Search Results (119)

Mechanistic interpretation in transition metal electrocatalysts for water splitting, particularly for the oxygen evolution reaction (OER), remains challenging despite major advances in operando spectroscopy, isotope labelling, and electrochemical analysis. Mechanistic claims are frequently supported by incomplete or overinterpreted evidence, leading to persistent ambiguity in active site identification, rate-limiting step assignment, and pathway discrimination. This review adopts a claim-centric framework that organises experimental approaches around the specific mechanistic assertions they aim to support, rather than cataloguing catalyst classes or performance metrics, and formalises this perspective as a decision-guided framework for mechanistic validation. We critically assess how techniques such as isotope labelling, operando spectroscopy, and electrokinetic analysis can and cannot substantiate claims related to adsorbate-versus lattice-oxygen-mediated pathways, reconstruction-defined active phases, and dynamic surface behaviour. Application of this framework to common mechanistic archetypes in OER electrocatalysis shows that surface reconstruction and condition-dependent pathway switching limit static mechanistic assignments, and that single-technique interpretations are rarely definitive. By clarifying the minimum evidentiary standards required for common mechanistic claims, this review aims to promote more rigorous, transparent, and falsifiable mechanistic analysis, supporting durable progress beyond descriptor-driven correlations and isolated performance benchmarks. Full article

Energy-Dispersive X-ray Diffraction (EDXRD) employs a polychromatic (white) X-ray beam and an energy-discriminating detector at a fixed scattering geometry to measure diffracted intensity as a function of photon energy. This technique enables the rapid acquisition of diffraction data over a wide range of d-spacings without mechanical scanning of the scattering angle, making it particularly valuable for time-resolved, bulk-penetrating, and operando studies. In this review, we provide a comprehensive overview of EDXRD, covering the fundamental principles and underlying physics, experimental methodologies and data analysis workflows, synchrotron white-beam implementations compared to monochromatic approaches, detector strategies, parameter optimization for accurate and efficient measurements, and representative applications in high-pressure science and battery research. Finally, we discuss current challenges and future prospects, including advances in detector technology, machine learning-assisted spectral analysis, and the development of standardized, automated EDXRD systems. Full article

Electrochemical CO₂ reduction (CO₂RR) is a promising route to transform a major greenhouse gas into value-added fuels and chemicals. However, its deployment is still hindered by the sluggish activation of CO₂, poor selectivity toward multielectron products, and competition with the hydrogen evolution reaction (HER). Single-atom catalysts (SACs) have emerged as powerful materials to address these challenges because they combine maximal metal utilization with well-defined coordination environments whose electronic structure can be precisely tuned through metal–support interactions. This minireview summarizes current understanding of how structural, electronic, and chemical features of SAC supports (e.g., porosity, heteroatom doping, vacancies, and surface functionalization) govern the adsorption and conversion of key CO₂RR intermediates and thus control product distributions from CO to CH₄, CH₃OH and C₂⁺ species. Particular emphasis is placed on selectivity descriptors (e.g., coordination number, d-band position, binding energies of *COOH and *OCHO) and on rational design strategies that exploit curvature, microenvironment engineering, and electronic metal–support interactions to direct the reaction along desired pathways. Representative SAC systems based primarily on N-doped carbons, complemented by selected examples on oxides and MXenes are discussed in terms of Faradaic efficiency (FE), current density and operational stability under practically relevant conditions. Finally, the review highlights remaining bottlenecks and outlines future directions, including operando spectroscopy and data-driven analysis of dynamic single-site ensembles, machine-learning-assisted DFT screening, scalable mechanochemical synthesis, and integration of SACs into industrially viable electrolyzers for carbon-neutral chemical production. Full article

This paper summarizes the main applications of isotopic substitution in infrared surface studies, including surface characterization, determination of the structure of adsorbed species, and clarification of catalytic reaction mechanisms. While acknowledging the key pioneering contributions to the field, we focus on the recent developments and the future potential of the technique. The applications are grouped into two main categories, according to the extent of isotopic substitution. The first category involves systems in which one or more atoms in specific positions are fully replaced by their isotopes. This classical approach remains fundamental for establishing whether the spectral signature of a given compound is related to the presence of a specific atom. The second category concerns partial isotopic exchange. These studies unravel different vibrational interactions and provide valuable structural information that cannot be obtained through full substitution. Finally, we discuss some applications related to the mechanisms of catalytic reactions. The perspective concludes with a discussion of the emerging opportunities and future perspectives for more systematic and effective implementation of isotopic substitution in infrared surface studies. Full article

