Search Results (30)

The urgent need for sustainable CO₂ conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V_O-Bi₂WO₆ (FM/V_O-BWO) for photocatalytic CO₂ reduction. Positron annihilation lifetime spectroscopy (PALS) was employed to confirm the existence of oxygen vacancies, while spherical aberration-corrected transmission electron microscope (STEM) characterization verified the successful construction of heterointerfaces. X-ray absorption fine structure (XAFS) spectra confirmed that the defect configuration and heterostructure changed the surface chemical valence state. The optimized 1.0FM/V_O-BWO composite demonstrated exceptional photocatalytic performance, achieving CO and CH₄ yields of 60.48 and 4.3 μmol/g, respectively, under visible-light 11.8- and 1.5-fold enhancements over pristine Bi₂WO₆. The enhanced performance is attributed to oxygen vacancy-induced active sites facilitating CO₂ adsorption/activation. In situ molecular spectroscopy confirmed the formation of critical CO₂-derived intermediates (COOH* and CHO*) through surface interactions involving four-coordinated and two-coordinated hydrogen-bonded water molecules. Furthermore, the accelerated interfacial charge transfer efficiency mediated by the Z-scheme heterojunction has been conclusively demonstrated. This work establishes a paradigm for defect-mediated heterojunction design, offering a sustainable route for solar fuel production. Full article

The electrochemical carbon dioxide reduction reaction (CO₂RR) represents a promising approach for achieving CO₂ resource utilization. Carbon-based materials featuring single-atom transition metal-nitrogen coordination (M-N_x) have attracted considerable research attention due to their ability to maximize catalytic efficiency while minimizing metal atom usage. However, conventional synthesis methods often encounter challenges with metal particle agglomeration. In this study, we developed a Ni-doped polyvinylidene fluoride (PVDF) fiber membrane via electrospinning, subsequently transformed into a nitrogen-doped three-dimensional self-supporting single-atom Ni catalyst (Ni-N-CF) through controlled carbonization. PVDF was partially defluorinated and crosslinked, and the single carbon chain is changed into a reticulated structure, which ensured that the structure did not collapse during carbonization and effectively solved the problem of runaway M-Nx composite in the high-temperature pyrolysis process. Grounded in X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), nitrogen coordinates with nickel atoms to form a Ni-N structure, which keeps nickel in a low oxidation state, thereby facilitating CO₂RR. When applied to CO₂RR, the Ni-N-CF catalyst demonstrated exceptional CO selectivity with a Faradaic efficiency (FE) of 92%. The unique self-supporting architecture effectively addressed traditional electrode instability issues caused by catalyst detachment. These results indicate that by tuning the local coordination structure of atomically dispersed Ni, the original inert reaction sites can be activated into efficient catalytic centers. This work can provide a new strategy for designing high-performance single-atom catalysts and structurally stable electrodes. Full article

Two new Ag(I) complexes with coumaric carboxylic acid derivatives have been synthesized. Structural studies of these noncrystalline complexes have been performed using a methodology that combines laboratory and synchrotron techniques, supported by density functional theory calculations. The arrangement of ligands around the Ag(I) cation has been refined using infrared, extended X-ray absorption fine structure, and X-ray absorption near edge structure spectroscopies. Different coordination modes of carboxylate ligands are observed for the studied compounds. Carboxylate bridges are characteristic for the Ag(I) complex with 4-oxo-4H-1-benzopyran-2-carboxylic acid (1), while a bidentate chelating motif was found for the complex with 2-oxo-2H-1-benzopyran-3-carboxylic acid (2). Additionally, the carbonyl oxygen atom of the coumarin ring coordinates to the silver cation in complex 2, while it is inactive in complex 1. Antimicrobial evaluation has been performed for both compounds. The complexes show activity against selected bacteria as well as Candida yeast. This activity is slightly lower for bacteria and the same or higher for Candida in relation to the reference substances: ciprofloxacin or fluconazole. Full article

