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Results for “operando spectroscopy”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Surface Oxygen Depletion of Layered Transition Metal Oxides in Li-Ion Batteries Studied by Operando Ambient Pressure X-ray Photoelectron Spectroscopy

A new operando spectro-electrochemical setup was developed to study oxygen depletion from the surface of layered transition metal oxide particles at high degrees of delithiation. An NCM111 working electrode was paired with a chemically delithiated LiFePO 4 counter electrode in a fuel cell-inspired membrane electrode assembly (MEA). A propylene carbonate-soaked Li-ion conducting ionomer served as an electrolyte, providing both good electrochemical performance and direct probing of the NCM111 particles during cycling by ambient pressure X-ray photoelectron spectroscopy. The irreversible emergence of an oxygen-depleted phase in the O 1s spectra of the layered oxide particles was observed upon the first delithiation to high state-of-charge, which is in excellent agreement with oxygen release analysis via mass spectrometry analysis of such MEAs. By comparing the metal oxide-based O 1s spectral features to the Ni 2p 3/2 intensity, we can calculate the transition metal-to-oxygen ratio of the metal oxide close to the particle surface, which shows good agreement with the formation of a spinel-like stoichiometry as an oxygen-depleted phase. This new setup enables a deeper understanding of interfacial changes of layered oxide-based cathode active materials for Li-ion batteries upon cycling.

25 ENERGY STORAGE↗
DOE OSTI2021

Modification of the Coordination Environment of Active Sites on MoC for High-Efficiency CH 4 Production

Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis, but it is highly challenging. Guided by our first-principles calculations, we experimentally accomplish the modification of the coordination environment of active sites on MoC nanoparticle surfaces by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites' affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites and reduces the over-adsorption of OH on the Mo active sites, as predicted by the calculations. The atomic-level modification is well confirmed by atomic-resolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolyte. Meantime, it also exhibits a negligible activity loss over 50 h.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper

The reaction microenvironment plays a key role in dictating the selectivity of electrochemical CO 2 reduction. However, understanding the chemical nature of this microenvironment under operating conditions remains a substantial challenge. For this study, we employed attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) in operando for simultaneous measurements of reaction kinetics and concentrations of reactants and intermediates at the reaction interface, all under controlled mass transport conditions. These operando measurements enable direct correlations between the reaction microenvironment, mass transport, and kinetics for a Cu electrocatalyst, such as higher local concentrations of CO 2 under faster mass transport corresponding to higher rates of CO 2 reduction. We observed that faster mass transport decreased the *CO coverage at less negative potentials (-0.6 V RHE ) and increased the *CO coverage at more negative potentials (-1.1 V RHE ). We developed a transport-coupled kinetic model that captures these spectroscopic observations and provides insight into the processes controlling interfacial concentrations of reactants and intermediates, aiding future efforts toward tailoring reaction microenvironments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Inner Shell Spectroscopy beamline at NSLS-II: a facility for in situ and operando X-ray absorption spectroscopy for materials research

The Inner Shell Spectroscopy (ISS) beamline on the 8-ID station at the National Synchrotron Light Source II (NSLS-II), Upton, NY, USA, is a high-throughput X-ray absorption spectroscopy beamline designed for in situ, operando, and time-resolved material characterization using high monochromatic flux and scanning speed. This contribution discusses the technical specifications of the beamline in terms of optics, heat load management, monochromator motion control, and data acquisition and processing. Results of the beamline tests demonstrating the quality of the data obtainable on the instrument, possible energy scanning speeds, as well as long-term beamline stability are shown. The ability to directly control the monochromator trajectory to define the acquisition time for each spectral region is highlighted. Examples of studies performed on the beamline are presented. The paper is concluded with a brief outlook for future developments.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO 2

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO 2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO 2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO 2 from gas mixtures via O$-$C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13 C-labeled CO 2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol -1 between CO 2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO 2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO 2 insertion. In conclusion, the as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO 2 in crystalline scaffolds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Soft x-ray absorption spectroscopy and magnetic circular dichroism as operando probes of complex oxide electrolyte gate transistors

