets. Tablets containing form-II crystals and/or an amorphous solid dispersion (ASD) of bromhexine hydrochloride (BRH) were prepared and measured at a synchrotron radiation facility. The XAFS spectra of form-II crystals and the ASD of BRH were obtained after properly calibrating the irradiated X-ray energies. Their XAFS spectra showed small but marked differences. Form-II crystals and the ASD could be distinguished and visualized in the 2D-XAFS transmission and CT-XAFS slice images. Both 2D-XAFS and CT-XAFS provided detailed structural information and may be a useful alternative method in the development stage of solid dosage formulations.

Unveiling the significant promoting effect of SO2 on Ir/SiO2 catalyst for the CO-SCR of NOx in the presence of O2

Selective catalytic reduction of NOx by CO (CO-SCR) in the presence of O2 is challenging because in this process CO is prone to being oxidized by O2, thus inhibiting NOx reduction by CO. Furthermore, SO2 typically leads to the deactivation of the CO-SCR catalyst. Herein, a significant promoting effect of SO2 on Ir/SiO2 catalyst for the CO-SCR of NOx in the presence of O2 is reported. In-situ X-ray Absorption Fine Structure (XAFS) and X-ray photoelectron spectroscopy (XPS) analysis showed that SO2 does not affect the chemical nature of Ir0 under reaction conditions. However, SO2 can be oxidized to sulfate and deposit on the catalyst surface. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that the presence of SO2 can inhibit the CO + O2 reaction, thus leaving more CO available to reduce NOx over the active Ir0 sites. As a result, the reduction of NOx is remarkably promoted even in the presence of O2 and SO2.

Fe-nanocluster embedded biomass-derived carbon for efficient photo-Fenton-like activity in water purification

Single-atom catalysts (SACs) as photo-Fenton-like catalysts have attracted widespread attention in water purification. However, the development of SACs with renewability, cleanliness, high mass loading, and raw material abundance is a formidable challenge to achieve efficient pollutant removal. In this study, we fabricated high-performance Fe-nanocluster embedded biomass-derived carbon (Fe/Bio-C) from Ficus altissima wastes for quinolone antibiotics degradation. The high-angle annular dark-field scanning transmission electron microscopy with aberration correction (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that the Fe/Bio-C exhibited a porous structure with abundant Fe-N4 active sites. The Fe/Bio-C catalysts achieved an exceptional efficiency of 98.6 % for the removal of the representative quinolone antibiotic, namely lomefloxacin (LOM), within 30 min. Furthermore, an in-depth exploration was conducted to assess the influence of reaction parameters on degradation performance, kinetics, toxicity, and mechanism. The free radical quenching experiments and electron paramagnetic resonance (EPR) spectra demonstrated the existence of ·O2−, 1O2, ·OH, SO4·− in the reaction system and the ·O2− radicals played a relatively important role in the degradation progress. This work broaden the avenue for constructing metal-nanocluster photocatalysts with the high reactivity, low metal leaching, and universality to various pollutants.

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).

Accelerating nano-XANES imaging via feature selection

We utilize feature selection to reduce experimental time by ∼80% of a nanoscale X-ray Absorption Fine Structure (XANES) spectroscopy imaging study of a sample with Fe-bearing mineral phases.

Harmonic response of Gd-doped Mn-ferrite nanoparticles under AC magnetic field and optimization of Gd doping for MPI applications

This study synthesized Gd-doped Mn-ferrite nanoparticles for magnetic particle imaging (MPI) applications with doping levels (x) of 0, 0.05, 0.07, and 0.10. Analyses using X-ray diffraction measurements unequivocally confirmed the presence of a spinel-type crystal structure in the synthesized particles and X-ray absorption fine-structure spectroscopy confirmed the incorporation of Gd atoms in place of Mn within the crystal lattice. Magnetization and harmonic measurements under an AC magnetic field revealed that particles with a high initial permeability and low coercivity showed a high response intensity. Notably, particles possessing a Gd doping level of x = 0.07 displayed the highest response and were considered promising as MPI materials.

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.

