Oxidation State Research Articles

Exploring Reversible Redox Behavior in the 6H-BaFeO3-δ (0 < δ < 0.4) System: Impact of Fe3+/Fe4+ Ratio on CO Oxidation.

This work is devoted to evaluating the relationship between the oxygen content and catalytic activity in the CO oxidation process of the 6H-type BaFeO3-δ system. Strong evidence is provided about the improvement of catalytic performance with increasing Fe average oxidation state, thus suggesting the involvement of lattice oxygen in the catalytic process. The compositional and structural changes taking place in both the anionic and cationic sublattices of the catalysts during redox cycles have been determined by temperature-resolved neutron diffraction. The obtained results evidence a structural transition from hexagonal (P63/mmc) to orthorhombic (Cmcm) symmetry. This transition is linked to octahedra distortion when the Fe3+ concentration exceeds 40% (δ values higher than 0.2). The topotactical character of the redox process is maintained in the δ range 0 < δ < 0.4. This suggests that the cationic framework is only subjected to slight structural modifications during the oxygen exchange process occurring during the catalytic cycle.

Probing the Interfacial Molecular Structure of a Co‐Prussian Blue In Situ

AbstractMolecular‐level insight into the interfacial composition of electrodes at the solid‐electrolyte and the solid‐electrode interface is essential to understanding the charge transfer processes, which are vital for electrochemical (EC) and photoelectrochemical (PEC) applications. However, spectroscopic access to both interfaces, particularly upon application of an external bias, remains a challenge. Here, in situ surface sensitive vibrational sum‐frequency generation (VSFG) spectroscopy is used for the first time to directly access the interfacial structure of a cobalt‐containing Prussian blue analog (Co‐PBA) in contact with the electrolyte and TiO2/Au surface. Structural and compositional changes of the Prussian blue layer during electrochemical oxidation are studied by monitoring the stretching vibration of the CN group. At open circuit potential, VSFG reveals a non‐homogeneous distribution of oxidation states of metal sites: FeIII–CN–CoII and FeII–CN–CoIII coordination motifs are dominantly observed at the Co‐PBA|TiO2 interface, while it is only the FeII–CN–CoII unit at the electrolyte interface. Upon increasing the potential applied to the electrode, the partial oxidation of FeII–CN–CoII to FeIII–CN–CoII is observed followed by its transformation to FeII–CN–CoIII via charge transfer and, finally, the formation of FeIII–CN–CoIII species at the interface with TiO2 and the electrolyte.

Electronic Delocalization and σ-Aromaticity in Heterometallic Cluster with Multiple Thorium-Palladium Bonds.

Research on metal-metal bonds involving f-block actinides, such as thorium, lags far behind the well-studied metal-metal bonds of d-block transition metals. The complexes with Th-TM bonds are extremely rare; all previously identified examples have only a single Th-TM bond with the Th center at an invariably +IV oxidation state. Herein, we report a series of Th2Pdn (n = 2, 3, and 6) clusters (complexes 3, 4, and 7) with multiple Th(III)-Pd bonds. Theoretical studies reveal that the Th2Pdn unit allows electronic delocalization and σ aromaticity, leading to unexpected closed-shell singlet structures for these Th(III) species. This electronic delocalization is evident in the highest occupied molecular orbital of Th(III) complexes and facilitates a 2e reduction of alkyne by complex 7, resulting in the formation of 8. Complexes 7 and 8 are distinctive in featuring a Th2Pd6 core with six and eight Th-Pd bonds, respectively, making them the largest known d-f heterometallic clusters exhibiting metal-metal bonding.