Lithium iron phosphate (LiFePO₄, LFP) batteries dominate grid-scale energy storage, yet their cycle life is capped by its capacity fade issues. Conventional failure workflows suffer from redundant tests, high cost, and long turnaround time because the underlying mechanisms remain unclear. Herein, multi-scale characterization coupled with electrochemical tests have been quantitatively established to reveal four synergistic fade modes of LFP: active-Li loss, FePO₄ secondary-phase formation, SEI rupture, and particle fracture. A two-tier “screen–validate” protocol is proposed to accurately and efficiently disclose its mechanism. In the screening tier, capacity, cyclic voltammetry, electrochemical impedance spectroscopy, low-magnification scanning electron microscopy, and snapshot X-ray diffraction (XRD) rapidly flag the most probable failure cause. The validation tier then deploys mechanism-matched in situ/ex situ tools (operando XRD, TEM, XPS, ToF-SIMS, etc.) to build a comprehensive evidence chain of dynamic structural evolution, materials loss tracking, and quantitative proof. The streamlined workflow preserves scientific rigor and reproducibility while cutting analysis time and cost, offering a closed-loop route for fast failure diagnosis and targeted optimization of next-generation LFP batteries. Full article

The spontaneous formation and stability of a protective passive film on a metal surface are crucial for the metal material’s corrosion resistance during its service life. Passive films have been extensively studied, and our understanding of passive films has been significantly improved with the development of advanced analytical techniques. Modern synchrotron X-ray sources offer unprecedented possibilities for detailed analyses of passive films and for in situ and operando studies of passive films in both gaseous/aqueous environments, as well as in electrochemical environments. This mini review presents a short summary of recent studies on passive films, mainly focusing on stainless steels and nickel-base alloys, which utilize state-of-the-art synchrotron X-ray techniques, particularly X-ray photoelectron spectroscopy (XPS), often in combination with other synchrotron techniques such as X-ray adsorption, diffraction, reflectivity, and fluorescence. These reports demonstrate that synchrotron-based techniques greatly improve probing sensitivity and spatial resolution, enabling in situ and operando studies of passive films at solid–liquid interfaces. These studies reveal changes in the passive film and underlying alloy layer, highlighting the important role of hydroxides, as well as the inhomogeneity in passive films associated with the complex microstructures in advanced industrial alloys. Full article

Quantum-dot light-emitting diodes (QLEDs) have emerged as promising candidates for next-generation display technologies owing to their high color purity and external quantum efficiency. Despite rapid advancements in device performance, operational stability and long-term reliability remain critical challenges, particularly for cadmium-free and blue-emitting QLEDs. This review provides a comprehensive overview of the degradation mechanisms of QLEDs, emphasizing the relationship between environmental factors, such as moisture, oxygen, and thermal stress, and excitonic factors, including charge-injection imbalance, Auger recombination, and interface deterioration. We further highlight the role of nondestructive characterization techniques, including impedance spectroscopy, Fourier transform infrared spectroscopy, transient photoluminescence, transient electroluminescence, transient absorption, and electroabsorption spectroscopy, in probing real-time charge dynamics and material degradation. By integrating the insights from these operando analyses, this review offers a detailed perspective on the origins of device degradation and provides guidance for rational design strategies aimed at enhancing the operational stability and commercialization potential of QLEDs. Full article

X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) are analytical techniques enabling precise analysis of the electronic structure and local atomic environment in chemical compounds and materials. Their application spans materials science, chemistry, biology, and environmental sciences, supporting studies on catalytic mechanisms, redox processes, and metal speciation. A key advantage of both techniques is element selectivity, allowing the analysis of specific elements without matrix interference. Their high sensitivity to chemical state and coordination enables determination of oxidation states, electronic configuration, and local geometry. These methods are applicable to solids, liquids, and gases without special sample preparation. Modern XAS and XES studies are typically performed using synchrotron radiation, which provides an intense, monochromatic X-ray source and allows advanced in situ and operando experiments. Sub-techniques such as XANES (X-ray absorption near-edge structure), EXAFS (Extended X-ray Absorption Fine Structure), and RIXS (resonant inelastic X-ray scattering) offer enhanced insights into oxidation states, local structure, and electronic excitations. Despite their broad scientific use, applications in pharmaceutical research remain limited. Nevertheless, recent studies highlight their potential in analyzing crystalline active pharmaceutical ingredients (APIs), drug–biomolecule interactions, and differences in drug activity. This review introduces the fundamental aspects of XAS and XES, with an emphasis on practical considerations for pharmaceutical applications, including experimental design and basic spectral interpretation. Full article

