Probing the dynamics of plasmon-excited hexanethiol-capped gold nanoparticles by picosecond X-ray absorption spectroscopy

Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au-Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1

High energy resolution off-resonant spectroscopy for X-ray absorption spectra free of self-absorption effects

X-ray emission spectra recorded in the off-resonant regime carry information on the density of unoccupied states. It is known that by employing the Kramers-Heisenberg formalism, the high energy resolution off-resonant spectroscopy (HEROS) is equivalent to the x-ray absorption spectroscopy (XAS) technique and provides the same electronic state information. Moreover, in the present Letter we demonstrate that the shape of HEROS spectra is not modified by self-absorption effects. Therefore, in contrast to the fluorescence-based XAS techniques, the recorded shape of the spectra is independent of the sample concentration or thickness. The HEROS may thus be used as an experimental technique when precise information about specific absorption features and their strengths is crucial for chemical speciation or theoretical evaluation

Detection of Key Transient Cu Intermediates in SSZ-13 During NH₃-SCR deNOₓ by Modulation Excitation IR spectroscopy

The small pore zeolite Cu-SSZ-13 is an efficient material for the standard selective catalytic reduction of nitrogen oxides (NOₓ) by ammonia (NH₃). In this work, Cu-SSZ-13 has been studied at 250 °C under high conversion using a modulation excitation approach and analysed with phase sensitive detection (PSD). While the complementary X-ray absorption near edge structure (XANES) spectroscopy measurements showed that the experiments were performed under cyclic Cu^{+}/Cu^{2+} redox, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) experiments provide spectroscopic evidence for previously postulated intermediates Cu–N([double bond, length as m-dash]O)–NH_{2} and Cu–NO_{3} in the NH_{3}-SCR deNO_{x} mechanism and for the role of [Cu^{2+}(OH^{−})]^{+}

Quick EXAFS setup at the SuperXAS beamline for in situ X ray absorption spectroscopy with 10 ms time resolution

The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup

Scientific Opportunities for Heterogeneous Catalysis Research at the SuperXAS and SNBL Beam Lines

In this short review, we describe the complementary experimental capabilities for catalysis research at two beam lines available to the Swiss community, SuperXAS at SLS (Swiss Light Source, Villigen) and SNBL (Swiss Norwegian Beam lines) at ESRF (European Synchrotron Radiation Facility, Grenoble). Over the years, these two facilities have been developed to provide powerful techniques for structural studies under in situ and operando conditions. These techniques, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES) in combination with Raman or infrared spectroscopy provide new avenues for structure–performance studies of catalysts. Several exemplary studies are used to demonstrate the capability of these facilities

Detection of key transient Cu intermediates in SSZ-13 during NH3-SCR deNOx by modulation excitation IR spectroscopy

The small pore zeolite Cu-SSZ-13 is an efficient material for the standard selective catalytic reduction of nitrogen oxides (NOx) by ammonia (NH3). In this work, Cu-SSZ-13 has been studied at 250 °C under high conversion using a modulation excitation approach and analysed with phase sensitive detection (PSD). While the complementary X-ray absorption near edge structure (XANES) spectroscopy measurements showed that the experiments were performed under cyclic Cu+/Cu2+ redox, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) experiments provide spectroscopic evidence for previously postulated intermediates Cu–N([double bond, length as m-dash]O)–NH2 and Cu–NO3 in the NH3-SCR deNOx mechanism and for the role of [Cu2+(OH−)]+. These results therefore help in building towards a more comprehensive understanding of the reaction mechanism which to date has only been postulated in silico

Speciation of phosphorus in a fertilized, reduced-till soil system: in-field treatment incubation study