Probing the Electrode-Liquid Interface Using Operando total-Reflection X-Ray Absorption Spectroscopy

Traditional operando methods to study electrochemical (EC) processes, although successful, are based on EC measurements, lacking in direct sensitivity of chemical and structural changes. A fundamental understanding of the underlying mechanism occurring during an EC reaction could allow to improve performances and properties of applied material systems. EC processes are localized at the electrode-electrolyte interfacial regions, but several surface sensitive experimental techniques are often limited to ex situ conditions, owing to the need of a Ultra High Vacuum (UHV) environment, e.g., Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Low Energy Electron Diffraction (LEED), etc.1 On the contrary, synchrotron-based hard x-rays provide an intense and highly energetic source that can penetrate the electrolyte without undergoing significant attenuation. Furthermore, the x-ray beam can be focused on a flat metal surface adopting a grazing incidence geometry, increasing surface sensitivity up to a few nanometers in subcritical condition. The latter case is achieved when the incident angle is set below the critical angle for total external reflection (TER), characterized by the occurrence of an evanescent wave confined at the surface. As a result, x-ray photon-in photon-out techniques can be used to probe the electrode-liquid interface in working conditions.2,3 In this contribution, we performed operando Grazing Incidence X-ray Absorption Spectroscopy (GI-XAS) in total external reflection (TER) mode4 (Fig. 1) at P64 (DESY, Hamburg), using our EC setup designed for multimodal studies with hard x-ray scattering and spectroscopy techniques3. XAS can provide unique information about the local chemical and structural environment of absorbing atoms during electrochemical polarization. The electro-oxidation of polycrystalline gold, relevant for the understanding of electrolysis, and the surface passive film development and breakdown of Ni-Cr-Mo corrosion resistant alloys, have been investigated. Despite the presence of the electrolyte and the PEEK walls of the EC cell, 1-3 nm thick surface oxides film can be detected in TER mode using energies down to 8 keV. Advantages and challenges of this method will be discussed showing experimental results. Figure 1 Left: Schematic of our EC cell showing sample geometry for GI-XAS in TER mode, the incidence angle q is always lower than the critical angle. Right: GI-XAS in TER mode from a Ni 59 alloy sample at the Ni k-edge at increasing EC polarization in 1M NaCl and pH 12. Maurice, V. Progress in corrosion science at atomic and nanometric scales. Progress in Materials Science 40 (2018).Timoshenko, J. & Roldan Cuenya, B. In Situ / Operando Electrocatalyst Characterization by X-ray Absorption Spectroscopy. Chem. Rev. 121, 882–961 (2021).Långberg, M. Redefining passivity breakdown of super duplex stainless steel by electrochemical operando synchrotron near surface X-ray analyses. npj Materials Degradation, 3(1): p. 22. (2019).D. Gajdek. Structural Changes in Monolayer Cobalt Oxides under Ambient Pressure CO and O 2 Studied by In Situ Grazing-Incidence X-ray Absorption Fine Structure Spectroscopy, J. Phys. Chem. C, vol. 126, n. 7, pagg. 3411–3418 (2022) Figure 1

Mixed-Dimensional Partial Dealloyed PtCuBi/C as High-Performance Electrocatalysts for Methanol Oxidation with Enhanced CO Tolerance.

Developing efficient electrocatalysts for methanol oxidation reaction (MOR) is crucial in advancing the commercialization of direct methanol fuel cells (DMFCs). Herein, carbon-supported 0D/2D PtCuBi/C (0D/2D PtCuBi/C) catalysts are fabricated through a solvothermal method, followed by a partial electrochemical dealloying process to form a novel mixed-dimensional electrochemically dealloyed PtCuBi/C (0D/2D D-PtCuBi/C) catalysts. Benefiting from distinctive mixed-dimensional structure and composition, the as-obtained 0D/2D D-PtCuBi/C catalysts possess abundant accessible active sites. The introduction of Cu as a water-activating element weakens the COads , and oxophilic metal Bi facilitates the OHads , thereby enhancing its tolerance to CO poisoning and promoting MOR activity. The X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS) collectively reveal the electron transfer from Cu and Bi to Pt, the electron-enrichment effect induced by dealloying, and the strong interactions among Pt-M (Cu, Pt, and Bi) multi-active sites, which improve the tuning of the electronic structure and enhancement of electron transfer ability. Impressively, the optimized 0D/2D D-PtCuBi/C catalysts exhibit the superior mass activity (MA) of 17.68 A mgPt -1 for MOR, which is 14.86 times higher than that of commercial Pt/C. This study offers a proposed strategy for Pt-based alloy catalysts, enabling their use as efficient anodic materials in fuel cell applications.