New spin-electronics compositions: Large ferromagnetic order of BaSn0.98-xFe0.02CuxO3 (x = 0.02, 0.04, 0.06) semiconductor

Inducing robust ferromagnetic order in dilute magnetic semiconductor materials is an essential topic for spin-based electronics devices. Herein, the escalating concentration of nonmagnetic Cu ions was employed to strongly reinforce the room temperature ferromagnetism of 2% Fe doped BaSnO3 structure. BaSn0.98-xFe0.02CuxO3 (x = 0.02, 0.04 or 0.06) compositions were prepared by adapted sol gel method. In all compositions, pure single phase with cubic structure of BaSnO3 was identified by the X-ray diffraction (XRD) technique. Pure BaSnO3 gives a band gap energy of 3.25 eV which red shifted to 3.1, 3.12 and 3.13 eV after incorporation of (2% Fe, 2% Cu), (2% Fe, 4% Cu) and (2% Fe, 6% Cu) ions, respectively. The scanning electron microscope (SEM) images reflects that the Fe/Cu blends obstruct the grains growth of BaSnO3 and also influenced on the particles shape and porosity. The energy dispersive X-ray (EDX) maps confirmed the homogenous spatial distribution of Fe and Cu in the codoped BaSnO3 structure. The X-ray photoelectron spectroscopy (XPS) results of BaSn0.92Fe0.02Cu0.06O3 prove that Ba, Sn, O, Fe and Cu elements possess the oxidation states of +2, +4, −2, +3 and +1/+2, respectively. The magnetic performance of BaSnO3 structure exhibits a minor ferromagnetic loop with measured coercivity (Hc) of 330 Oe, magnetization (Ms) of 0.0023 emu/g and retentivity of 0.00077 emu/g. Interestingly, the addition of 6 wt% Cu (nonmagnetic dopant) plus 2 wt% Fe (magnetic dopant) strongly boosts the saturation magnetization value of BaSnO3 to 1.85 emu/g. The results open the door to tune the ferromagnetic order of BaSnO3 using nonmagnetic dopant to avoid the formation of magnetic impurities. The F-center exchange interaction and the bound magnetic polarons model were used to explain the measured room temperature ferromagnetism.

WLI, XPS and SEM/FIB/EDS Surface Characterization of an Electrically Fluted Bearing Raceway

Electrical bearing currents may disturb the performance of the bearings via electro-corrosion if they surpass a limit of ca. 0.1 to 0.3 A/mm2. A continuous current flow, or, after a longer time span, an alternating current or a repeating impulse-like current, damages the raceway surface, leading in many cases to a fluting pattern on the raceway. Increased bearing vibration, audible noise, and decreased bearing lubrication as a result may demand a replacement of the bearings. Here, an electrically corroded axial ball bearing (type 51208) with fluting patterns is investigated. The bearing was lubricated with grease lubrication and was exposed to 4 A DC current flow. It is shown that the electric current flow causes higher concentrations of iron oxides and iron carbides on the bearing raceway surface together with increased surface roughness, leading to a mixed lubrication also at elevated bearing speeds up to 1500 rpm. The “electrically insulating” iron oxide layer and the “mechanically hard” iron carbide layer on the bearing steel are analysed by WLI, XPS, SEM, and EDS. White Light Interferometry (WLI) is used to provide an accurate measurement of the surface topography and roughness. X-ray Photoelectron Spectroscopy (XPS) measurements are conducted to analyze the chemical surface composition and oxidation states. Scanning Electron Microscopy (SEM) is applied for high-resolution imaging of the surface morphology, while the Focused Ion Beam (FIB) is used to cut a trench into the bearing surface to inspect the surface layers. With the Energy Dispersive X-ray spectrometry (EDS), the presence of composing elements is identified, determining their relative concentrations. The electrically-caused iron oxide and iron carbide may develop periodically along the raceway due to the perpendicular vibrations of the rolling ball on the raceway, leading gradually to the fluting pattern. Still, a simulation of this vibration-induced fluting-generation process from the start with the first surface craters—of the molten local contact spots—to the final fluting pattern is missing.