Electrolyte-based transistors utilizing ionic liquids/gels have been highly successful in the study of charge-density-controlled phenomena, particularly in oxides. Experimental probes beyond transport have played a significant role, despite challenges in their application in electric double-layer transistors. Here, we demonstrate the application of synchrotron soft x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) as operando probes of the charge state and magnetism in ion-gel-gated ferromagnetic perovskite films. Electrochemical response via oxygen vacancies at positive gate bias in LaAlO 3 (001)/La 0.5 Sr 0.5 CoO 3-δ is used as a test case. XAS/XMCD measurements of 4–25 unit-cell-thick films first probe the evolution of hole doping (from the O K-edge pre-peak) and ferromagnetism (at the Co L-edges), to establish a baseline. Operando soft XAS/XMCD of electrolyte-gated films is then demonstrated, using optimized spin-coated gels with a thickness of ~1 μm and a specific composition. The application of gate voltages up to +4 V is shown to dramatically suppress the O K-edge XAS pre-peak intensity and Co L-edge XMCD, thus enabling the Co valence and ferromagnetism to be tracked upon gate-induced reduction. Soft XAS and XMCD, with appropriate electrolyte design, are thus established to be viable for the operando characterization of electrolyte-gated oxides.

Yu, Biqiong↗
DOE OSTI2026

Identification of In Situ Generated High-Spin Fe(II)-N 4 Active Sites for Acidic Oxygen Reduction Reaction via Operando 57 Fe Mössbauer Spectroscopy

Iron-nitrogen-carbon (FeNC) catalysts are considered among the most promising alternative to Pt catalysts in acidic oxygen reduction reaction (ORR), yet the geometric and electronic structures of the true active site under reaction conditions have not been clearly elucidated. Herein, we synthesized a representative FeNC catalyst by pyrolyzing Fe 3+ absorbed on ZIF-8-derived N-doped carbon at a mild temperature under the H 2 /Ar atmosphere, where a formation mechanism of FeN 4 sites through a Zn-mediated Fe nanoparticle atomization process was proposed. The resulting FeNC-750 catalyst shows high acidic ORR activity with a half-wave potential of 0.838 V and a peak power density of 1 W cm -2 in proton-exchange membrane fuel cell (PEMFC). By using operando 57 Fe Mössbauer spectroscopy on FeNC-750, it was revealed that the pyrrolic N-coordinated high-spin Fe 2+ N 4 sites, which are in situ generated from high-spin Fe 3+ N 4 during ORR, are identified as catalytic active states. Density functional theory calculations further verified that, compared to the pyridinic N-coordinated low-spin Fe 2+ N 4 , the pyrrolic N-coordinated high-spin Fe 2+ exhibits optimized adsorption energy for reaction intermediates, thereby lowering the energy barrier of the rate-determining step (RDS) and facilitating OH* desorption. In conclusion, this work provides both experimental and theoretical evidence of the true active site in the FeNC during acidic ORR, offering significant insights for the rational design of high-performance materials for acidic fuel cells.

FeNC catalyst↗
DOE OSTI2023

Investigating Hydrogen Isotope Exchange Reactions on Lithium Aluminate Pellets in TPBAR (FY22 Report)

We developed a novel operando Raman spectroscopy method for investigation of hydrogen (H) isotope exchange reactions in the lithium aluminate (γ-LiAlO 2 ) that allows modeling of tritium behaviors in high temperature and in an irradiated environment. The lithium aluminate pellet is a main component in the Tritium-Producing Burnable Absorber Rod (TPBAR). We used deuterium ( 2 H or D) as a surrogate to simulate tritium ( 3 H or T). We used a surface analysis tools in situ/operando Raman spectroscopy to observe the transformation OH and OD compositional changes. We also used ToF-SIMS to analyze the lithium aluminate pellet control sample to build the base line for future in situ/operando analysis. To conduct operando Raman spectroscopy, we developed a custom reaction cell with a detachable micro heater using microelectromechanical systems (MEMS) and 3D printing techniques. Multiple versions were developed and tested. Using the new reaction cell, we demonstrated operando Raman spectroscopy of water (H 2 O) and deuterated water (D 2 O) with nitrogen (N 2 ) exposure onto the lithium aluminate (LiAlO2) pellet specimen, respectively, using a wet gas injection setup. We also successfully developed a detachable microheater that can heat up to ~250°C for ~90 mins. The Raman spectra did not show clear H 2 O and D 2 O characteristic peaks, which indicates that introducing H 2 O and D 2 O onto the surface of the pellet is challenging due to its dense structure nature. Our efforts suggest that various improvements are needed, such as increasing reaction cell operating gas pressure and thinning pellet sample thickness, to obtain meaningful measurements.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2021