Handheld Crop Pest Sensor Using Binary Catalyst-Loaded Nano-SnO2 Particles for Oxidative Signal Amplification.

In agriculture, pest management is a major challenge. Crop releases volatiles in response to the pest; hence, sensing these volatile signals at a very early stage will ease pest management. Here, binary catalyst-loaded SnO2 nanoparticles of <5 nm were synthesized for the repeated capture and oxidation of the signature volatile and its products to amplify the chemoresistive signal to detect concentrations as low as ≈120 ppb. The sensitivity may be due to the presence of the elements in the Sn-Fe-Pt bond evidenced by extended X-ray absorption fine-structure spectroscopy (EXAFS) that captures and oxidize the volatile without escaping. This strong catalyst may oxidize nontarget volatiles and can cause false signals; hence, a molecular sieve filter has been coupled to ensure high selectivity for the detection ofTuta absolutainfestation in tomato. Finally, with the support of a mobile power bank, the optimized sensor has been assembled into a lightweight handheld device.

Dissolution behavior and aging of iron–uranium oxide

Understanding the dissolution behavior of the fuel debris is necessary for the safe decommissioning of Fukushima Daiichi Nuclear Power Plants. The dissolution behavior of FeUO4 compounds formed by a high-temperature reaction of UO2 with iron, a stainless-steel component of reactor structural materials, was investigated under atmospheric conditions. The compounds were prepared in an electric furnace using U3O8 and Fe3O4 as starting materials, and their solid states were analyzed using X-ray diffraction, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and X-ray absorption fine-structure spectroscopy. The fission products were produced via thermal-neutron irradiation. The concentration of nuclides dissolved in water was examined by performing static leaching tests of FeUO4 compounds for up to three months. A redox reaction was proposed to occur between trivalent Fe and pentavalent U ions in the early stage of FeUO4 dissolution. It was thermodynamically deduced that the reduced divalent Fe ion was finally oxidized into a trivalent ion in the presence of dissolved oxygen, and iron hydroxide limited the solubility of Fe. Meanwhile, the concentration of hexavalent U (i.e., uranyl ion) was limited owing to the presence of secondary minerals such as metaschoepite and sodium uranate and subsequently decreased, possibly owing to sorption on Fe oxides, for example. The concentrations of multivalent ions of fission products, such as Ru and Ce, also decreased, likely for the reason above. By contrast, the concentration of soluble Cs ions did not decrease. The validity of this interpretation was supported by comparing the results with the dissolution behavior of a reference sample (Fe-free U3O8).

Single-atom Pd anchored in the porphyrin-center of ultrathin 2D-MOFs as the active center to enhance photocatalytic hydrogen-evolution and NO-removal

Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis. However, how to prevent the aggregation of single atoms during the preparation and catalytic processes remained a great challenge. Herein, a novel ultrathin two-dimensional porphyrin-based single-atom photocatalyst Ti-MOF (abbreviated as TMPd) obtained through a simple hydrothermal synthesis strategy was used for photocatalytic hydrogen evolution and NO removal, in which the single-atom Pd tightly anchored in the center of porphyrin to ensure single-atom Pd stable existence. Compared with most reported MOFs-based photocatalysts, the TMPd showed an excellent hydrogen evolution rate (1.32 mmol g−1 h−1) and the NO removal efficiency (62%) under visible light irradiation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy (XAFS) proved that pd in TMPd existed in an isolated state, and the atomic force microscope (AFM) proved the ultrathin morphology of TMPd. DFT calculations had demonstrated that single-atom Pd could serve as the active center and more effectively achieve electron transfer, indicating that single-atom Pd played a vital role in photocatalytic hydrogen evolution. In addition, a possible photocatalytic pathway of NO removal was proposed based on ESR and in-situ infrared spectra, in which the catalysts anchored with single-atom Pd could produce more active substances and more effectively oxidize NO to NO2− or NO3−. The results suggested that coordinating single-atom metal species as the active site in the center of porphyrin could be a feasible strategy to obtain various ultrathin porphyrin-based single-atom photocatalysts to acquire excellent photocatalytic performance further.