Ammonia decomposition over vanadium oxide supported Ni catalyst for hydrogen production

The performance of vanadium oxides as support is investigated to develop a new nickel catalyst for ammonia decomposition to produce hydrogen. The catalytic activity is in the order of Ni/V2O3 > Ni/VO2 > Ni/V2O5, depending on the oxidation states of vanadium oxide. The VOx supports in all of the spent catalysts are V2O3, suggesting that V2O3 is the stable phase of VOx support during the ammonia decomposition. 3 wt%Ni/V2O3 gives an ammonia conversion of 38.3% (SV = 3000 L kg−1h−1) at 530 °C. Excellent active sites with a TOF of 33.6 s−1 at 500 °C form on 3 wt%Ni/V2O3. Ni/VOx works effectively as a catalyst for ammonia decomposition to produce hydrogen.

Microbe-Derived Antioxidants Protect IPEC-1 Cells from H2O2-Induced Oxidative Stress, Inflammation and Tight Junction Protein Disruption via Activating the Nrf2 Pathway to Inhibit the ROS/NLRP3/IL-1β Signaling Pathway.

Oxidative stress can induce inflammation and tight junction disruption in enterocytes. The initiation of inflammation is thought to commence with the activation of the ROS/NLRP3/IL-1β signaling pathway, marking a crucial starting point in the process. In our previous studies, we found that microbe-derived antioxidants (MAs) showed significant potential in enhancing both antioxidant capabilities and anti-inflammatory effects. The main aim of this research was to investigate the ability of MAs to protect cells from oxidative stress caused by H2O2, to reduce inflammatory responses, and to maintain the integrity of tight junction proteins by modulating the ROS/NLRP3/IL-1β signaling pathway. IPEC-1 cells (1 × 104 cells/well) were initially exposed to 100 mg/L of MAs for 12 h, after which they were subjected to 1 mM H2O2 treatment for 1 h. We utilized small interfering RNA (siRNA) to inhibit the expression of NLRP3 and Nrf2. Inflammatory factors such as IL-1β and antioxidant enzyme activity levels were detected by ELISA. Oxidative stress marker ROS was examined by fluorescence analysis. The NLRP3/IL-1β signaling pathway, Nrf2/HO-1 signaling pathway and tight junction proteins (ZO-1 and Occludin) were detected by RT-qPCR or Western blotting. In our research, it was observed that MA treatment effectively suppressed the notable increase in H2O2-induced inflammatory markers (TNF-α, IL-1β, and IL-18), decreased ROS accumulation, mitigated the expression of NLRP3, ASC, and caspase-1, and promoted the expression of ZO-1 and Occludin. After silencing the NLRP3 gene with siRNA, the protective influence of MAs was observed to be linked with the NLRP3 inflammasome. Additional investigations demonstrated that the treatment with MAs triggered the activation of Nrf2, facilitating its translocation into the nucleus. This process resulted in a notable upregulation of Nrf2, NQO1, and HO-1 expression, along with the initiation of the Nrf2-HO-1 signaling pathway. Consequently, there was an enhancement in the activities of antioxidant enzymes like SOD, GSH-Px, and CAT, which effectively mitigated the accumulation of ROS, thereby ameliorating the oxidative stress state. The antioxidant effectiveness of MAs was additionally heightened in the presence of SFN, an activator of Nrf2. The antioxidant and anti-inflammatory functions of MAs and their role in regulating intestinal epithelial tight junction protein disruption were significantly affected after siRNA knockdown of the Nrf2 gene. These findings suggest that MAs have the potential to reduce H2O2-triggered oxidative stress, inflammation, and disruption of intestinal epithelial tight junction proteins in IPEC-1 cells. This reduction is achieved by blocking the ROS/NLRP3/IL-1β signaling pathway through the activation of the Nrf2 pathway.