X-ray absorption fine structure (XAFS) spectroscopy, temperature-programmed reduction (TPR), and temperature-programmed hydride decomposition (TPHD) were employed to elucidate the structures of a series of PdRe/Al₂O₃ bimetallic catalysts for the selective hydrogenation of furfural. TPR evidenced low-temperature Re reduction in the bimetallic catalysts consistent of the migration of [ReO₄]⁻ (perrhenate) species to hydrogen-covered Pd nanoparticles on highly hydroxylated γ-Al₂O₃. TPHD revealed a strong suppression of β-PdH_x formation in the reduced catalysts prepared by (i) co-impregnation and (ii) [HReO₄] impregnation of the reduced Pd/Al₂O₃, indicating the formation of Pd-rich alloy nanoparticles; however, reduced catalysts prepared by (iii) [Pd(NH₃)₄]²⁺ impregnation of calcined Re/Al₂O₃ and subsequent re-calcination did not. Re L_III X-ray absorption edge shifts were used to determine the average Re oxidation states after reduction at 400 °C. XAFS spectroscopy and high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM) revealed that a reduced 5 wt.% Re/Al₂O₃ catalyst contained small Re clusters and nanoparticles comprising Re atoms in low positive oxidation states (~1.5+) and incompletely reduced Re species (primarily Re⁴⁺). XAFS spectroscopy of the bimetallic catalysts evidenced Pd-Re bonding consistent with Pd-rich alloy formation. The Pd and Re total first-shell coordination numbers suggest that either Re is segregated to the surface (and Pd to the core) of alloy nanoparticles and/or segregated Pd nanoparticles are larger than Re nanoparticles (or clusters). The Cowley short-range order parameters are strongly positive indicating a high degree of heterogeneity (clustering or segregation of metal atoms) in these bimetallic catalysts. Catalysts prepared using the Pd(NH₃)₄[ReO₄]₂ double complex salt (DCS) exhibit greater Pd-Re intermixing but remain heterogeneous on the atomic scale. Full article

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. Full article

During the methanol-to-aromatics (MTA) process, a large amount of water is generated, while the influence and mechanism of water on the activity and selectivity of the light olefin aromatization reaction are still unclear. Therefore, a study was conducted to systematically investigate the effects of water on the reactivity and the product distribution in ethylene aromatization using infrared spectroscopy (IR), intelligent gravitation analyzer (IGA), and X-ray absorption fine structure (XAFS) characterizations. The results demonstrated that the presence of water reduced ethylene conversion and aromatic selectivity while increasing hydrogen selectivity at the same contact time. This indicated that water had an effect on the reaction pathway by promoting the dehydrogenation reaction and suppressing the hydrogen transfer reaction. A detailed analysis using linear combination fitting (LCF) of Zn K-edge X-ray absorption near-edge spectroscopy (XANES) on Zn/HZSM-5 catalysts showed significant variations in the state of existence and the distribution of Zn species on the deactivated catalysts, depending on different reaction atmospheres and water contents. The presence of water strongly hindered the conversion of ZnOH⁺ species, which served as the active centers for the dehydrogenation reaction, to ZnO on the catalyst. As a result, the dehydrogenation activity remained high in the presence of water. This study using IR and IGA techniques revealed that water on the Zn/HZSM-5 catalyst inhibited the adsorption of ethylene on the zeolite, resulting in a noticeable decrease in ethylene conversion and a decrease in aromatic selectivity. These findings contribute to a deeper understanding of the aromatization reaction process and provide data support for the design of efficient aromatization catalysts. Full article

In this paper, a relationship between the structure and the electrical properties of a nanocrystalline composite ceramics xNa₂O·(100 − x)V₂O₅ with ‘x’ of 5, 15, 25, 35, and 45 mol%, abbreviated as xNV, was investigated by X-ray diffractometry (XRD), X-ray absorption spectroscopy (XAS), Cyclic Voltammetry (CV), Electrochemical impedance spectroscopy (EIS), and cathode active performance in Na-ion battery (SIB). For the expected sodium vanadium bronzes (Na_xV₂O₅) precipitation, the preparation of xNV was performed by keeping the system in the molten state at 1200 °C for one hour, followed by a temperature decrease in the electric furnace to room temperature at a cooling rate of 10 °C min⁻¹. XRD patterns of the 15NV ceramic exhibited the formation of Na_0.33V₂O₅ and NaV₃O₈ crystalline phases. Moreover, the V K-edge XANES showed that the absorption edge energy of ceramics 15NV recorded at 5479 eV is smaller than that of V₂O₅ at 5481 eV, evidently indicating a partial reduction from V⁵⁺ to V⁴⁺ due to the precipitation of Na_0.33V₂O₅. In the cyclic voltammetry, reduction peaks of 15NV were observed at 1.12, 1.78 V, and 2.69 V, while the oxidation peak showed up only at 2.36 V. The values of the reduction peaks were related to the NaV₃O₈ crystalline phase. Moreover, the diffusion coefficient of Na⁺ (D_Na⁺) gradually decreased from 8.28 × 10⁻¹¹ cm² s⁻¹ to 1.23 × 10⁻¹² cm² s⁻¹ with increasing Na₂O content (x) from 5 to 45 mol%. In the evaluation of the active cathode performance of xNV in SIB, ceramics 15NV showed the highest discharge capacity 203 mAh g⁻¹ at a current rate of 50 mA g⁻¹. In the wider voltage range from 0.8 to 3.6 V, the capacity retention was maintained at 50% after 30 cycles, while it was significantly improved to 90% in the narrower voltage range from 1.8 to 4.0 V, although the initial capacity decreased to 56 mAh g⁻¹. It is concluded that the precipitation of the Na_0.33V₂O₅ phase improved the structural and electrical properties of 15NV, which provides a high capacity for the Na-ion battery when incorporated as a cathode active material. Full article

