ABSTRACT
[NiFe]-hydrogenases are biotechnologically relevant enzymes catalyzing the reversible splitting of H2 into 2e- and 2H+ under ambient conditions. Catalysis takes place at the heterobimetallic NiFe(CN)2(CO) center, whose multistep biosynthesis involves careful handling of two transition metals as well as potentially harmful CO and CN- molecules. Here, we investigated the sequential assembly of the [NiFe] cofactor, previously based on primarily indirect evidence, using four different purified maturation intermediates of the catalytic subunit, HoxG, of the O2-tolerant membrane-bound hydrogenase from Cupriavidus necator. These included the cofactor-free apo-HoxG, a nickel-free version carrying only the Fe(CN)2(CO) fragment, a precursor that contained all cofactor components but remained redox inactive and the fully mature HoxG. Through biochemical analyses combined with comprehensive spectroscopic investigation using infrared, electronic paramagnetic resonance, Mössbauer, X-ray absorption and nuclear resonance vibrational spectroscopies, we obtained detailed insight into the sophisticated maturation process of [NiFe]-hydrogenase.
Subject(s)
Cupriavidus necator , Hydrogenase , Catalytic Domain , Hydrogenase/chemistry , Hydrogenase/metabolism , Cupriavidus necator/chemistry , Cupriavidus necator/metabolism , Oxidation-Reduction , NickelABSTRACT
For a future hydrogen economy, non-precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal-nitrogen-carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN4 ) show promising performance, but an optimization rooted in structure-property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well-defined molecules to MNC systems. This work combines experiment and theory to evaluate the influence of porphyrin substituents on the electronic and electrocatalytic properties of MN4 centers with respect to the hydrogen evolution reaction (HER) in aqueous electrolyte. We found that the choice of substituent affects their utilization on the carbon support and their electrocatalytic performance. We propose an HER mechanism for supported iron porphyrin complexes involving a [FeII (Pâ )]- radical anion intermediate, in which a porphinic nitrogen atom acts as an internal base. While this work focuses on the HER, the limited influence of a simultaneous interaction with the support and an aqueous electrolyte will likely be transferrable to other catalytic applications.
ABSTRACT
α-Sb2O4 (cervantite) and ß-Sb2O4 (clinocervantite) are mixed valence compounds with equal proportions of SbIII and SbV as represented in the formula SbIIISbVO4. Their structure and properties can be difficult to calculate owing to the SbIII lone-pair electrons. Here, we present a study of the lattice dynamics and vibrational properties using a combination of inelastic neutron scattering, Mössbauer spectroscopy, nuclear inelastic scattering, and density functional theory (DFT) calculations. DFT calculations that account for lone-pair electrons match the experimental densities of phonon states. Mössbauer spectroscopy reveals the ß phase to be significantly harder than the α phase. Calculations with O vacancies reveal the possibility for nonstoichiometric proportions of SbIII and SbV in both phases. An open question is what drives the stability of the α phase over the ß phase, as the latter shows pronounced kinetic stability and lower symmetry despite being in the high-temperature phase. Since the vibrational entropy difference is small, it is unlikely to stabilize the α phase. Our results suggest that the α phase is more stable only because the material is not fully stoichiometric.
ABSTRACT
Continued efforts are made on the development of earth-abundant metal catalysts for dehydrogenation/hydrolysis of amine boranes. In this study, complex [K-18-crown-6-ether][(NO)2Fe(µ-MePyr)(µ-CO)Fe(NO)2] (3-K-crown, MePyr = 3-methylpyrazolate) was explored as a pre-catalyst for the dehydrogenation of dimethylamine borane (DMAB). Upon evolution of H2(g) from DMAB triggered by 3-K-crown, parallel conversion of 3-K-crown into [(NO)2Fe(N,N'-MePyrBH2NMe2)]- (5) and an iron-hydride intermediate [(NO)2(CO)Fe(µ-H)Fe(CO)(NO)2]- (A) was evidenced by X-ray diffraction/nuclear magnetic resonance/infrared/nuclear resonance vibrational spectroscopy experiments and supported by density functional theory calculations. Subsequent transformation of A into complex [(NO)2Fe(µ-CO)2Fe(NO)2]- (6) is synchronized with the deactivated generation of H2(g). Through reaction of complex [Na-18-crown-6-ether][(NO)2Fe(η2-BH4)] (4-Na-crown) with CO(g) as an alternative synthetic route, isolated intermediate [Na-18-crown-6-ether][(NO)2(CO)Fe(µ-H)Fe(CO)(NO)2] (A-Na-crown) featuring catalytic reactivity toward dehydrogenation of DMAB supports a substrate-gated transformation of a pre-catalyst [(NO)2Fe(µ-MePyr)(µ-CO)Fe(NO)2]- (3) into the iron-hydride species A as an intermediate during the generation of H2(g).