Effect of annealing temperature on the properties and the chromium oxidation state of ZnAl1.94Cr0.06O4 nanoparticles prepared by coprecipitation method

Nanostructured materials doped with Cr+3 have potential applications. However, it has been reported that heat treatment can modify the oxidation state of Cr+3, resulting in the formation of toxic Cr+6 in host matrices such as TiO2, Al2O3, SiO2, ZrO2, and Fe(OH)3. The possibility of this occurrence in nanostructured ZnAl2O4:Cr+3 has not been previously considered. In this study, we report the effect of annealing temperatures within the range of 600–1300 °C on the structure, morphology, optical properties, and, more specifically, the chromium oxidation state of ZnAl1.94Cr0.06O4 nanoparticles obtained through the coprecipitation method. The obtention of single-phase systems with a crystal size ranging from 5.25 nm to 142.75 nm was determined by X-ray diffraction and Rietveld refinement. At 800 °C, a more significant oxidation of Cr+3 was observed, evident in the increased absorption intensity of UV–vis bands associated with Cr+6 and a reduction in magnetic susceptibility at ambient temperature. At 1200 °C, a complete reduction of Cr+6 occurred, leading to the appearance of bands related to Cr+3 in the UV–vis absorption spectra and increased magnetic susceptibility; the results were confirmed by X-ray photoelectron spectroscopy. The outcomes of this study offer new insights into the thermal stability of chromium in ZnAl2O4 nanoparticles.

The investigation of thickness-dependent mono-fractal, optical and optoelectronics properties of sputtered silver thin film for silicon solar cell

Here we report, the room temperature deposition of silver (Ag) thin films on silicon, glass and silicon solar cell substrates by magnetron sputtering. The effect of thickness on the deposited thin films and their morphological, fractal, optical and solar cell parameters have been extensively investigated. AFM results show that the Ag thin films are composed of different-size of nano-grains and the grain size increases with increasing thickness. Mono-fractal parameters, namely fractal dimension (Df) and Hurst exponent (H), were determined from the power spectral density function. X-ray photoelectron spectroscopy studies indicate that the deposited samples exhibit the presence of oxidation state of Ag (0) in thin films, confirming the stable structure. The optical analysis shows that the transmittance of the deposited thin films decreases with increasing thickness, on the other hand, the silver thin film with thickness of 20 nm shows surface Plasmon resonance (SPR) at 436 nm. Current-voltage (I–V) curves were measured in dark and under illumination mode at standard testing conditions, i.e., 300K, 1000 W/m2 and 1.5 AM global using a solar simulator. These measurement studies indicate that thicknesses are effectively impacts on photovoltaic performance. The calculated values of change in solar efficiency (Δη) are 0.26, −0.20, −0.76 and −6.88 % for thin films with nominal thickness 0.5, 1, 2 and 20 nm respectively.

Supersymmetric index for small black holes

Supersymmetric elementary string states in the compactified heterotic string theory are described by small black holes that have zero area event horizon. In this paper we compute the supersymmetric index of such elementary string states using gravitational path integral. The dominant contribution to the path integral comes from an Euclidean rotating black hole solution of the supergravity theory with a finite area event horizon, but the logarithm of the index, computed from the saddle point, vanishes. Nevertheless we show that the solution is singular on certain subspaces of the horizon where higher derivative corrections can be important, and once the higher derivative corrections are taken into account the solution could yield a finite result for the logarithm of the index whose form agrees with the microscopic results up to an overall numerical constant. While the numerical constant is not determined in our analysis, we show that it is independent of the details of the compactification and even the number of non-compact dimensions, in agreement with the microscopic results.

Synthesis and characterization of absorption-enhanced alumina solid particle materials for direct irradiation solar-thermal conversion