The influence of Yb³⁺ cations substitution for Pr³⁺ on the structure and catalytic activity of (Pr_1−xYb_x)₂Zr₂O₇ powders synthesized via coprecipitation followed by calcination is studied using a combination of long- (s-XRD), medium- (Raman, FT-IR, and SEM-EDS) and short-range (XAFS) sensitive methods, as well as adsorption and catalytic techniques. It is established that chemical composition and calcination temperature are the two major factors that govern the phase composition, crystallographic, and local-structure parameters of these polycrystalline materials. The crystallographic and local-structure parameters of (Pr_1−xYb_x)₂Zr₂O₇ samples prepared at 1400 °C/3 h demonstrate a tight correlation with their catalytic activity towards propane cracking. The progressive replacement of Pr³⁺ with Yb³⁺ cations gives rise to an increase in the catalytic activity. A mechanism of the catalytic cracking of propane is proposed, which considers the geometrical match between the metal–oxygen (Pr–O, Yb–O, and Zr–O) bond lengths within the active sites and the size of adsorbed propane molecule to be the decisive factor governing the reaction route. Full article

Asymmetry, such as non-centrosymmetry in the crystal or chiral structure and local symmetry breaking, plays an important role in the discovery of new phenomena. The honeycomb structure is an example of an asymmetric structure. Ce${}_2$Pt${}_6$Al${}_{15}$ is a candidate for a frustrated system with honeycomb Ce-layers, which have been reported to show near the quantum critical point. However, the ground state of Ce${}_2$Pt${}_6$Al${}_{15}$ depends on the sample, and analysis of the crystal structure is difficult due to the presence of stacking disorder. We synthesized polycrystalline Ce${}_2$Pt${}_6$Al${}_{15}$ using arc melting method (AM-Ce${}_2$Pt${}_6$Al${}_{15}$) and single-crystalline Ce${}_2$Pt${}_6$Al${}_{15}$ using flux method (F-Ce${}_2$Pt${}_6$Al${}_{15}$). The prepared samples were characterized by electron probe micro-analysis (EPMA), single and powder X-ray diffraction methods, measured magnetic properties and X-ray absorption spectroscopy (XAS). The composition ratio of AM-Ce${}_2$Pt${}_6$Al${}_{15}$ was stoichiometric, although it contained a small amount (i.e., a few percent) of the impurity Ce${}_2$Pt${}_9$Al${}_{16}$. Meanwhile, the composition ratio of F-Ce${}_2$Pt${}_6$Al${}_{15}$ deviated from stoichiometry. The X-ray absorption fine structure (XAFS) spectrum of AM-Ce${}_2$Pt${}_6$Al${}_{15}$ at the Ce L${}_3$-edge was similar to that of CeF${}_3$, which possesses the Ce${}^{3+}$ configuration, indicating that the valence of Ce in Ce${}_2$Pt${}_6$Al${}_{15}$ is trivalent; this result is consistent with that for the magnetic susceptibility. To determine the precise structure, we analyzed the extended X-ray absorption fine structure (EXAFS) spectra of Ce L${}_3$- and Pt L${}_3$-edges for Ce${}_2$Pt${}_6$Al${}_{15}$, and found that the EXAFS spectra of Ce${}_2$Pt${}_6$Al${}_{15}$ can be explained not as a hexagonal Sc${}_{0.6}$Fe${}_2$Si${}_{4.9}$-type structure but, instead, as an orthorhombic structure with honeycomb structure. Full article