Citation: Khatiwada, Raju, Ganga M. Hettiarachchi, David B. Mengel, and Mingwei Fei. “Speciation of Phosphorus in a Fertilized, Reduced-Till Soil System: In-Field Treatment Incubation Study.” Soil Science Society of America Journal 76, no. 6 (2012): 2006–18. https://doi.org/10.2136/sssaj2011.0299.Phosphorus management in reduced-tillage systems is a great concern for farmers. Conclusive positive results of deep-banding P fertilizers compared with broadcast application and the chemistry of reduced-tillage systems remain unclear. Knowledge of the dominant solid P species present in soil following application of P fertilizers and the resulting potential P availability would help us understand and efficiently manage P in reduced-tillage systems. The objective of this research was to study the influence of placement (broadcast vs. deep-band P), fertilizer source (granular vs. liquid P), and time on the reaction products of P under field conditions. Changes in soil pH, resin-extractable P, total P, and speciation of P were determined at different distances from the point of fertilizer application at 5 wk and 6 mo after P application at a rate of 75 kg ha−1 to a soil system that was under long-term reduced tillage. Resin-extractable P was lower for broadcast treatments compared with deep-band treatments for both time periods. Resin-extractable P was greater in the liquid P-treated soils than in the granular P-treated soils. Speciation results showed that granular P fertilizers tended to form Fe–P-like forms, whereas liquid forms remained in adsorbed P-like forms in the soil 5 wk after application; moreover, speciation results showed granular P fertilizers precipitated less when deep-banded. During the 6-mo period following application, reaction products of broadcast granular, broadcast liquid, and deep-band granular fertilizers transformed to Ca-phosphate or mixtures of Ca-, Fe- and adsorbed-phosphate-like forms, whereas deep-band liquid P remained as mainly adsorbed P-like forms. Deep-banding of P would most likely provide a solution that is both agronomically and environmentally efficient for reduced-till farmers

Unravelling structure sensitivity in CO2 hydrogenation over nickel

Continuous efforts in the field of materials science have allowed us to generate smaller and smaller metal nanoparticles, creating new opportunities to understand catalytic properties that depend on the metal particle size. Structure sensitivity is the phenomenon where not all surface atoms in a supported metal catalyst have the same activity. Understanding structure sensitivity can assist in the rational design of catalysts, allowing control over mechanisms, activity and selectivity, and thus even the viability of a catalytic reaction. Here, using a unique set of well-defined silica-supported Ni nanoclusters (1–7 nm) and advanced characterization methods, we prove how structure sensitivity influences the mechanism of catalytic CO2 reduction, the nature of which has been long debated. These findings bring fundamental new understanding of CO2 hydrogenation over Ni and allow us to control both activity and selectivity, which can be a means for CO2 emission abatement through its valorization as a low- or even negative-cost feedstock on a low-cost transition-metal catalyst

Parasympathetic nervous system dysfunction, as identified by pupil light reflex, and its possible connection to hearing impairment

Context Although the pupil light reflex has been widely used as a clinical diagnostic tool for autonomic nervous system dysfunction, there is no systematic review available to summarize the evidence that the pupil light reflex is a sensitive method to detect parasympathetic dysfunction. Meanwhile, the relationship between parasympathetic functioning and hearing impairment is relatively unknown. Objectives To 1) review the evidence for the pupil light reflex being a sensitive method to evaluate parasympathetic dysfunction, 2) review the evidence relating hearing impairment and parasympathetic activity and 3) seek evidence of possible connections between hearing impairment and the pupil light reflex. Methods Literature searches were performed in five electronic databases. All selected articles were categorized into three sections: pupil light reflex and parasympathetic dysfunction, hearing impairment and parasympathetic activity, pupil light reflex and hearing impairment. Results Thirty-eight articles were included in this review. Among them, 36 articles addressed the pupil light reflex and parasympathetic dysfunction. We summarized the information in these data according to different types of parasympathetic-related diseases. Most of the studies showed a difference on at least one pupil light reflex parameter between patients and healthy controls. Two articles discussed the relationship between hearing impairment and parasympathetic activity. Both studies reported a reduced parasympathetic activity in the hearing impaired groups. The searches identified no results for pupil light reflex and hearing impairment. Discussion and Conclusions As the first systematic review of the evidence, our findings suggest that the pupil light reflex is a sensitive tool to assess the presence of parasympathetic dysfunction. Maximum constriction velocity and relative constriction amplitude appear to be the most sensitive parameters. There are only two studies investigating the relationship between parasympathetic activity and hearing impairment, hence further research is needed. The pupil light reflex could be a candidate measurement tool to achieve this goal