Based on solar-thermal application more than 1000 °C, a novel combination of sol-gel synthesis and stepwise calcination to prepare metal-ion doped alumina composite particles as heat transfer media were proposed, enhancing solar energy absorption and lowering preparation temperature. Investigations focused on the elemental distribution, phase composition, oxidation states, optical properties and thermal stability of the composites, which were doped with Cr, Co, Cu, Fe, and Mn metal ions in a 100:5 M ratio. The first-principles calculations elucidate the mechanism behind the impact of transition metal ions on alumina’s optical properties. Results show that introducing a small quantity of metal atoms results in new impurity energy levels and electron states around EF = 0. Specifically, the band gap energy of Cu- and Mn–Al2O3 decreases from 6.017 eV to 4.464 eV and 2.170 eV, respectively. Correspondingly, the absorptivity of these composite particles increases from around 20 %–76.6 %. And Tauc analysis indicates a decrease in the optical band gap of the particle materials from 5.37 eV to a range of 2.88–4.90 eV. Additionally, doping with Mn, Fe, and Cu accelerates the in-situ formation of α-Al2O3 crystals, with a phase transition temperature below 1000 °C and a crystallinity exceeding 93 %. Thermal stability tests show that the particles are highly stable, exhibiting a mere 0.49 % mass change between 30 °C and 1200 °C. The stepwise inert annealing strategy and metal-iron doping positively influence the optical performance of alumina, synthesizing long-term high-temperature stable alumina ceramic particles with absorptance enhancement and a low α-Al2O3 phase transition temperature. These attributes make a favorable choice for solar-thermal applications in direct irradiation.

Design and Development of Sustainable Cu2 (II)- and Mn2 (III)-Embedded Bifunctional Electrocatalysts: Enhanced Hydrogen and Oxygen Generation.

Nowadays, environmentally friendly, low-cost-effective, and sustainable electrocatalysts used widely for hydrogen and oxygen evolution reactions have come into the limelight as a new research topic for scientists. This study highlights the preparation of two unique and symmetrical dinuclear Cu (II) and Mn (III) bifunctional catalysts by a facile simple slow evaporation and diffusion route. [C32H24Cu2F4N4O4] (1) and [C32H24Mn2F4N4O4] (2) both have monoclinic (C2/c (15)) crystal systems, with oxidation states +2 and +3, respectively. Prominent SPR peaks at 372 and 412 nm indicate an M-L charge transfer transition in both complexes. The synthesized electrocatalysts display exceptional catalytic activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Complex 1 exhibits enhanced hydrogen generation in 0.5 M H2SO4 with a small overpotential of 216 mV at -10 mA cm-2 along with a significantly lower Tafel value of 97 mV/dec compared to Complex 2. Moreover, Complex 1 is highly active for the OER in 1 M KOH with a small Tafel slope of 103 mV/dec and a low overpotential of 340 mV to acquire 10 mA cm-2 current density, compared to Complex 2. Complex 1 and Complex 2 remain stable up to 20 h in acidic electrolyte and up to 36 h and 20 h in the basic electrolyte, respectively.

Laser-assisted synthesis of MnOx and 3D graphene composites for wide-voltage flexible planar microcapacitors

Herein, we propose a simple and eco-friendly strategy based on laser direct writing technology to regulate the valence state of Mn-based oxides nanoparticles anchored on three-dimensional(3D) framework of laser-induced graphene (LIG) for the application of high-performance flexible planar interdigital microsupercapacitors (MSCs). Under the laser radiation, a polyimide (PI) and MnO2 composite film was directly converted into 3D graphene and MnOx (MnO, MnO2 and Mn3O4 mixture). Furthermore, the results reveal that LIG/MnOx MSCs device exhibits a high specific capacitance of 23.3 mF cm−2, which is about 29 times higher than that of LIG MSCs (0.8 mF cm−2). Moreover, LIG/MnOx MSCs possess a high energy density of 7.28 μWh cm−2, outstanding cycle stability with the capacitance retention rate of 97.4 % after 10,000 cycles, and excellent mechanical flexibility. Therefore, this preparation strategy of LIG/MnOx provides a reference for the performance regulation of Mn-based oxides and the low-cost construction of MSCs devices with high energy density, which carries significant research implications for diverse flexible wearable electronic applications in the forthcoming days.

