Time-resolved Soft X-ray Absorption Research Articles

Key Role of Oxidising Species for Water Oxidation on Iridium Oxides Revealed By Time-Resolved Optical and X-Ray Spectroscopies

Iridium oxide is the state-of-the-art electrocatalyst for water oxidation in polymer electrolyte membrane (PEM) electrolysers, crucial for green hydrogen production. Despite its extensive industrial use, the water oxidation mechanism on this metal oxide and the key factors controlling the reaction rate remain unclear. Understanding these controls at a fundamental level on such benchmark metal oxides is vital for designing more active and stable electrocatalysts for water oxidation in PEM electrolysers.In this talk, I will present our research on probing oxygen evolution reaction (OER) relevant species on iridium-based catalysts. This involves a combination of time-resolved operando optical spectroscopy, soft and hard X-ray absorption spectroscopy (XAS), and electrochemical mass spectrometry. Initially, I will discuss the intermediate and catalytically active states of iridium oxides. This is based on correlating optically detected states with oxygen molecular products identified through on-chip electrochemical mass spectrometry. Subsequently, I will demonstrate how we used optical spectroscopy to quantify these states as a function of potential. The nature of these states, including the Ir oxidation state and surface adsorbates on iridium sites, will be elucidated using a combination of time-resolved Ir-L edge XAS, O-K edge XAS, and supported by Density Functional Theory (DFT).With these quantification results of active species for OER, I will compare the intrinsic kinetics of two state-of-the-art iridium oxide structures - amorphous IrOx versus crystalline rutile IrO2.[1] The effect of the electrolyte on the intrinsic activity of iridium oxides will also be discussed.[2] Finally, based on this molecular-level understanding, I will present a modified volcano model for OER catalyst design. This model considers the impact of adsorbate-adsorbate interactions on binding energetics, demonstrating critical design principles for high intrinsic activity OER catalysts.The authors acknowledge the funding support from the Imperial College-Chinese Scholarship Council Studentship and bp-ICAM 92, which made this research possible.[1] Caiwu Liang, Reshma Rao, Karine Svane et al. Unravelling the effects of active site densities and energetics on the water oxidation activity of iridium oxides, 07 March 2023, PREPRINT (Version 1) available at Research Square [https://doi.org/10.21203/rs.3.rs-2605628/v1][2] Caiwu Liang, Yu Katayama, Yemin Tao, Asuka Morinaga, Benjamin Moss, Verónica Celorrio, et al. Role of electrolyte pH on water oxidation for iridium oxides. ChemRxiv. Cambridge: Cambridge Open Engage; 2023

Operando time-resolved soft x-ray absorption spectroscopy for photoexcitation processes of metal complexes in solutions.

Operando time-resolved soft x-ray absorption spectroscopy (TR-SXAS) is an effective method to reveal the photochemical processes of metal complexes in solutions. In this study, we have developed the TR-SXAS measurement system for observing various photochemical reactions in solutions by the combination of laser pump pulses with soft x-ray probe pulses from the synchrotron radiation. For the evaluation of the developed TR-SXAS system, we have measured nitrogen K-edge x-ray absorption spectroscopy (XAS) spectra of aqueous iron phenanthroline solutions during a photoinduced spin transition process. The decay process of the high spin state to the low spin state in the iron complex has been obtained from the ligand side by N K-edge XAS, and the time constant is close to that obtained from the central metal side by time-resolved Fe K-edge XAS in the previous studies.

Towards Understanding Excited-State Properties of Organic Molecules Using Time-Resolved Soft X-ray Absorption Spectroscopy.