Electrochemical growth of PAH-dendrimers supramolecular films. An integrated experimental-theoretical approach

The electrochemical oxidation of a polyphenylene-based dendrimer containing 96 sp2 carbon atoms (PPD) allows obtaining a more extended conjugated carbon framework, polymer PPD (pPPD), starting from the parent fused-benzene-based PPD. The structure and electronic properties of the polymeric thin film obtained by electrochemical oxidation have been characterized by Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy. Structural properties of the thin film formed upon electrochemical oxidation of PPD, are characterized by Matrix-Assisted Laser Desorption/Ionization (MALDI-TOF) and Gel-Permeation Chromatography (GPC) measurements. The degree of order of the layers as well as the virtual, and occupied, electronic states are addressed and exploited to obtain information on conjugation and oligomer size within the polymeric pPPD film. The experimental results are compared with DFT, B3LYP/6–31G(d), calculations. The overall results suggest that the thin film formed on the electrode surface is mainly formed by PPD dimer and trimer upon electrochemical oxidation.

In-depth study of the removal of Mn(II) by Fe(VI) treatment and the profound influence of NOM on floc formation and properties

The presence of manganese(II) in drinking water sources poses a significant treatment difficulty for water utilities, thus necessitating the development of effective removal strategies. Treatment by Fe(VI), a combined oxidant and coagulant, has been identified as a potential green solution; however, its effectiveness is hampered by natural organic matter (NOM), and this underlying mechanism is not fully understood. Here, we investigated the inhibitory effect of three different types of NOM, representing terrestrial, aquatic, and microbial origins, on Mn(II) removal and floc growth during Fe(VI) coagulation. Results revealed that Fe(VI) coagulation effectively removes Mn(II), but NOM could inhibit its effectiveness by competing in oxidation reactions, forming NOM-Fe complexes, and altering floc aggregation. Humic acid was found to exhibit the strongest inhibition due to its unsaturated heterocyclic species that strongly bond to flocs and react with Fe(VI). For the first time, this study has presented a comprehensive elucidation of the atomic-level structure of Fe(VI) hydrolysis products by employing Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS). Results demonstrated that NOM strengthened single-corner and double-corner coordination between FeO6 octahedrons that were consumed by Mn(II), resulting in an increased contribution of γ-FeOOH in the core-shell structure (γ-FeOOH shell and γ-F2O3 core), thereby inhibiting coagulation effects. Furthermore, NOM impeded the formation of stable manganite, resulting in more low-valence Mn(III) being incorporated in the form of an unstable intermediate. These findings provide a deeper understanding of the complex interplay between Fe coagulants, heavy metal pollution, and NOM in water treatment and offer insight into the limitations of Fe(VI) in practical applications.

Atomic scale structure and bond stretching force constants in stoichiometric and off-stoichiometric kesterites.

The deviation from stoichiometry and the understanding of its consequences are key factors for the application of kesterites as solar cell absorbers. Therefore, this study investigates the local atomic structure of off-stoichiometric Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and Cu2ZnGeSe4 (CZGSe) by means of Extended X-ray Absorption Fine Structure Spectroscopy. Temperature dependent measurements yield the bond stretching force constants of all cation-anion bonds in stoichiometric CZTS and CZTSe and nearly stoichiometric CZGSe. Low temperature measurements allow high precision analysis of the influence of off-stoichiometry on the element specific average bond lengths and their variances. The overall comparison between the materials is in excellent agreement with measures like ionic/atomic radii and bond ionicities. Furthermore, the small uncertainties allow the identification of systematic trends in the Cu-Se and Zn-Se bond lengths of CZTSe and CZGSe. These trends are discussed in context of the types and concentrations of certain point defects, which gives insight into the possible local configurations and their influence on the average structural parameters. The findings complement the understanding of the effect of off-stoichiometry on the local structure of kesterites, which affects their electronic properties and thus their application for solar cells.

Modulating the Coordination Environment of Carbon-Dot-Supported Fe Single-Atom Nanozymes for Enhanced Tumor Therapy.

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2 homolyticcleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.