Enhancing the inherent catalytic activity and stability of TiO 2 supported Pt single-atoms at CeO x –TiO 2 interfaces

Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO 2 and Pt/CeO x –TiO 2 . Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO 2 supporting particles and CeO x clusters formed on the surface of TiO 2 , we preferentially synthesized Pt-SAs pinned at the CeO x –TiO 2 interfaces on CeO x –TiO 2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeO x –TiO 2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeO x –TiO 2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO 2 . The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Finally, our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Real-time interface investigation on degradation mechanism of organic light-emitting diode by in-operando X-ray spectroscopies

Understanding the chemical evolution at the interface of organic light-emitting diodes (OLEDs) under working conditions is critical for addressing device failure and further improving performance. In this work, an in-operando approach was developed employing synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the electronic structures and chemical degradation mechanisms of a model tris(8-hydroxyquinoline) aluminum (Alq 3 )-based OLED device under working condition. The results identify that Mg atoms from the electrode migrate into the Alq 3 organic layer under a potential bias and replace Al atom sites, forming the unstable Mgq 3 species which lead to device degradation. Here, the findings from the classic and simple model device elucidate the degradation mechanisms occurred at the interface of OLED devices, which may facilitate the development of more efficient and stable OLED devices with complex structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing the electrical double layer by operando X‐ray photoelectron spectroscopy through a graphene‐carbon nanotube composite window

Abstract The electrical double layer is known to spontaneously form at the electrode‐electrolyte interface, impacting many important chemical and physical processes as well as applications including electrocatalysis, electroorganic synthesis, nanomaterial preparation, energy storage, and even emulsion stabilization. However, it has been challenging to study this fundamental phenomenon at the molecular level because the electrical double layer is deeply “buried” by the bulk electrolyte solution. Here, we report a quantitative probing of the electrical double layer of ionic liquids from the solid side of a photoelectron‐transparent graphene‐carbon nanotube hybrid membrane electrode using X‐ray photoelectron spectroscopy. The membrane window is ultrathin (1‐1.5 nm), large (~1 cm 2 ), and robust, enabling a tight seal of the electrolyte and quantitative measurement with excellent photoelectron signals. By operando monitoring the population changes of cations and anions in response to the applied electrical potentials, we experimentally resolve the chemical structure and dynamics of the electrical double layer, which corroborate results from molecular dynamics simulations. image

Wang, Peng↗
DOE OSTI2023

Disordered Au Nanoclusters for Efficient Ammonia Electrosynthesis

The electrochemical nitrogen (N 2 ) reduction reaction (N 2 RR) under mild conditions is a promising and environmentally friendly alternative to the traditional Haber-Bosch process with high energy consumption and greenhouse emission for the synthesis of ammonia (NH 3 ), but high-yielding production is rendered challenging by the strong nonpolar N≡N bond in N 2 molecules, which hinders their dissociation or activation. In this study, disordered Au nanoclusters anchored on two-dimensional ultrathin Ti 3 C 2 T x MXene nanosheets are explored as highly active and selective electrocatalysts for efficient N 2 -to-NH 3 conversion, exhibiting exceptional activity with an NH 3 yield rate of 88.3±1.7 μg h –1 mg cat. –1 and a faradaic efficiency of 9.3±0.4 %. Further, a combination of in situ near-ambient pressure X-ray photoelectron spectroscopy and operando X-ray absorption fine structure spectroscopy is employed to unveil the uniqueness of this catalyst for N 2 RR. The disordered structure is found to serve as the active site for N 2 chemisorption and activation during the N 2 RR process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nickel-rich Nickel Manganese Cobalt (NMC622) Cathode Lithiation Mechanism and Extended Cycling Effects Using Operando X-ray Absorption Spectroscopy

