Search Results (95)

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

Measuring molecular dynamics improves understanding of the structure–function relationships of materials. In this study, we present a novel technique for observing material dynamics using transmission electron microscopy (TEM), in which the gold nanoparticles are employed as motion probes for tracing the polymer dynamics in real space. A thin layer of polymer materials was generated on the 2 μm diameter holes of Quantifoil grids, and gold nanoparticles were dispersed on the membrane surface. By tracking the movement of gold nanoparticles from a series of TEM images taken under continuous temperature control, we obtained mean squared displacement (MSD) curves. The dynamics of poly{2-(perfluorooctyl)ethyl acrylate} (PC₈FA) and poly(stearyl acrylate) (PSA) were analyzed. In the temperature-dependent analysis of the MSD, sharp peaks were observed for both PC₈FA and PSA at positions corresponding to their melting and crystallization temperatures. These results demonstrate the capability of TEM to provide valuable insights into the dynamics of polymer materials, highlighting its potential for widespread application in materials sciences. 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

Laser conversion of commercial polymers to laser-induced graphene (LIG) using inexpensive and accessible CO₂ lasers has enabled the rapid prototyping of promising electronic and electrochemical devices. Frequently used to pattern interdigitated supercapacitors, few approaches have been developed to pattern batteries—in particular, full cells. Herein, we report an LIG-based approach to a planar, interdigitated Li-S battery. We show that sulfur can be deposited by selective nucleation and growth on the LIG cathode fingers in a supersaturated sulfur solution. Melt imbibition then leads to loadings as high as 3.9 mg/cm² and 75 wt% sulfur. Lithium metal anodes are electrodeposited onto the LIG anode fingers by a silver-seeded, pulse-reverse-pulse method that enables loadings up to 10.5 mAh/cm² to be deposited without short-circuiting the interdigitated structure. The resulting binder/separator-free flexible battery achieves a capacity of over 1 mAh/cm² and an energy density of 200 mWh/cm³. Unfortunately, due to the use of near stoichiometric lithium, the cycle-life is sensitive to lithium degradation. While future work will be necessary to make this a practical, flexible battery, the interdigitated structure is well-suited to future operando and ex situ studies of Li-S and related battery chemistries. Full article

Advanced batteries require advanced characterization techniques, and neutron scattering is one of the most powerful experimental methods available for studying next-generation battery materials. Neutron scattering offers a non-destructive method to probe the complex structural and chemical processes occurring in batteries during operation in truly in situ/in operando measurements with a high sensitivity to battery-relevant elements such as lithium. Neutrons have energies comparable to the energies of excitations in materials and wavelengths comparable to atomic distances in the solid state, thus giving access to study structural and dynamical properties of materials on an atomic scale. In this review, a broad overview of selected neutron scattering techniques is presented to illustrate how neutron scattering can be used to gain invaluable information of solid-state battery materials, with a focus on in situ/in operando methods. These techniques span multiple decades of length and time scales to uncover the complex processes taking place fundamentally on the atomic scale and to determine how these processes impact the macroscale properties and performance of functional battery systems. This review serves the solid-state battery research community by examining how the unique capabilities of neutron scattering can be applied to answer critical and unresolved questions of materials research in this field. A thorough and broad perspective is provided with numerous practical examples showing these techniques in action for battery research. Full article

Fast electrochemical phenomena occurring in supercapacitors are hard to analyze by ex situ or in situ techniques because many of them are meta-stable (the supercapacitor relaxes once it is not further polarized). In a steady state, one observes the effect of charge storage but not necessarily the mechanism. This is a problem for Raman spectroscopy, too, even though Raman spectra of the electrodes of supercapacitors are commonly recorded ex situ or in a steady state in situ. Raman operando is desired, but it represents a technological challenge since the electrochemical events in a supercapacitor are very fast (occurring within seconds), and in contrast, Raman requires from seconds to minutes to collect enough photons for reliable spectra. This work presents the development of electrodes made of thin layers of iron oxide grown solvothermally on Si wafers, with a porosified surface and resistivity of 0.005 Ωcm, to study their performance as electrodes in supercapacitors and analyze their energy storage mechanisms by cyclic voltammetry and Raman operando. Being flat and containing just iron oxide and silicon, these electrodes allow for studying interfacial phenomena with minor interferents. Full article