The extension of the pump-probe approach known from UV/VIS spectroscopy to very short wavelengths together with advanced simulation techniques allows a detailed analysis of excited-state dynamics in organic molecules or biomolecular structures on a nanosecond to femtosecond time level. Optical pump soft X-ray probe spectroscopy is a relatively new approach to detect and characterize optically dark states in organic molecules, exciton dynamics or transient ligand-to-metal charge transfer states. In this paper, we describe two experimental setups for transient soft X-ray absorption spectroscopy based on an LPP emitting picosecond and sub-nanosecond soft X-ray pulses in the photon energy range between 50 and 1500 eV. We apply these setups for near-edge X-ray absorption fine structure (NEXAFS) investigations of thin films of a metal-free porphyrin, an aggregate forming carbocyanine and a nickel oxide molecule. NEXAFS investigations have been carried out at the carbon, nitrogen and oxygen K-edge as well as on the Ni L-edge. From time-resolved NEXAFS carbon, K-edge measurements of the metal-free porphyrin first insights into a long-lived trap state are gained. Our findings are discussed and compared with density functional theory calculations.

Quantitative evaluation of transient valence orbital occupations in a 3d transition metal complex as seen from the metal and ligand perspective

It is demonstrated for the case of photo-excited ferrocyanide how time-resolved soft X-ray absorption spectroscopy in transmission geometry at the ligand K-edge and metal L3-edge provides quantitatively equivalent valence electronic structure information, where signatures of photo-oxidation are assessed locally at the metal as well as the ligand. This allows for a direct and independent quantification of the number of photo-oxidized molecules at two soft X-ray absorption edges highlighting the sensitivity of X-ray absorption spectroscopy to the valence orbital occupation of 3d transition metal complexes throughout the soft X-ray range.

Diagnostic Studies on Ni-Rich NMC Layered Cathode Materials By Using Synchrotron-Based X-Ray Techniques

Layered Ni-rich LiNixMnyCozO2 (NMC, x ≥ 0.6, x+y+z=1) cathode have attracted significant interest as the cathode materials for rechargeable lithium batteries (LIBs) owing to their high capacity, excellent rate capability and low cost. However, some drawbacks such as capacity fade during cycling and low thermal-abuse tolerance at elevated temperature, prohibiting their use in practical batteries. In addition, when in highly charged states, the reduction of Ni ions during thermal heating releases oxygen from the crystal structure, which can lead thermal runaway and violent reactions with the flammable electrolyte. To overcome performance degradation and improve battery safety, several strategies including lattice doping, surface treatment/modification, tuning the material compositions has been proposed and demonstrated. As one of promising approaches, concentration gradient LiNixMnyCozO2 (CG-NMC) cathode material, in which the Ni concentration decreases and the Mn concentration increases linearly toward the particle surface, has received considerable attention due to its high capacity and improved structural stability. [1-3] The concept of CG-NMC opens many new possibilities for developing high Ni content NMC cathode with high capacity and improved safety characteristic for practical LIB applications. It is well-accepted that the material design of Ni-rich core and Mn-rich surface leads to the high capacity and better thermal stability, compared with normal NMC cathode materials. However, more detailed working mechanisms of CG-NMC cathode have not been fully understood yet. In this study, the structural and chemical changes of normal NMC and CG-NMC cathode materials with various testing conditions including cycling numbers, different cut-off voltages, thermal heating, will be investigated by using synchrotron based time-resolved X-ray diffraction (TR-XRD), hard and soft X-ray absorption spectroscopy (XAS) techniques. Due to its structural and chemical inhomogeneity of CG-NMC cathode materials, the combined use of various types of characterization techniques is essential. Combinations of TR-XRD, hard and soft XAS techniques allow us to distinguish the electronic and crystal structure differences between the bulk and surface of cathode materials in various conditions. The result will provide valuable information for the development and optimize Ni-rich NMC cathode materials with increased capacity and better thermal stability. Acknowledgement The work at Brookhaven National Lab. was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies (BMR and VTO Battery500 projects) under Contract Number DE-AC02-98CH10886. The work was collaborated with UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357.

Time-resolved soft X-ray absorption spectroscopy in transmission mode on liquids at MHz repetition rates.

We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology.