New azomethine compounds of 2-(N-tosylamino)benzaldehyde or 5-chloro-2-(N-tosylamino)benzaldehyde and the corresponding chlorine-substituted anilines, zinc(II) complexes based on them have been synthesized. The structures of azomethines and their complexes were determined by elemental analysis, IR, ¹H NMR, X-ray spectroscopy, and X-ray diffraction. It is found that all ZnL₂ complexes have a tetrahedral structure according to XAFS and X-ray diffraction data. The photoluminescent properties of azomethines and zinc complexes in methylene chloride solution and in solid form have been studied. It is shown that the photoluminescence quantum yields of solid samples of the complexes are an order of magnitude higher compared to the solutions and range from 11.34% to 48.3%. The thermal properties of Zn(II) complexes were determined by thermal gravimetric analysis (TGA) and differential scanning calorimetry. The TGA curves of all the compounds suggest their high thermal stability up to temperatures higher than 290 °C. The electrochemical properties of all complexes were investigated by the cyclic voltammetry method. The multilayered devices ITO/PEDOT:PSS/NPD/Zn complex/ TPBI/LiF/Al with wide electroluminescence (EL) color range spanning the range from bluish-green (494 nm) to green (533 nm) and the high values of brightness, current and power efficiency were fabricated. The biological activity of azomethines and zinc complexes has been studied. In the case of complexes, the protistocidal activity of the zinc complex with azomethine of 5-chloro-2-(N-tosylamino)benzaldehyde with 4-chloroaniline was two times higher than the activity of the reference drug toltrazuril. Full article

Thermophotovoltaic conversion using heat to generate electricity in photovoltaic cells based on the detraction of thermal radiation suffers from many engineering challenges. The focus of this paper is to study the nanostructure of AlGaAsSb for thermophotovoltaic energy conversion using lattice-matched heterostructures of GaSb-based materials in order to overcome the current challenges. The XAFS spectroscopy technique was used to analyze electronic structures and optical properties of GaSb, (Al, In) GaSbAs. The XAFS spectroscopy analysis showed a powerful decay at peak intensity that reveals to be related to a loss in Sb amount and light As atoms replaced in Sb atoms by 25%. Moreover, it was found that Al/In doped samples have highly symmetric data features (same atomic species substitution). The narrow direct bandgap energy, E_g of Al_0.125Ga_0.875Sb_0.75As_0.25 material raised (0.4–0.6 eV) compared to conventional photovoltaic cell bandgap energy (which is generally less than 0.4 eV) with weak absorption coefficients. The thermoelectric properties of AlGaAsSb computed via Botlztrap code showed that the electrons made up the majority of the charge carriers in AlGaAsSb. This nanostructure material exhibited a higher and acceptable figure of merit and demonstrated a promising thermoelectric material for solar thermophotovoltaic applications. Full article

The effect of synthesis conditions on the features of the long- and short-range order of Ln${}_2$(WO${}_4$)${}_3$ (Ln = Gd, Dy, Ho, Yb) powders synthesized via coprecipitation of salts has been studied by a complex of physico-chemical techniques including synchrotron X-ray powder diffraction, X-ray absorption spectroscopy, Raman and infrared spectroscopy, and simultaneous thermal analysis. It was found that crystallization of amorphous precursors begins at 600 °C/3 h and leads to the formation of the monoclinic structure with sp. gr. C12/c1(15) for Ln${}_2$(WO${}_4$)${}_3$ (Ln = Gd, Dy) and with sp. gr. P12${}_1$/a1(14) for Ln = Yb, whereas crystallization of Ho precursor requires even higher temperature. After annealing at 1000 °C, the P12${}_1$/a1(14) phase becomes the dominant phase component for all heavy lanthanoid types except for Ln = Gd. It was shown that the Ln (Ln = Dy, Ho, and Yb) tungstates with the P12${}_1$/a1(14) monoclinic structure correspond to trihydrates Ln${}_2$(WO${}_4$)${}_3$·3H${}_2$O formed due to a rapid spontaneous hydration under ambient conditions. It was concluded that the proneness to hydration is due to a specific structure of the P12${}_1$/a1(14) phase with large voids available to water molecules. Modifications in the local structure of Ln-O coordination shell accompanying the structure type change and hydration are monitored using EXAFS spectroscopy. Full article

