Three-dimensional structure and defects in colloidal photonic crystals revealed by tomographic scanning transmission X-ray microscopy

Self-assembled colloidal crystals have attracted major attention because of their potential as low-cost three-dimensional (3D) photonic crystals. Although a high degree of perfection is crucial for the properties of these materials, little is known about their exact structure and internal defects. In this study, we use tomographic scanning transmission X-ray microscopy (STXM) to access the internal structure of self-assembled colloidal photonic crystals with high spatial resolution in three dimensions for the first time. The positions of individual particles of 236 nm in diameter are identified in three dimensions, and the local crystal structure is revealed. Through image analysis, structural defects, such as vacancies and stacking faults, are identified. Tomographic STXM is shown to be an attractive and complementary imaging tool for photonic materials and other strongly absorbing or scattering materials that cannot be characterized by either transmission or scanning electron microscopy or optical nanoscopy.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Homogeneous electrical explosion of tungsten wire in vacuum

Experimental results on Joule energy deposition upon initiation of a fast electrical explosion of 16-μm tungsten wire in vacuum at current densities of more than 10⁸ A/cm² are reported. We have found that explosion with a fast current rise time (～170 A/ns into a short) results in homogeneous and enhanced deposition of electrical energy into the tungsten before surface flashover. The maximum tungsten wire resistivity reaches a value of up to ～185 μΩ cm before surface flashover that significantly exceeds the melting boundary and corresponds to a temperature of ～1 eV. The highest values for light radiation and expansion velocity of wire ～1 km/s were observed for the fast explosion. For the explosion mode with a slower current rise time (～22 A/ns into a short), we observed the existence of an “energy deposition barrier” for tungsten wire. In the slow explosion mode, the current is reconnected to the surface shunting discharge before melting. The maximum tungsten wire resistivity in this case reaches the value of ～120 μΩ cm, which is less than indicative of melting. Also, the energy deposition along the wire is strongly inhomogeneous, and wire is disintegrated into parts. We attribute the early reconnection of the current to the surface discharge for the slow explosion to high electron emission from the wire surface, which starts before melting.     

Photoredox catalysis via consecutive 2LMCT- and 3MLCT-excitation of an Fe(iii/ii)–N-heterocyclic carbene complex

Fe–N-heterocyclic carbene (NHC) complexes attract increasing attention as photosensitisers and photoredox catalysts. Such applications generally rely on sufficiently long excited state lifetimes and efficient bimolecular quenching, which leads to there being few examples of successful usage of Fe–NHC complexes to date. Here, we have employed [Fe(iii)(btz)₃]³⁺ (btz = (3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene))) in the addition of alkyl halides to alkenes and alkynes via visible light-mediated atom transfer radical addition (ATRA). Unlike other Fe–NHC complexes, [Fe(iii/ii)(btz)₃]^3+/2+ benefits from sizable charge transfer excited state lifetimes ≥0.1 ns in both oxidation states, and the Fe(iii) ²LMCT and Fe(ii) ³MLCT states are strong oxidants and reductants, respectively. The combined reactivity of both excited states enables efficient one-electron reduction of the alkyl halide substrate under green light irradiation. The two-photon mechanism proceeds via reductive quenching of the Fe(iii) ²LMCT state by a sacrificial electron donor and subsequent excitation of the Fe(ii) product to its highly reducing ³MLCT state. This route is shown to be more efficient than the alternative, where oxidative quenching of the less reducing Fe(iii) ²LMCT state by the alkyl halide drives the reaction, in the absence of a sacrificial electron donor.

An iron complex with N-heterocyclic carbene ligands engages in efficient photoredox catalysis via excited state electron transfer reactions of its Fe(ii) and Fe(iii) oxidation states.     

Deactivation of Cu-Exchanged Automotive-Emission NH3-SCR Catalysts Elucidated with Nanoscale Resolution Using Scanning Transmission X-ray Microscopy

To gain insight into the underlying mechanisms of catalyst durability for the selective catalytic reduction (SCR) of NO_x with an ammonia reductant, we employed scanning transmission X-ray microscopy (STXM) to study Cu-exchanged zeolites with the CHA and MFI framework structures before and after simulated 135 000-mile aging. X-ray absorption near-edge structure (XANES) measurements were performed at the Al K- and Cu L-edges. The local environment of framework Al, the oxidation state of Cu, and geometric changes were analyzed, showing a multi-factor-induced catalytic deactivation. In Cu-exchanged MFI, a transformation of Cu^II to Cu^I and Cu_xO_y was observed. We also found a spatial correlation between extra-framework Al and deactivated Cu species near the surface of the zeolite as well as a weak positive correlation between the amount of Cu^I and tri-coordinated Al. By inspecting both Al and Cu in fresh and aged Cu-exchanged zeolites, we conclude that the importance of the preservation of isolated Cu^II sites trumps that of Brønsted acid sites for NH₃-SCR activity.     

Magnetic and crystallographic properties of several C1b type Heusler compounds

The compounds NiMnSb and IrMnGa were studied by neutron diffraction. The former compound has the cubic Cl_b crystal structure with an ideal site occupancy of the atoms. Below 750 K the compound is ferromagnetically ordered. The magnetic moments are confined to the Mn atoms (4.0μ_B/Mn). The compound IrMnGa has a crystal structure related to the C1_b type but characterized by a high atomic disorder. Results of magnetic measurements are presented for NiMnSb, CuMnSb and IrMnGa. The results of these measurements are in accord with the occurrence of high atomic ordering in the first two compounds but point to high atomic disorder in the latter material. Total energies and Mn moments derived from band-structure calculations are presented for three different types of site occupancies in NiMnSb. The lowest total energy as well as the correct value for the Mn moment correspond to the site occupancy found by means of the neutron diffraction.     

Stereospecific preparation of (±)-4,4-dinor-9βH-pimara-7,15-diene,a model for the total synthesis of momilactone type diterpenes

The synthesis of (±)-4,4-dinor-9βH-pimara-7,15-diene, 4, a model compound for momilactones, has been achieved via stereospecific Diels-Alder reaction and alkylation.     

Conduction bands and invariant energy gaps in alkali bromides

Electronic structure calculations of the alkali bromides LiBr, NaBr, KBr, RbBr and CsBr are reported. It is shown that the conduction band has primarily bromine character. The size of the band gaps of bromides and alkali halides in general is reinterpreted. Received: 26 January 1998 / Revised: 16 March 1998 / Accepted: 23 March 1998