Electron dynamics induced by resonant absorption of light is of fundamental importance in nature and has been the subject of countless studies in many scientific areas. Above the ionization threshold ...of atomic or molecular systems, the presence of discrete states leads to autoionization, which is an interference between two quantum paths: direct ionization and excitation of the discrete state coupled to the continuum. Traditionally studied with synchrotron radiation, the probability for autoionization exhibits a universal Fano intensity profile as a function of excitation energy. However, without additional phase information, the full temporal dynamics cannot be recovered. Here we use tunable attosecond pulses combined with weak infrared radiation in an interferometric setup to measure not only the intensity but also the phase variation of the photoionization amplitude across an autoionization resonance in argon. The phase variation can be used as a fingerprint of the interactions between the discrete state and the ionization continua, indicating a new route towards monitoring electron correlations in time.
Pt-TiO2-C composites with different titanium oxide loading were synthesized by photo-deposition and chemical vapor deposition methods. The changes in their electronic properties improve the ...electrochemical activity toward the oxygen reduction reaction (ORR) compared to the Pt-C catalyst synthesized at the same conditions. The platinum samples were physically characterized by means of Transmission Electron Microscopy (TEM), Small Angle X-ray Scattering (SAXS), X-ray Absorption Spectroscopy (XAS) and X-ray Photo-electron Spectroscopy (XPS). Their electrochemical activity was also investigated by cyclic and linear voltammetry techniques. TEM analysis shows homogeneously dispersed platinum nanoparticles with an average particle size of 2 nm in all the synthesized samples. Form factor (morphology model) and particle size were determined by SAXS, the data adjusted to spherical Pt nanoparticles in both synthesis methods. XAS studies at the Pt L3-edge shows a close interaction of Pt with the support material, i.e. C or TiO2. XPS analysis reveals surface modifications that induce electronic changes on Pt-TiO2-C. Significant differences in the ORR electrochemical activity were correlated to the TiO2 loading and the synthesis procedure.
► The activity of Pt-TiO2-C composites for the ORR was determined. ► The oxide loading effect on the ORR activity was evaluated. ► XAS and XPS results confirm a strong metal–support interaction. ► The role of TiO2 can be addressed as co-catalyst of Pt for the ORR.
This work presents an x-ray absorption measurement by use of ionizing radiation generated by a femtosecond pulsed laser source. The spectrometer was a microcalorimetric array whose pixels are capable ...of accurately measuring energies of individual radiation quanta. An isotropic continuum x-ray spectrum in the few-keV range was generated from a laser plasma source with a water-jet target. X rays were transmitted through a ferrocene powder sample to the detector, whose pixels have average photon energy resolution ΔE=3.14 eV full-width-at-half-maximum at 5.9 keV. The bond distance of ferrocene was retrieved from this first hard-x-ray absorption fine-structure spectrum collected with an energy-dispersive detector. This technique will be broadly enabling for time-resolved observations of structural dynamics in photoactive systems.
We have studied the photoinduced low spin (LS) to high spin (HS) conversion of Fe(bipy)(3)(2+) in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, ...time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate, we observed the interplay between intramolecular dynamics and the intermolecular caging solvent response with better than 100 ps time resolution. On this time scale, the initial ultrafast spin transition and the associated intramolecular geometric structure changes are long completed, as is the solvent heating due to the initial energy dissipation from the excited HS molecule. Combining information from X-ray emission spectroscopy and scattering, the excitation fraction as well as the temperature and density changes of the solvent can be closely followed on the subnanosecond time scale of the HS lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics of the caging solvent, in particular, a decrease in the number of water molecules in the first solvation shell is inferred, as predicted by recent theoretical work.
A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time ...resolution of tens of microseconds and high detection efficiency for samples with sub-millimolar concentrations. A continuous wave laser is used for the photoexcitation, with the distance between laser and X-ray beams and velocity of liquid flow determining the time delay, while the focusing of both beams and the flow speed profile define the time resolution. This method is compared with the alternative measurement technique that utilizes a 1 kHz repetition rate laser and multiple X-ray probe pulses. Such an experiment was performed at beamline 11ID-D of the Advanced Photon Source. Advantages, limitations, and potential for improvement of the pump-flow-probe setup are discussed by analyzing the photon statistics. Both methods with Co K-edge probing were applied to the investigation of a cobaloxime-based photocatalytic reaction. The interplay between optimizing for efficient photoexcitation and time resolution as well and the effect of sample degradation for these two setups are discussed.