Ni-rich NMC materials are a particularly promising class of Li-ion cathodes for various applications. LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) offers a unique balance of thermal stability and energy density, thus attracting attention for electric vehicle implementation. However, upon extended cycling, capacity fade is prevalent due to structural degradation, which is a major drawback for layered oxide cathodes. Therefore, exploring the underlying phenomena that drive detrimental structural response can lead to future improvements. For the first time, operando X-ray absorption spectroscopy (XAS) was performed on NMC622 pouch cells at three different stages. An extensive description of the first cycle (de)lithiation mechanisms was achieved through X-ray absorption near-edge structure analyses and extended X-ray absorption fine structure modeling. Transition metal specific electrochemical participation and structural variation revealed that much of the delivered capacity and distortion is a result of Ni redox behavior, while the local structure of Co and Mn are impacted due to their interdependencies. Key mechanistic components were identified, as the local structural variation from redox processes and Ni 3+ Jahn–Teller distortion were decoupled. Further, operando XAS was used to investigate the structural response of NMC622 to extended cycling and was supported by X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy analyses. In this work, reduced capacity was found in the cell after 100 cycles and is attributed to structural degradation and cathode–electrolyte interphase buildup from repeated Li (de)insertion processes, which limit the electrochemical reversibility of Ni and Co through increased polarization. These results expand the understanding of a Ni-rich NMC material under extended cycling, which is vital to the future design of electrode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

In Operando Angle‐Resolved Photoemission Spectroscopy with Nanoscale Spatial Resolution: Spatial Mapping of the Electronic Structure of Twisted Bilayer Graphene

To pinpoint the electronic and structural mechanisms that affect intrinsic and extrinsic performance limits of 2D material devices, it is of critical importance to resolve the electronic properties on the mesoscopic length scale of such devices under operating conditions. Herein, angle‐resolved photoemission spectroscopy with nanoscale spatial resolution (nanoARPES) is used to map the quasiparticle electronic structure of a twisted bilayer graphene device. The dispersion and linewidth of the Dirac cones associated with top and bottom graphene layers are determined as a function of spatial position on the device under both static and operating conditions. The analysis reveals that microscopic rotational domains in the two graphene layers establish a range of twist angles from 9.8° to 12.7°. Application of current and electrostatic gating lead to strong electric fields with peak strengths of 0.75 V/μm at the rotational domain boundaries in the device. These proof‐of‐principle results demonstrate the potential of nanoARPES to link mesoscale structural variations with electronic states in operating device conditions and to disentangle such extrinsic factors from the intrinsic quasiparticle dispersion.

Majchrzak, Paulina↗
DOE OSTI2025

Deciphering the local structure of Prussian blue analogue cathodes with Raman spectroscopy for sodium-ion batteries

Iron-based Prussian blue analogues (PBAs) have gained attention as low-cost, relatively higher-potential cathodes for sodium-ion batteries, due to their open 3D-framework structures. However, understanding the local structural changes is critical to unveiling the intercalation pathways and degradation mechanisms. We employ here operando Raman spectroscopy to probe the changes in the cyanide vibrational modes during cycling and degradation after cycling, which are not adequately resolved by X-ray diffraction due to the low structure factor and limited X-ray sensitivity of the cyanide groups. Vibrational spectroscopy has thus proven essential for deciphering these complex materials. Additionally, we implement pre-sodiation strategies to assess the impact of sodium inventory loss by pairing PBAs with a hard carbon anode in a full-cell configuration. Operando galvanostatic electrochemical impedance spectroscopy (EIS) and ex situ X-ray photoelectron spectroscopy (XPS) further elucidate the interface evolution and the role of water molecules in forming the cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI). The insights gained advance the understanding of PBAs and enhance their practical viability.

25 ENERGY STORAGE↗
DOE OSTI2024

Monitoring Redox Processes in Lithium-Ion Batteries by Laboratory-Scale Operando X-ray Emission Spectroscopy

Tracking changes in the chemical state of transition metals in alkali-ion batteries is crucial to understanding the redox chemistry during operation. X-ray absorption spectroscopy (XAS) is often used to follow the chemistry through observed changes in the chemical state and local atomic structure as a function of the state-of-charge (SoC) in batteries. In this study, we utilize an operando X-ray emission spectroscopy (XES) method to observe changes in the chemical state of active elements in batteries during operation. Operando XES and XAS were compared by using a laboratory-scale setup for four different battery systems: LiCoO 2 (LCO), Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 (NMC111), Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 (NMC811), and LiFePO 4 (LFP) under a constant current charging the battery in 10 h (C/10 charge rate). We show that XES, despite narrower chemical shifts in comparison to XAS, allows us to fingerprint the battery SOC in real time. We further demonstrate that XES can be used to track the change in net spin of the probed atoms by analyzing changes in the emission peak shape. As a test case, the connection between net spin and the local chemical and structural environment was investigated by using XES and XAS in the case of electrochemically delithiated LCO in the range of 2–10% lithium removal.

25 ENERGY STORAGE↗