Kinetic study of propane ODH on electrospun vanadium oxide-based submicron diameter fiber catalyst

A rigorous kinetic study of the oxidative dehydrogenation (ODH) reaction of propane on a vanadium oxide-based submicron diameter fiber catalyst has been developed. The proposed kinetic model simulates the conversion-selectivity profiles, the surface coverage of the different adsorbed species and the oxidation state of the catalyst for the studied operating conditions of temperature, space–time and inlet partial pressures of propane and oxygen. The activation energy of the rate determining step (RDS), the first hydrogen abstraction from propane, is 104 kJ·mol−1. The model predicts that although the reaction seems to be pseudo-zero order with respect to oxygen in a broad range of conditions, the catalyst may not be fully oxidized during reaction. The accuracy of the model when predicting the oxidation state of the catalyst has been experimentally confirmed by analyzing the catalytic fixed bed after reaction. The reduction degree of the catalyst will depend on its intrinsic chemical nature and reaction conditions, increasing with the space–time and in detriment of the overall reaction rate. Consequently, the propane turnover frequency (TOF) will also depend on the reaction conditions and space–time, even changing along the fixed-bed reactor.

Scaling-Up Microwave-Assisted Synthesis of Highly Defective Pd@UiO-66-NH2 Catalysts for Selective Olefin Hydrogenation under Ambient Conditions.

The need to develop green and cost-effective industrial catalytic processes has led to growing interest in preparing more robust, efficient, and selective heterogeneous catalysts at a large scale. In this regard, microwave-assisted synthesis is a fast method for fabricating heterogeneous catalysts (including metal oxides, zeolites, metal-organic frameworks, and supported metal nanoparticles) with enhanced catalytic properties, enabling synthesis scale-up. Herein, the synthesis of nanosized UiO-66-NH2 was optimized via a microwave-assisted hydrothermal method to obtain defective matrices essential for the stabilization of metal nanoparticles, promoting catalytically active sites for hydrogenation reactions (760 kg·m-3·day-1 space time yield, STY). Then, this protocol was scaled up in a multimodal microwave reactor, reaching 86% yield (ca. 1 g, 1450 kg·m-3·day-1 STY) in only 30 min. Afterward, Pd nanoparticles were formed in situ decorating the nanoMOF by an effective and fast microwave-assisted hydrothermal method, resulting in the formation of Pd@UiO-66-NH2 composites. Both the localization and oxidation states of Pd nanoparticles (NPs) in the MOF were achieved using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optimal composite, loaded with 1.7 wt % Pd, exhibited an extraordinary catalytic activity (>95% yield, 100% selectivity) under mild conditions (1 bar H2, 25 °C, 1 h reaction time), not only in the selective hydrogenation of a variety of single alkenes (1-hexene, 1-octene, 1-tridecene, cyclohexene, and tetraphenyl ethylene) but also in the conversion of a complex mixture of alkenes (i.e., 1-hexene, 1-tridecene, and anethole). The results showed a powerful interaction and synergy between the active phase (Pd NPs) and the catalytic porous scaffold (UiO-66-NH2), which are essential for the selectivity and recyclability.

Methyl 3,4-dihydroxybenzoate alleviates oxidative damage in granulosa cells by activating Nrf2 antioxidant pathway

Oxidative damage induced granulosa cells (GCs) apoptosis was considered as a significant cause of compromised follicle quality, antioxidants therapy has emerged as a potential method for improving endometriosis pregnancy outcomes. Here, we found that GCs from endometriosis patients show increased oxidative stress level. Methyl 3,4-dihydroxybenzoate (MDHB), a small molecule compound that is extracted from natural plants, reversed tert-butyl hydroperoxide (TBHP) induced GCs oxidative damage. Therefore, the aim of this study was to assess the protective effect of MDHB for GCs and its potential mechanisms. TUNEL staining and immunoblotting of cleaved caspase-3/7/9 showed MDHB attenuated TBHP induced GCs apoptosis. Mechanistically, MDHB treatment decreased cellular and mitochondria ROS production, improved the mitochondrial function by rescuing the mitochondrial membrane potential (MMP) and ATP production. Meanwhile, MDHB protein upregulated the expression of vital antioxidant transcriptional factor Nrf2 and antioxidant enzymes SOD1, NQO1 and GCLC to inhibited oxidative stress state, further beneficial to oocytes and embryos quality. Therefore, MDHB may represent a potential drug candidate in protecting granulosa cells in endometriosis, which can improve pregnancy outcomes for endometriosis-associated infertility.