ABSTRACT
In this manuscript, characterization of single-crystalline (111) plates prepared from type-Ib diamonds with a nitrogen content of 100-150â ppm by means of high-resolution rocking-curve imaging (RCI) is reported. Contrary to common opinion regarding the intrinsically poor diffraction quality of type-I diamonds, RCI showed the presence of nearly defect-free areas of several millimetres squared in the central part of the diamond plates. The observed broadening of the rocking curves is a result of the cutting and polishing processes, causing strains around the edges of the plates and rare defects. An improvement of the preparation technique will thus allow single-crystalline diamond plates to be made for Laue and Bragg monochromators and beam splitters from type-Ib material with areas large enough to be used as optical elements at fourth-generation synchrotron facilities.
ABSTRACT
Nuclear resonant reflectivity (NRR) from an Fe60Al40 film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20â keV Ne+ ions of gradually varying fluence of 0-3.0â ×â 1014â ionsâ cm-2, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed. The observed depth selectivity of the method has been explained by application of the standing wave approach. From the time spectra of the nuclear resonant scattering in several reflection directions the depth profiles for different hyperfine fields were extracted. The results show that the highest magnetic hyperfine fields (â¼18-23â T) are initially created in the central part of the film and partially at the bottom interface with the SiO2 substrate. The evolution of the ferromagnetic onset, commencing at a fixed depth within the film and propagating towards the interfaces, has been directly observed. At higher fluence (3.0â ×â 1014â ionsâ cm-2) the depth distribution of the ferromagnetic fractions became more homogeneous across the film depth, in accordance with previous results.
ABSTRACT
The IRIXS Spectrograph represents a new design of an ultra-high-resolution resonant inelastic X-ray scattering (RIXS) spectrometer that operates at the Ru L3-edge (2840â eV). First proposed in the field of hard X-rays by Shvyd'ko [(2015), Phys. Rev. A, 91, 053817], the X-ray spectrograph uses a combination of laterally graded multilayer mirrors and collimating/dispersing Ge(111) crystals optics in a novel spectral imaging approach to overcome the energy resolution limitation of a traditional Rowland-type spectrometer [Gretarsson et al. (2020), J. Synchrotron Rad. 27, 538-544]. In combination with a dispersionless nested four-bounce high-resolution monochromator design that utilizes Si(111) and Al2O3(110) crystals, an overall energy resolution better than 35â meV full width at half-maximum has been achieved at the Ru L3-edge, in excellent agreement with ray-tracing simulations.
ABSTRACT
Mössbauer spectroscopy, nuclear forward scattering, and Raman spectroscopy were applied to study redox transformations of the synthesized mixed-valence (III/V) antimony oxide. The transformations were induced by a culture of a hyperthermophilic archaeon of the genus Pyrobaculum. The applied methods allowed us to reveal the minor decrease of ca. 11.0 ± 1.2% of the antimony(V) content of the mixed-valence oxide with the concomitant increase of antimony(III). The method sensitivities for the quantitative assessment of the Sb(III/V) ratio have been considered.
Subject(s)
Antimony/analysis , Oxides/analysis , Pyrobaculum/chemistry , Antimony/metabolism , Oxidation-Reduction , Oxides/metabolism , Pyrobaculum/metabolism , Spectroscopy, Mossbauer , Spectrum Analysis, RamanABSTRACT
A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100â GPa and temperatures up to 3000â K, is given. The XES spectra of laser-heated Mg0.67Fe0.33O demonstrate the potential to map the iron spin state in the pressure-temperature range of the Earth's lower mantle, and the NIS spectra of laser-heated FeSi give access to the sound velocity of this candidate of a phase inside the Earth's core. This portable system represents one of the few bridges across the gap between laser heating and high-resolution X-ray spectroscopies with signal collection near 90°.
ABSTRACT
α-Sb2O3 (senarmontite), ß-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and ß-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb-O-Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at â¼340 cm-1. Softer lattice vibrational modes occur in orthorhombic ß-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained ß structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb2O3 at 880 K accounts for about half of the α-ß transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.
ABSTRACT
The capability to perform high-pressure low-temperature nuclear inelastic scattering on 125Te and 121Sb with a sapphire backscattering monochromator is presented. This technique was applied to measure nuclear inelastic scattering in TeO2 at pressures up to 10 GPa and temperatures down to 25 K. The evaluated partial Te densities of phonon states were compared with theoretical calculations and with Raman scattering measured under the same conditions. The high-pressure cell developed in this work can also be used for other techniques at pressures up to at least 100 GPa.