In various applications, dry friction could induce vibrations. A well-known example is frictional braking systems in ground transportation vehicles involving a sliding contact between a rotating and a stationary part. In such scenarios, the emission of high-intensity noise, commonly known as squeal, can present human health risks based on the noise’s intensity, frequency, and occurrences. Despite the importance of squeal in the context of advancing urbanization, the parameters determining its occurrence remain uncertain due to the complexity of the involved phenomena. This study aims to identify a relevant operando indicator for predicting squeal occurrences. To this end, a pin-on-disc test rig was developed to replicate various contact conditions found in road profiles and investigate resulting squealing. Each test involves a multimodal instrumentation, complemented by surface observations. It is illustrated that the enhanced thermal indicator identified is relevant because it is sensitive to the thermomechanical and tribological phenomena involved in squealing. Full article

This work presents advancements in a rotating glow-to-arc plasma reactor, designed for stable gas conversion of robust molecules like CO₂, N₂, and CH₄. Plasma-based systems play a critical role in Power-to-X research, offering electrified, sustainable pathways for industrial gas conversion. Here, we scaled the reactor’s power from 200 W to 1.2 kW in a CO₂ plasma, which introduced instability due to uplift forces and arc behavior. These were mitigated by integrating silicon carbide (SiC) ceramic foam as a mechanical restriction, significantly enhancing stability by reducing arc movement, confining convection, and balancing volumetric flow within the arc. Using high-speed camera analysis and in situ electronic frequency measurements, we identified dominant frequencies tied to operational parameters, supporting potential in operando monitoring and control. Arc-rotation frequencies from 5 to 50 Hz and higher frequencies (500 to 2700 Hz) related to arc chattering reveal the system’s dynamic response to power and flow changes. Furthermore, refining the specific energy input ($SEI$) to account for plasma residence time allowed for a more precise calculation of effective $SEI$, optimizing energy delivery to target molecules. Our findings underscore the reactor’s promise for scalable, efficient gas conversion in sustainable energy applications. Full article

High-quality, reproducible tip coatings are essential for minimizing faradaic currents in electrochemical scanning tunneling microscopy (EC-STM), especially during in situ and operando measurements. The variability inherent in manual coating methods, influenced by the operator’s skill and a lack of standardization, can lead to inconsistent results, increased research costs, and a greater workload. This study introduces an Automated Tip Coater (ATC) designed to automate and standardize the tip coating process. The ATC features a tip movement system using stepper motors, a rotation module with a DC motor, and a heating block based on a soldering iron. It is controlled by an Arduino development board, supported by motor drivers, and has a user-friendly interface with an OLED display and encoder. The ATC coating mechanism includes a redesigned plate with a reduced gap size and a milled tray to precisely control the amount of insulating material applied to the tip. A fast cyclic voltammetry test in a 0.1 M HClO₄ electrolyte demonstrated that over 75% of ATC-coated tips achieved excellent insulation with leakage currents below ±50 pA—and 30% below ±10 pA—suitable for highly sensitive experiments. Further measurements with EC-STM using the newly coated tips investigated the electrochemical behavior of highly oriented pyrolytic graphite (HOPG), revealing detailed atomic structures under dynamic electrochemical conditions. The ATC significantly enhances reproducibility, reduces dependency on operator skills, and lowers research costs while improving the accuracy and reliability of EC-STM measurements. Full article

The advancement of solid-state hydrogen storage materials is critical for the realization of a sustainable hydrogen economy. This comprehensive review elucidates the state-of-the-art characterization techniques employed in solid-state hydrogen storage research, emphasizing their principles, advantages, limitations, and synergistic applications. We critically analyze conventional methods such as the Sieverts technique, gravimetric analysis, and secondary ion mass spectrometry (SIMS), alongside composite and structure approaches including Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This review highlights the crucial role of in situ and operando characterization in unraveling the complex mechanisms of hydrogen sorption and desorption. We address the challenges associated with characterizing metal-based solid-state hydrogen storage materials discussing innovative strategies to overcome these obstacles. Furthermore, we explore the integration of advanced computational modeling and data-driven approaches with experimental techniques to enhance our understanding of hydrogen–material interactions at the atomic and molecular levels. This paper also provides a critical assessment of the practical considerations in characterization, including equipment accessibility, sample preparation protocols, and cost-effectiveness. By synthesizing recent advancements and identifying key research directions, this review aims to guide future efforts in the development and optimization of high-performance solid-state hydrogen storage materials, ultimately contributing to the broader goal of sustainable energy systems. Full article