The vibration properties of materials play a role in their conduction of electric charges. Ionic conductors such as electrodes and solid electrolytes are also relevant in this respect. The vibration properties are typically assessed with infrared and Raman spectroscopy, and inelastic neutron scattering, which all allow for the derivation of the phonon density of states (PDOS) in part of a full portion of the Brioullin zone. Nuclear resonant vibration spectroscopy (NRVS) is a novel method that produces the element-specific PDOS from Mössbauer-active isotopes in a compound. We employed NRVS operando on a pouch cell battery containing a Li⁵⁷FePO₄ electrode, and thus could derive the PDOS of the ⁵⁷Fe in the electrode during charging and discharging. The spectra reveal reversible vibrational changes associated with the two-phase conversion between LiFePO₄ and FePO₄, as well as signatures of metastable intermediate states. We demonstrate how the NRVS data can be used to tune the atomistic simulations to accurately reconstruct the full vibration structures of the battery materials in operando conditions. Unlike optical techniques, NRVS provides bulk-sensitive, element-specific access to the full phonon spectrum under realistic operando conditions. These results establish NRVS as a powerful method to probe lattice dynamics in working batteries and to advance the understanding of ion transport and phase transformation mechanisms in electrode materials. Full article

Hydrogen (H₂) has become a more important alternative source in the current energy transition process. Beyond its role in clean energy production, it also serves as a key reactant in a wide range of industrial chemical transformations, such as hydrogenation and hydroprocessing. A fundamental step in many of these processes is the dissociation of hydrogen on catalyst surfaces. This short review provides an overview of the fundamental mechanisms involved in hydrogen dissociation over catalysts, with a specific emphasis on heterolytic pathways. Meanwhile, the influence of surface coordination environments on hydrogen activation is discussed, focusing on key factors—Lewis acid–base pairs, lattice oxygen and oxygen vacancies, and metal–support interfaces. With recognizing the significance of understanding the reaction mechanisms, we provide a critical review of experimental techniques, including spectroscopy, temperature-programmed methods, and kinetic analysis, that have been successfully applied or appear promising for probing active sites, reaction dynamics, chemisorbed intermediates, and elementary steps. Our goal is to highlight how these techniques contribute to a mechanistic understanding and to outline future directions, making this review a valuable resource for both new and experienced researchers. Full article

This study used in situ modulation excitation spectroscopy (MES) with varying frequencies in a single experiment to identify surface species during ethanol oxidation on Au/SiO₂, Au/TiO₂, Au/ZnO, and Au/SrTiO₃. Fixed-bed reactor (FBR) tests (1 kPa ethanol, 1.5 kPa O₂, 513 K) showed that Au/SiO₂ and Au/SrTiO₃ had higher ethanol conversions. Au/SiO₂ favored acetaldehyde, while Au/SrTiO₃ yielded more acetates (acetic acid and ethyl acetate). Operando modulation excitation (ME)–phase sensitive detection (PSD)–DRIFTS, with ethanol and oxygen modulation, identified surface ethanol, acetaldehyde, acetates, ethoxy, and hydroxyl species. Oxygen modulation showed charge transfer to supports in Au/TiO₂ and Au/ZnO. At the fundamental frequency (f₀ = 1/90 Hz), ME–PSD–DRIFTS showed minimal adsorbed ethanol on Au/SiO₂, indicating high ethanol conversion. Au/SrTiO₃ had higher acetaldehyde consumption, correlating with increased acetates, consistent with FBR results. ME–PSD–DRIFTS at lower frequencies (0.07f₀, 0.5 f₀) and higher harmonics (2f₀, 3f₀) showed rapid ethoxy formation/decomposition, and slower acetaldehyde reactions, confirming acetaldehyde as a primary product and acetates as secondary products. Oxygen modulation revealed rapid hydrogen spillover and hydroxyl changes. Overall, operando spectroscopy via mass spectrometry confirmed the FBR findings. Full article