ABSTRACT
Hard-x-ray spectroscopy relies on a suite of modern techniques for studies of vibrational, electronic, and magnetic excitations in condensed matter. At present, the energy resolution of these techniques can be improved only by decreasing the spectral window of the involved optics-monochromators and analyzers-thereby sacrificing the intensity. Here, we demonstrate hard-x-ray spectroscopy with greatly improved energy resolution without narrowing the spectral window by adapting principles of spectrographic imaging to the hard-x-ray regime. Similar to Newton's classical prism, the hard-x-ray spectrograph disperses different "colors"-i.e., energies-of x-ray photons in space. Then, selecting each energy component with a slit ensures high energy resolution, whereas measuring x-ray spectra with all components of a broad spectral window keeps the intensity. We employ the principles of spectrographic imaging for phonon spectroscopy. Here the new approach revealed anomalous soft atomic dynamics in α-iron, a phenomenon which was not previously reported in the literature. We argue that hard-x-ray spectrographic imaging also could be a path to discovering new physics in studies of electronic and magnetic excitations.
ABSTRACT
The relationship between vacancy ordering and magnetism in TlFe(1.6)Se(2) has been investigated via single crystal neutron diffraction, nuclear forward scattering, and transmission electron microscopy. The examination of chemically and structurally homogeneous crystals allows the true ground state to be revealed, which is characterized by Fe moments lying in the ab plane below 100 K. This is in sharp contrast to crystals containing regions of order and disorder, where a competition between c axis and ab plane orientations of the moments is observed. The properties of partially disordered TlFe(1.6)Se(2) are, therefore, not associated with solely the ordered or disordered regions. This contrasts the viewpoint that phase separation results in independent physical properties in intercalated iron selenides, suggesting a coupling between ordered and disordered regions may play an important role in the superconducting analogues.
ABSTRACT
Phonon modes play a vital role in the cooperative phenomenon of light-induced spin transitions in spin crossover (SCO) molecular complexes. Although the cooperative vibrations, which occur over several hundreds of picoseconds to nanoseconds after photoexcitation, are understood to play a crucial role in this phase transition, they have not been precisely identified. Therefore, we have performed a novel optical laser pump-nuclear resonance probe experiment to identify the Fe-projected vibrational density of states (pDOS) during the first few nanoseconds after laser excitation of the mononuclear Fe(II) SCO complex [Fe(PM-BiA)2(NCS)2]. Evaluation of the so obtained nanosecond-resolved pDOS yields an excitation of â¼8% of the total volume of the complex from the low-spin to high-spin state. Density functional theory calculations allow simulation of the observed changes in the pDOS and thus identification of the transient inter- and intramolecular vibrational modes at nanosecond time scales.
ABSTRACT
The high brilliance of modern synchrotron radiation sources facilitates experiments with high-energy x-rays across a range of disciplines, including the study of the electronic and magnetic correlations using elastic and inelastic scattering techniques. Here we report on Nuclear Resonance Scattering at the 73 keV nuclear level in 193Ir. The transitions between the hyperfine split levels show an untypically high E2/M1 multi-polarity mixing ratio combined with an increased sensitivity to certain changes in the hyperfine field direction compared to non-mixing transitions. The method opens a new way for probing local magnetic and electronic properties of correlated materials containing iridium and provides novel insights into anisotropic magnetism in iridates. In particular, unexpected out-of-plane components of magnetic hyperfine fields and non-zero electric field gradients in Sr2IrO4 have been detected and attributed to the strong spin-orbit interaction in this iridate. Due to the high, 62% natural abundance of the 193Ir isotope, no isotopic enrichment of the samples is required, qualifying the method for a broad range of applications.
ABSTRACT
The lattice dynamics in an array of 56 nm diameter Bi2Te3 nanowires embedded in a self-ordered amorphous alumina membrane were investigated microscopically using (125)Te nuclear inelastic scattering. The element specific density of phonon states is measured on nanowires in two perpendicular orientations and the speed of sound is extracted. Combined high energy synchrotron radiation diffraction and transmission electron microscopy was carried out on the same sample and the crystallinity was investigated. The nanowires grow almost perpendicular to the c-axis, partly with twinning. The average speed of sound in the 56 nm diameter Bi2Te3 nanowires is ~7% smaller with respect to bulk Bi2Te3 and a decrease in the macroscopic lattice thermal conductivity by ~13% due to nanostructuration and to the reduced speed of sound is predicted.