The field of energy storage and conversion materials has witnessed transformative advancements owing to the integration of advanced in situ characterization techniques. Among them, numerous real-time characterization techniques, especially in situ transmission electron microscopy (TEM)/scanning TEM (STEM) have tremendously increased the atomic-level understanding of the minute transition states in energy materials during electrochemical processes. Advanced forms of in situ/operando TEM and STEM microscopic techniques also provide incredible insights into material phenomena at the finest scale and aid to monitor phase transformations and degradation mechanisms in lithium-ion batteries. Notably, the solid–electrolyte interface (SEI) is one the most significant factors that associated with the performance of rechargeable batteries. The SEI critically controls the electrochemical reactions occur at the electrode–electrolyte interface. Intricate chemical reactions in energy materials interfaces can be effectively monitored using temperature-sensitive in situ STEM techniques, deciphering the reaction mechanisms prevailing in the degradation pathways of energy materials with nano- to micrometer-scale spatial resolution. Further, the advent of cryogenic (Cryo)-TEM has enhanced these studies by preserving the native state of sensitive materials. Cryo-TEM also allows the observation of metastable phases and reaction intermediates that are otherwise challenging to capture. Along with these sophisticated techniques, Focused ion beam (FIB) induction has also been instrumental in preparing site-specific cross-sectional samples, facilitating the high-resolution analysis of interfaces and layers within energy devices. The holistic integration of these advanced characterization techniques provides a comprehensive understanding of the dynamic changes in energy materials. This review highlights the recent progress in employing state-of-the-art characterization techniques such as in situ TEM, STEM, Cryo-TEM, and FIB for detailed investigation into the structural and chemical dynamics of energy storage and conversion materials. Full article

In advancing sodium-ion battery technology, we introduce a novel application of Na₃NiZr(PO₄)₃ with a NASICON structure as an anode material. This research unveils, for the first time, its exceptional ability to maintain high specific capacity and unprecedented cycle stability under extreme current densities up to 1000 mA·g⁻¹, within a low voltage window of 0.01–2.5 V. The core of our findings lies in the material’s remarkable capacity retention and stability, which is a leap forward in addressing long-standing challenges in energy storage. Through cutting-edge in situ/operando X-ray diffraction analysis, we provide a perspective on the structural evolution of Na₃NiZr(PO₄)₃ during operation, offering deep insights into the mechanisms that underpin its superior performance. Full article

Modern catalysts are complex systems whose performance depends both on space and time domains and, most importantly, on the operational environment. As a direct consequence, understanding their functionalities requires sophisticated techniques and tools for measurement and simulation, addressing the proper spatial and temporal scale and being capable of mimicking the working conditions of every single component, such as catalyst supports, electrodes, electrolytes, as well as of the entire assembly, e.g., in the case of fuel cells or batteries. Scanning photoelectron spectro-microscopy (SPEM) is one of the approaches that allow combining X-ray photoelectron spectroscopy with sub-micron spatial resolution; in particular, the SPEM hosted at the ESCA Microscopy beamline at Elettra has been upgraded to conduct in situ and operando experiments. Three different case studies are presented to illustrate the capabilities of the SPEM in the investigation of catalytic materials in different conditions and processes. Full article

Lithium-ion batteries (LIBs) have the advantage of high energy density, which has attracted the wide attention of researchers. Nevertheless, the growth of lithium dendrites on the anode surface causes short life and poor safety, which limits their application. Therefore, it is necessary to deeply understand the growth mechanism of lithium dendrites. Here, the growth mechanism of lithium dendrites is briefly summarized, and the real-time monitoring technologies of lithium dendrite growth in recent years are reviewed. The real-time monitoring technologies summarized here include in situ X-ray, in situ Raman, in situ resonance, in situ microscopy, in situ neutrons, and sensors, and their representative studies are summarized. This paper is expected to provide some guidance for the research of lithium dendrites, so as to promote the development of LIBs. Full article