Characterization and differentiation of dissolved organic matter in leachate derived from an old Japanese landfill site through Orbitrap mass spectrometry

AbstractElucidating the characteristics of dissolved organic matter (DOM) is crucial to assessing its impact on the bioavailability and mobility of pollutants in landfill leachate. This study reports a comprehensive 5–month investigation into the characteristics of DOM in leachate from an old Japanese landfill, collected at six different sampling points. The molecular composition, chemical properties, and structural characteristics of DOM were assessed using Orbitrap mass spectrometry and spectral analysis. The leachate DOM mainly consisted of CHO-containing molecules (58.5–88.9%), low-oxygen unsaturated phenolic compounds (40.5–54.0%), and aliphatic compounds (19.4–47.3%), with slight variation among sampling points. A significant portion of the nominal oxidation state of carbon was in the reduced zone (76.2–95.4%). The results underscore the distinct molecular composition of DOM in mature Japanese landfill leachate compared to young and mature leachates from other countries. Two of six sampling points, with notable differences in molecular characteristics, were compared and elucidated. The composition of landfill waste, rather than landfill age, was the main factor affecting the characteristics and differentiation of leachate DOM.

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes.

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO2, H2O, and O2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. The emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

Highly Exothermic and Fast Mechanochemical Redox and Intercalation Reactions of V2O5 with Sodium Hydride.

Vanadium oxides exhibit promising characteristics for electrochemical energy storage, owing to their capability to switch between different oxidation states, in combination with the incorporation of alkali metals. Here, we report on a systematic investigation of the mechanochemical reduction of V2O5 with NaH. In contrast to conventional high-temperature synthesis methods, the mechanochemical reaction occurs already after a few minutes. We observed a mixture of different (sodium) vanadium oxides with vanadium oxidation states ranging from +III to +V. Remarkably, these highly exothermic self-propagating reactions occur even within a rudimentary pistil-mortar setup. Hereby, the hydride concentration has a greater effect on the final sample composition than the milling time. In general, higher percentages of sodium vanadates are formed instead of vanadium oxides, and the lower oxidation states of vanadium are accessible with increasing amounts of NaH. Theoretical calculations confirm these experimental observations and emphasize the central role of sodium vanadates, especially with vanadium in the +V oxidation state, in carrying out the observed exothermic reactions. This comprehensive study sheds light on the mechanochemical reduction of vanadium oxides and underlines their potential for further development of electrochemical energy storage systems.

Size-Dependent Catalysis in Fenton-like Chemistry: From Nanoparticles to Single Atoms.

State-of-the-art Fenton-like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements in heterogeneous metal-based catalysts within AOPs, covering nanoparticles (NPs), single-atom catalysts (SACs), and ultra-small atom clusters. A distinct connection between the physical properties of these catalysts, such as size, degree of unsaturation, electronic structure, and oxidation state, and their impacts on catalytic behavior and efficacy in Fenton-like reactions. In-depth comparative analysis of metal NPs and SACs is conducted focusing on how particle size variations and metal-support interactions affect oxidation species and pathways. The review highlights the cutting-edge characterization techniques and theoretical calculations, indispensable for deciphering the complex electronic and structural characteristics of active sites in downsized metal particles. Additionally, the review underscores innovative strategies for immobilizing these catalysts onto membrane surfaces, offering a solution to the inherent challenges of powdered catalysts. Recent advances in pilot-scale or engineering applications of Fenton-like-based devices are also summarized for the first time. The paper concludes by charting new research directions, emphasizing advanced catalyst design, precise identification of reactive oxygen species, and in-depth mechanistic studies. These efforts aim to enhance the application potential of nanotechnology-based AOPs in real-world wastewater treatment.