As a core component of the X-ray absorption fine structure spectroscopy (XAFS) system, the multi-channel double-crystal monochromator (DCM) can improve the time resolution of the system significantly. In contrast to the conventional single-channel DCM, the multi-channel DCM includes more pairs of crystals that are located separately in the master and slave motor axis with the same driving direction. However, a mismatched parallelism in the pitch direction, which can result from the manual mounting operation between the two separated crystals, directly affects the performance of the flux and the angular stability of the monochromatic beam. This poses a significant challenge to the precision position tracking of this system. In this paper, the mounting errors were translated into repetitive errors in the slave motor when the master motor was rotated at a constant velocity. Therefore, the iterative learning control (ILC) was considered in order to improve the tracking accuracy of the slave motor motion. The zero-magnitude error controller (ZMETC) was used to calculate the learning function to accelerate the convergence of the control inputs, and the convergence conditions of the control signal and error were also given. To validate the effectiveness of the proposed method, comparative experiments were performed on the motor motion platform. Experimental results indicated that the ILC effectively decreased the parallelism errors of the multi-channel DCM under various trajectories by comparing them with feedback controllers and the ZMETC, respectively. Full article

Methane reforming with carbon dioxide (DRM) is one promising way to achieve carbon neutrality and convert methane to syngas for high-value chemical production. Catalyst development with better performance is the key to its potential large-scale industrial application due to its deactivation caused by carbon deposition and metal sintering. Hence, a Ni/CeO₂ catalyst (Ni/CeO₂-M) with higher CO₂ conversion and better stability is prepared, supported on CeO₂ precipitated via a novel microimpinging stream reactor. A series of ex-situ or in-situ characterizations, such as CO titration measurements, two-step transient surface reaction (two-step TSR), CO₂ and CH₄ temperature-programmed surface reaction (CO₂-TPSR and CH₄-TPSR), X-ray absorption fine structure (XAFS), and in-situ Raman spectroscopy study, were used to investigate its structure and mechanism. In contrast to Ni supported on commercial CeO₂ (Ni/CeO₂-C), the Ni/CeO₂-M catalyst with stronger lattice oxygen mobility and higher oxygen storage capacity enhances its CO₂ activation ability and carbon deposition. The Ni particle size of the Ni/CeO₂-M catalyst decreased, and a higher oxidation state was obtained due to the strong metal–support interaction. Besides the reaction performance improvement of the Ni/CeO₂-M catalyst, the novel microimpinging stream reactor could achieve catalyst continuous production with a high preparation efficiency. This work provides a novel method for the high-performance catalyst preparation for DRM reaction and its mechanism study gives a deep insight into high-performance catalyst development via bottom-up study. Full article

Alkaline niobate and tantalate perovskites have attracted attention as polar dielectrics for electronics and telecommunications. Here, we studied the polar behaviour, lattice dynamics, and local structure in conventionally processed K_0.985Mn_0.015TaO_3±δ ceramics using a combination of variable-temperature dielectric and Raman spectroscopies, and X-ray absorption fine structure (XAFS) measurements, respectively. Mn doping induces a low-frequency dielectric relaxation in KTaO₃ (KT), which follows the Arrhenius law with an activation energy U ≈ 105 meV and the characteristic relaxation time τ₀ ≈ 4.6 × 10⁻¹⁴ s. Our XAFS results support preferential Mn occupancy of the cuboctahedral sites as Mn²⁺, with these cations strongly off-centred in the oversized oxygen cages. Such disordered Mn displacements generate electric dipoles, which are proposed as the source of the observed dielectric relaxation. We show that in Mn-doped ceramics, the low-frequency polar TO1 mode softens on cooling and, at low temperatures, exhibits a higher frequency than in undoped KT. This mode displays no detectable splitting, which contrasts with Li-doped KT that also contains off-centred Li⁺ species on the cuboctahedral sites. Therefore, we conclude that the coupling between the Mn displacements and the lattice is weaker than in the Li case, and Mn-doped KT therefore exhibits a dielectric relaxation but no ferroelectric transition. Full article