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries

The electronic structures of bare and ZrO2-coated Li(Ni0.8Co0.15Al0.05)O2 electrode systems were investigated using a combination of time-resolved X-ray diffraction and soft X-ray absorption spectroscopy (XAS) techniques. The ZrO2 coating on the surface of Li(Ni0.8Co0.15Al0.05)O2 was effective in elevating the onset temperature of the dissociation of charged Li0.33(Ni0.8Co0.15Al0.05)O2, which will enhance the safety of Li-ion cells. Soft XAS spectra of the Ni LII,III-edge in the partial electron yield mode were obtained, which showed that the enhanced electrochemical properties and thermal stability of the cathode materials by ZrO2 coating can be attributed to the suppression of unwanted Ni oxidation state changes at the surface. The electronic structural effects of a ZrO2 coating on Li(Ni0.8Co0.15Al0.05)O2 were examined by soft X-ray absorption spectroscopy. The coating stabilized the Ni oxidation state at the electrode surface against decomposition

Element-specific characterization of transient electronic structure of solvated Fe(II) complexes with time-resolved soft X-ray absorption spectroscopy.

Polypyridyl transition-metal complexes are an intriguing class of compounds due to the relatively facile chemical designs and variations in ligand-field strengths that allow for spin-state changes and hence electronic configurations in response to external perturbations such as pressure and light. Light-activated spin-conversion complexes have possible applications in a variety of molecular-based devices, and ultrafast excited-state evolution in these complexes is of fundamental interest for understanding of the origins of spin-state conversion in metal complexes. Knowledge of the interplay of structure and valence charge distributions is important to understand which degrees of freedom drive spin-conversion and which respond in a favorable (or unfavorable) manner. To track the response of the constituent components, various types of time-resolved X-ray probe methods have been utilized for a broad range of chemical and biological systems relevant to catalysis, solar energy conversions, and functional molecular devices. In particular, transient soft X-ray spectroscopy of solvated molecules can offer complementary information on the detailed electronic structures and valence charge distributions of photoinduced intermediate species: First-row transition-metal L-edges consist of 2p-3d transitions, which directly probe the unoccupied valence density of states and feature lifetime broadening in the range of 100 meV, making them sensitive spectral probes of metal-ligand interactions. In this Account, we present some of our recent progress in employing picosecond and femtosecond soft X-ray pulses from synchrotron sources to investigate element specific valence charge distributions and spin-state evolutions in Fe(II) polypyridyl complexes via core-level transitions. Our results on transient L-edge spectroscopy of Fe(II) complexes clearly show that the reduction in σ-donation is compensated by significant attenuation of π-backbonding upon spin-crossover. This underscores the important information contained in transient metal L-edge spectroscopy on changes in the 3d orbitals including oxidation states, orbital symmetries, and covalency, which largely define the chemistry of these complexes. In addition, ligand K-edge spectroscopy reveals the "ligand view" of the valence charge density by probing 1s-2p core-level transitions at the K-edge of light elements such as nitrogen, carbon, and oxygen. In the case of Fe(II) spin-conversion complexes, additional details of the metal-ligand interactions can be obtained by this type of X-ray spectroscopy. With new initiatives in and construction of X-ray free-electron laser sources, we expect time-resolved soft X-ray spectroscopy to pave a new way to study electronic and molecular dynamics of functional materials, thereby answering many interesting scientific questions in inorganic chemistry and material science.

Time-resolved soft x-ray absorption setup using multi-bunch operation modes at synchrotrons

Here, we report on a novel experimental apparatus for performing time-resolved soft x-ray absorption spectroscopy in the sub-ns time scale using non-hybrid multi-bunch mode synchrotron radiation. The present setup is based on a variable repetition rate Ti:sapphire laser (pump pulse) synchronized with the ~500 MHz x-ray synchrotron radiation bunches and on a detection system that discriminates and singles out the significant x-ray photon pulses by means of a custom made photon counting unit. The whole setup has been validated by measuring the time evolution of the L(3) absorption edge during the melting and the solidification of a Ge single crystal irradiated by an intense ultrafast laser pulse. These results pave the way for performing synchrotron time-resolved experiments in the sub-ns time domain with variable repetition rate exploiting the full flux of the synchrotron radiation.

Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

Solution-phase photoinduced low-spin to high-spin conversion in the Fe(II) polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)(3) is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) --> (1)MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L(2)- and L(3)-edges were observed concomitant with formation of the transient high-spin (5)T(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of approximately 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 A increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

Space- and time-resolved soft x-ray absorption spectroscopy of aluminum plasma induced by femtosecond-laser ablation

. We developed a space- and time-resolved soft x-ray absorption spectroscopy system for the study of ablation dynamics induced by femtosecond laser irradiation onto an aluminum target. The system consists of an x-ray microscope for imaging and a femtosecond-laserplasma x-ray source for time-resolved measurements. Ablation of neutral and condensed aluminum particles following plasma expansion was observed as shifts of the aluminum L-shell photoabsorption edge in space- and time resolved absorbance spectra.

Observation of femtosecond-laser-induced ablation plumes of aluminum using space- and time-resolved soft x-ray absorption spectroscopy

The dynamics of the laser ablation plume expansion of aluminum was investigated by using space- and time-resolved soft x-ray absorption spectroscopy. Blueshifts of the Al L-shell photoabsorption edge indicating the state of aluminum were observed in the plumes, which were generated by irradiating an aluminum target with 120fs near-infrared pulses at an intensity of 1014W∕cm2. The spatiotemporal evolution of the plumes exhibited a multilayer structure consisting of vaporized aluminum and condensed aluminum particles, following the expansion of plasma, with expansion velocities of 104m∕s for the atomic state and 103m∕s for the condensed state.

Soft x-ray imaging system for picosecond time-resolved absorption spectroscopy using a femtosecond-laser-plasma source

We have developed an imaging system for time-resolved soft x-ray absorption spectroscopy. The system consists of a femtosecond-laser-plasma x-ray source for time-resolved measurements and an x-ray microscope with critical illumination for imaging. The temporal and spatial resolutions were 23ps and better than 12.5μm, respectively. We applied this system to the measurement of an aluminum ablation plume induced by irradiation with a 120fs laser pulse. The shift of the L-shell photoabsorption edge in the expanding plume was observed in the spatiotemporally resolved absorbance spectrum. The space- and time-resolved x-ray absorption spectrum of an expanding laser ablation plume was clearly obtained using the developed system.

Interaction of Laser Light with Solids

Laser ablation using nanosecond pulsed laser light includes some important transient processes during and after laser irradiation. In this paper, the optical absorption of semiconductors and the energy relaxation of excited electrons and holes are briefly described, followed by rapid phase transformation such as transient melting and vaporization which lead to laser ablation of materials. Initial processes of vaporization of solids due to laser ablation have been investigated by several time-resolved measurements. Here we describe a method of time-resolved soft X-ray absorption spectroscopy measurement to show an example of the initial plume produced by laser ablation of Si. This technique gives us information of the time dependence of ejection of Si atoms and Si ions (Si+˜Si4+), and their time-dependent spatial profiles. In addition to nanosecond pulsed laser ablation, characteristics of femtosecond pulsed laser ablation is also discussed, which has been very important to applications.

Time-resolved soft x-ray absorption spectroscopy of silicon using femtosecond laser plasma x rays

We measured time-resolved soft x-ray absorption of photoexcited silicon by means of pump-probe spectroscopy, using a picosecond soft x-ray pulse from femtosecond laser-produced plasma as a probe. We observed a 5% increase in the absorption caused by 1010 W/cm2 intensity laser pulse irradiation near the LII,III edge at 100 eV. The change was observed only when the laser and the soft x-ray pulses overlapped on the sample both in time and space.

Dynamics of Si plume produced by laser ablation in ambient inert gas and formation of Si nanoclusters

We have performed (1) time-resolved soft X-ray absorption measurements on a time scale up to 15 μs after pulsed-laser ablation of silicon (Si) in an ambient Ar gas with a transient pressure of about 10 Torr and (2) investigation of the correlation between 1.6-eV photoluminescence (PL) from Si nanocluster-based films and the surface oxidation. No soft X-ray absorption lines corresponding to Si clusters were observed, indicating that it is likely that after 15 μs, significant clustering takes place and then Si nanoclusters can grow. From experiments involving hydrogen termination and hydrogen atom treatment in addition to natural oxidation, it is found that the 1.6-eV PL originates from the interface of a Si nanocluster core and a surface oxide layer and occurs without hydrogen atoms.