Viola Duppel

Crystalline Carbon Nitride Nanosheets for Improved Visible-Light Hydrogen Evolution

Nanosheets of a crystalline 2D carbon nitride were obtained by ionothermal synthesis of the layered bulk material poly(triazine imide), PTI, followed by one-step liquid exfoliation in water. Triazine-based nanosheets are 1-2 nm in height and afford chemically and colloidally stable suspensions under both basic and acidic conditions. We use solid-state NMR spectroscopy of isotopically enriched, restacked nanosheets as a tool to indirectly monitor the exfoliation process and carve out the chemical changes occurring upon exfoliation, as well as to determine the nanosheet thickness. PTI nanosheets show significantly enhanced visible-light driven photocatalytic activity toward hydrogen evolution compared to their bulk counterpart, which highlights the crucial role of morphology and surface area on the photocatalytic performance of carbon nitride materials.

Dirac cone protected by non-symmorphic symmetry and three-dimensional Dirac line node in ZrSiS

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra-high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond-shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two-dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac nodes.

Ultrathin 2D coordination polymer nanosheets by surfactant-mediated synthesis

Low-dimensional nanostructures offer a host of intriguing properties which are distinct from those of the bulk material, owing to size-confinement effects and amplified surface areas. Here, we report on the scalable, bottom-up synthesis of ultrathin coordination polymer nanosheets via surfactant-mediated synthesis and subsequent exfoliation. Layers of a two-dimensional (2D) zinc coordination polymer are self-assembled in the interlamellar space of a reverse microemulsion mesophase into stacks of nanosheets interleaved with cethyltrimethylammonium bromide (CTAB) at regular intervals, thus giving rise to a lamellar hybrid mesostructure with a lattice period of ~8 nm and an underlying highly crystalline substructure. The basic structural motif is composed of 2D acetato-benzimidazolato-zinc layers of tetrahedrally coordinated zinc joined together by anionic acetate and benzimidazolate ligands. The hierarchical structure was studied by PXRD, TEM, EDX, EELS, AFM, and solid-state NMR spectroscopy, revealing a high level of order on both the atomic and mesoscale, suggesting fairly strong interactions along the organic-inorganic hybrid interface. Exfoliation of the hybrid material in organic solvents such as THF and chloroform yields sheet- and belt-like nanostructures with lateral sizes between 10s and 100s of nanometers and a height of about 10 nm measured by AFM, which precisely maps the basal spacing of the lamellar mesostructure; further exfoliation results in nanobelts with minimum sizes around 4 nm. Finally, the sheetlike nanostructures behave as morphological chameleons, transforming into highly regular multiwalled coordination polymer nanotubes upon treatment with organic solvents.

Green chemistry and nanofabrication in a levitated Leidenfrost drop

Green nanotechnology focuses on the development of new and sustainable methods of creating nanoparticles, their localized assembly and integration into useful systems and devices in a cost-effective, simple and eco-friendly manner. Here we present our experimental findings on the use of the Leidenfrost drop as an overheated and charged green chemical reactor. Employing a droplet of aqueous solution on hot substrates, this method is capable of fabricating nanoparticles, creating nanoscale coatings on complex objects and designing porous metal in suspension and foam form, all in a levitated Leidenfrost drop. As examples of the potential applications of the Leidenfrost drop, fabrication of nanoporous black gold as a plasmonic wideband superabsorber, and synthesis of superhydrophilic and thermal resistive metal–polymer hybrid foams are demonstrated. We believe that the presented nanofabrication method may be a promising strategy towards the sustainable production of functional nanomaterials.

Gd2O3:Eu3+ particles prepared by glycine-nitrate combustion: Phase, concentration, annealing, and luminescence studies

Eu3+ doped Gd2O3 particles have been prepared by glycine-nitrate combustion route. Eu–O charge transfer peak shifts to higher wavelength from 260 to 273 nm with increasing Eu3+ concentration, whereas the linewidth at half maximum intensity varies with Eu3+ concentrations and annealing temperatures as well. Lifetime for D50 level of Eu3+ increases with annealing temperature from 500 to 900 °C, and this is related to decreasing surface to volume atomic ratio of particles. Asymmetric ratio defined by the ratio of intensity of electrical dipole transition to that of magnetic dipole transition is found to be 10, which is more than the reported values (3–4) indicating enhancement in luminescence by this synthesis route.