Establishing a tractable yet complete reaction coordinate for the spin-state interconversion in d4–d7 transition metal complexes is an integral aspect of controlling the dynamics that govern their ...functionality. For spin crossover phenomena, the limitations of a single-mode approximation that solely accounts for an isotropic increase in the metal–ligand bond length have long been recognized for all but the simple octahedral monodentate FeII compounds. However, identifying the coupled deformations that also impact on the unimolecular rate constants remains experimentally and theoretically challenging, especially for samples that do not display long-range order or when crystallization profoundly alters the dynamics. Owing to the rapid progress in ultrafast X-ray absorption spectroscopy (XAS), it is now possible to obtain transient structural information in any physical phase with unprecedented details. Using picosecond XAS and DFT modeling, the structure adopted by the photoinduced high-spin state of solvated Fe(terpy)22+ (terpy: 2,2′:6′,2″-terpyridine) has been recently established. Based on these results, the methodology of the continuous shape measure is applied to classify and quantify the short-lived distortion of the first coordination shell. The reaction coordinate of the spin-state interconversion is clearly identified as a double axial bending. This finding sets a benchmark for gauging the influence of first-sphere and second-sphere interactions in the family of FeII complexes that incorporate terpy derivatives. Some implications for the optimization of related photoactive FeII complexes are also outlined.
The fuel cell performance of membrane electrode assemblies with a Pt anode and Pd, PdCu or Pd sub(5)Cu sub(4)Pt cathodes has been tested during 116 h (beginning of life). The incorporation of Cu to ...Pd increases the fuel cell performance. Incorporation of Pt leads to further improvement. SEM micrographs of the as-prepared and the fuel cell-tested assemblies show the effects of the 116 h of continuous operation. Nafion membranes were characterized by small angle X-ray scattering. The results show a reduction of the size of the lamellar domains in the perfluorinated matrix after fuel cell testing, but no correlation with the cathode electrocatalyst material. The cathode electrocatalysts were characterized by ex-situ synchrotron radiation X-ray diffraction and X-ray absorption spectroscopy at the Pd L sub(3), Cu K and Pt L sub(3) edges. Re-organization of Pd sub(5)Cu sub(4)Pt electrocatalyst after fuel cell testing was observed. The Cu in the electrocatalyst can be described as a nano-mixture of metallic Cu, alloyed Cu and CuO. The CuO acts as a promoter of the ORR.
The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in ...our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.
Recessive cytosolic aminoacyl-tRNA synthetase (ARS) deficiencies are severe multiorgan diseases, with limited treatment options. By loading transfer RNAs (tRNAs) with their cognate amino acids, ARS ...are essential for protein translation. However, it remains unknown why ARS deficiencies lead to specific symptoms, especially early life and during infections. We set out to increase pathophysiological insight and improve therapeutic possibilities.
In fibroblasts from patients with isoleucyl-RS (IARS), leucyl-RS (LARS), phenylalanyl-RS-beta-subunit (FARSB), and seryl-RS (SARS) deficiencies, we investigated aminoacylation activity, thermostability, and sensitivity to ARS-specific amino acid concentrations, and developed personalized treatments.
Aminoacylation activity was reduced in all patients, and further diminished at 38.5/40 °C (P
and P
), consistent with infectious deteriorations. With lower cognate amino acid concentrations, patient fibroblast growth was severely affected. To prevent local and/or temporal deficiencies, we treated patients with corresponding amino acids (follow-up: 1/2-2 2/3rd years), and intensified treatment during infections. All patients showed beneficial treatment effects, most strikingly in growth (without tube feeding), head circumference, development, coping with infections, and oxygen dependency.
For these four ARS deficiencies, we observed a common disease mechanism of episodic insufficient aminoacylation to meet translational demands and illustrate the power of amino acid supplementation for the expanding ARS patient group. Moreover, we provide a strategy for personalized preclinical functional evaluation.
Mixtures of powders of platinum with nickel or cobalt to obtain Ni0.75Pt0.25 or Co0.75Pt0.25 were mechanical alloyed by high energy ball milling. The results of crystal structure, morphology and ...electrocatalytic performance are presented for mechanically activated powders after 3 and 9 h of ball milling. Total solid solutions of Ni and Co with platinum were analyzed by X-ray diffraction after 3 h of ball milling. After 9 h of ball milling, in both cases, the total solid solution was accompanied by the appearance of NiO or CoO and ZrO associated with a redox reaction with the milling media. The presence of zirconium monoxide was confirmed by energy dispersive spectroscopy analysis. In both cases, an amorphization was detected. X ray absorption spectroscopy measurements showed changes in atomic and electronic environment of platinum, a reduction of the distance to the first coordination sphere and increased d-band vacancy vs pure Pt and Pt nanoparticles were observed for both studied systems. The electrocatalytic activity was determined using cyclic and linear voltammetry. The Co0.75Pt0.25 alloy milled for 9 h showed a higher electrochemical activity for the oxygen reduction reaction (ORR) compared with the other samples, including Pt-Etek. The degree of the ORR electrochemical activity was correlated with the presence of ZrO, which could affect the oxygen adsorption and improve the catalytic activity for the oxygen reduction reaction.
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•Ni0.75Pt0.25 and Co0.75Pt0.25 alloys were obtained by means of mechanical alloying, and they showed activity towards ORR.•After 9 h of milling ZrO/CoO or ZrO/NiO were obtained.•After 9 h of milling Co0.75Pt0.25 increased Pt d-band vacancy compared with Pt nanoparticles and Pt foil.•The electrocatalytic activity of Co0.75Pt0.25/C-9 h in the ORR is higher than Pt ETEK.
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