Its crucial importance to the long-term operation of lithium-ion batteries has made the solid electrolyte interphase (SEI) the subject of intensive research efforts. These investigations are challenging, however, due to the very complex and fragile nature of this layer. With its typical thickness being in the range of some 10 nm and its chemical make-up being highly sensitive to even the smallest amounts of impurities, it becomes clear that artifacts are easily introduced in investigations of the SEI, especially if the measurements are performed ex situ. To help ameliorate these issues, we herein report a combination of non-destructive operando techniques that can be employed simultaneously in the same electrochemical cell to provide a plethora of physical, morphological, and electrochemical data on the macroscopic and microscopic scale. These techniques encompass atomic force microscopy (AFM), electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D), and impedance spectroscopy (EIS). This work focuses on how to combine these techniques in a single electrochemical cell, which is suitable to study SEI formation while avoiding noise, crosstalk, inhomogeneous SEI formation, and other pitfalls. Full article

Developing sustainable and efficient electrocatalysts for the oxygen evolution reaction (OER) is crucial for advancing energy storage technologies. This study explored the dual role of phosphorus as a dopant in carbon matrices and a key component in nickel phosphides (Ni₂P and Ni₁₂P₅), synthesized using dopamine (PDA) and ammonium phosphate as eco-friendly precursors. The phase formation of nickel phosphides was found to be highly dependent on the P/PDA ratio (0.15, 0.3, 0.6, and 0.9), allowing for the selective synthesis of Ni₂P or Ni₁₂P₅. Operando Raman spectroscopy revealed that both phases undergo surface transformation into nickel (oxy)hydroxide species under OER conditions, yet Ni₂P-based catalysts demonstrated superior activity and long-term stability. This enhancement is attributed to efficient electron transfer at the dynamic Ni₂P/NiOOH interface. Additionally, hollow nanostructures formed at intermediate P/PDA ratios (≤0.3) via the Kirkendall effect and Ostwald ripening contributed to an increased specific surface area and micropore volume, further improving the catalytic performance. Electrochemical impedance spectroscopy confirmed reduced interfacial resistance and enhanced charge transport. These findings offer new insights into the rational design of high-performance electrocatalysts and propose a green, tunable synthesis approach for advanced energy conversion applications. Full article

This study investigates the electrochemical degradation mechanisms of nickel–salen (NiSalen) polymers, with a focus on improving the material’s stability in supercapacitor applications. We analyzed the effects of steric hindrance near the nickel center by incorporating different bulky substituents into NiSalen complexes, aiming to mitigate water-induced degradation. Electrochemical performance was assessed using cyclic voltammetry, operando conductance, and impedance measurements, while X-ray photoelectron spectroscopy (XPS) provided insights into molecular degradation pathways. The results revealed that increased steric hindrance from methyl groups significantly reduced the degradation rate, particularly in water-containing electrolytes, by hindering water coordination to the Ni center. Among the studied polymers, the highly substituted poly[Ni(Saltmen)] exhibited superior stability with minimal capacity loss. Density functional theory (DFT) calculations further supported that steric protection around the Ni atom effectively lowers the probability of water coordination. These findings suggest that sterically enhanced NiSalen polymers may offer a promising path toward durable supercapacitor electrodes, highlighting the route of molecular engineering to enhance material stability. Full article

In hydrogen processes, managing CO emissions and removal by catalytic oxidation is crucial during H₂ production, storage/transportation, and use, ensuring the efficiency and safety of hydrogen systems and contributing to more sustainable energy solutions. Perovskite-structured transition metal oxide catalysts have been widely studied in various energy and environmental applications due to their extensive compositional modifications and electronic adjustments, facilitating catalytic behavior. Here, Ce-based perovskite catalysts with dual active metal doping at varying Co and Ni ratios are investigated to understand their structural and redox properties in CO oxidation. The reaction mechanism involves CO adsorption, oxygen activation, and redox cycling, confirming catalytic turnover. In situ DRIFTS analysis reveals real-time surface transformations with catalytic activity, which vary with Co and Ni doping ratio. Relatively, CO adsorption on Co³⁺ dominates the low-temperature activity, whereas Ni contributes to the efficiency at elevated temperatures. LCCNTxy (La_0.7Ce_0.1Co_xNi_yTi_0.6O₃) with x = 0.3 and y = 0.1 exhibits the highest performance, achieving T₁₀ above 40 °C and the fastest T₉₀ at 230 °C. This study highlights the compositional tuning in dual-doped perovskites and complementary roles of Co and Ni in CO oxidation for developing efficient industrial catalysts. Full article