Localized Synthesis of Iron Oxide Nanowires and Fabrication of High Performance Nanosensors Based on a Single Fe2O3 Nanowire

A composed morphology of iron oxide microstructures covered with very thin nanowires (NWs) with diameter of 15-50 nm has been presented. By oxidizing metallic Fe microparticles at 255 °C for 12 and 24 h, dense iron oxide NW networks bridging prepatterned Au/Cr pads are obtained. X-ray photoelectron spectroscopy studies reveal formation of α-Fe2 O3 and Fe3 O4 on the surface and it is confirmed by detailed high-resolution transmission electron microscopy and selected area electron diffraction (SAED) investigations that NWs are single phase α-Fe2 O3 and some domains of single phase Fe3 O4 . Localized synthesis of such nano- and microparticles directly on sensor platform/structure at 255 °C for 24 h and reoxidation at 650 °C for 0.2-2 h, yield in highly performance and reliable detection of acetone vapor with fast response and recovery times. First nanosensors on a single α-Fe2 O3 nanowire are fabricated and studied showing excellent performances and an increase in acetone response by decrease of their diameter was developed. The facile technological approach enables this nanomaterial as candidate for a range of applications in the field of nanoelectronics such as nanosensors and biomedicine devices, especially for breath analysis in the treatment of diabetes patients.

Superposition twinning supported by texture in ZnO nanospikes

The morphology and real structure of wurtzite-type ZnO nanospikes grown by the recently introduced flame transport synthesis have been examined by means of advanced transmission electron microscopy (TEM). The rapid synthesis produces nanospikes showing a well defined texture which restricts TEM experiments to a preferred viewing direction of [2 {\overline 1}{\overline 1}3]. Forced by the specific morphology, all of the observed nanospikes show a complicated superposition of twinned domains as an intrinsic real structural feature. The high-resolution contrasts are characterized by lamellar fringes parallel to the (1 {\overline 1} 0 {\overline 1}) planes, and the quasi-kinematic diffraction patterns contain satellite peaks based on multiple scattering. All these phenomena can be interpreted by comparison of experimental and simulated data relying on a supercell approach.

Cationically Charged MnIIAlIII LDH Nanosheets by Chemical Exfoliation and Their Use As Building Blocks in Graphene Oxide-Based Materials

We report on the synthesis and exfoliation of Mn(II)Al(III) sulfonate and sulfate layered double hydroxides (LDHs) and their combination with graphene oxide by charge-directed self-assembly. The synthesis of the LDH compounds has been accomplished either directly by coprecipitation of the respective hydroxides with sulfonate anions or by ion-exchange of the chloride-containing LDH with sodium dodecylsulfate. Exfoliation of the bulk material in formamide yields colloidal suspensions of positively charged nanosheets with lateral dimensions of tens to hundreds of nanometers and thicknesses down to 1.3 nm, ascertained by TEM and AFM. Flocculation of the LDH nanosheets with an aqueous graphene oxide suspension yields a hybrid material that can be converted to a reduced graphene oxide/LDH composite by hydrazine reduction. The hybrid materials were tested for pseudocapacitive electrochemical storage capacity and electrocatalytic oxygen evolution reactions and showed significant increases compared to the pristine materials.

Inorganic Double Helices in Semiconducting SnIP

SnIP is the first atomic-scale double helical semiconductor featuring a 1.86 eV bandgap, high structural and mechanical flexibility, and reasonable thermal stability up to 600 K. It is accessible on a gram scale and consists of a racemic mixture of right- and left-handed double helices composed by [SnI] and [P] helices. SnIP nanorods <20 nm in diameter can be accessed mechanically and chemically within minutes.

Non-symmorphic band degeneracy at the Fermi level in ZrSiTe

Non-symmorphic materials have recently been predicted to exhibit many different exotic features in their electronic structures. These originate from forced band degeneracies caused by the non-symmorphic symmetry, which not only creates the possibility to realize Dirac semimetals, but also recently resulted in the prediction of novel quasiparticles beyond the usual Dirac, Weyl or Majorana fermions, which can only exist in the solid state. Experimental realization of non-symmorphic materials that have the Fermi level located at the degenerate point is difficult, however, due to the requirement of an odd band filling. In order to investigate the effect of forced band degeneracies on the transport behavior, a material that has such a degeneracy at or close to the Fermi level is desired. Here, we show with angular resolved photoemission experiments supported by density functional calculations, that ZrSiTe hosts several fourfold degenerate Dirac crossings at the X point, resulting from non-symmorphic symmetry. These crossings form a Dirac line node along XR, which is located almost directly at the Fermi level and shows almost no dispersion in energy. ZrSiTe is thus the first real material that allows for transport measurements investigating Dirac fermions that originate from non-symmorphic symmetry.