Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Few-layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low-valence Metals.

ABSTRACT: The substitution of catalytic metals by p-block main elements has a tremendous impact not only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few-layer black phosphorous (FL-BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF0) up to two orders of magnitude higher than representative state-of-the-art metal complex catalysts at room temperature. The corresponding electron-rich BP intercalation compound (BPIC) KP6 shows a nearly twice TOF0 increase with respect to FL-BP. This increase in catalytic activity respect to the neutral counterpart also occurs in other 2D materials (graphene vs. KC8) and metal complex catalysts (Fe0 vs. Fe2- carbon monoxide complexes). This reactive parallelism opens the door for cross-fertilization between 2D materials and metal catalysts in organic synthesis.

SUBMITTER: Tejeda-Serrano M

PROVIDER: S-EPMC7216949 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Quantum-confinement and Structural Anisotropy result in Electrically-Tunable Dirac Cone in Few-layer Black Phosphorous.

Project description:Two-dimensional (2D) materials are well-known to exhibit interesting phenomena due to quantum confinement. Here, we show that quantum confinement, together with structural anisotropy, result in an electric-field-tunable Dirac cone in 2D black phosphorus. Using density functional theory calculations, we find that an electric field, E ext, applied normal to a 2D black phosphorus thin film, can reduce the direct band gap of few-layer black phosphorus, resulting in an insulator-to-metal transition at a critical field, Ec. Increasing E ext beyond Ec can induce a Dirac cone in the system, provided the black phosphorus film is sufficiently thin. The electric field strength can tune the position of the Dirac cone and the Dirac-Fermi velocities, the latter being similar in magnitude to that in graphene. We show that the Dirac cone arises from an anisotropic interaction term between the frontier orbitals that are spatially separated due to the applied field, on different halves of the 2D slab. When this interaction term becomes vanishingly small for thicker films, the Dirac cone can no longer be induced. Spin-orbit coupling can gap out the Dirac cone at certain electric fields; however, a further increase in field strength reduces the spin-orbit-induced gap, eventually resulting in a topological-insulator-to-Dirac-semimetal transition.

| S-EPMC4486999 | biostudies-literature

Interband Absorption in Few-Layer Graphene Quantum Dots: Effect of Heavy Metals.

Project description:Monolayer, bilayer, and trilayer graphene quantum dots (GQDs) with different binding abilities to elemental heavy metals (HMs: Cd, Hg, and Pb) were designed, and their electronic and optical properties were investigated theoretically to understand deeply the optical response under heavy metal exposure. To gain insight into the nature of interband absorption, we performed density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations for thickness-varying GQDs. We found that the interband absorption in GQDs can be efficiently tuned by controlling the thickness of GQDs to attain the desirable coloration of the interacting complex. We also show that the strength of the interaction between GQDs and Cd, Hg, and Pb is strongly dependent on the number of sp²-bonded layers. The results suggest that the thickness of GQDs plays an important role in governing the hybridization between locally-excited (LE) and charge-transfer (CT) states of the GQDs. Based on the partial density-of-states (DOS) analysis and in-depth knowledge of excited states, the mechanisms underlying the interband absorption are discussed. This study suggests that GQDs would show an improved sensing performance in the selective colorimetric detection of lead by the thickness control.

| S-EPMC6073920 | biostudies-literature

Few-layer HfS2 transistors.

Project description:HfS2 is the novel transition metal dichalcogenide, which has not been experimentally investigated as the material for electron devices. As per the theoretical calculations, HfS2 has the potential for well-balanced mobility (1,800 cm(2)/V·s) and bandgap (1.2 eV) and hence it can be a good candidate for realizing low-power devices. In this paper, the fundamental properties of few-layer HfS2 flakes were experimentally evaluated. Micromechanical exfoliation using scotch tape extracted atomically thin HfS2 flakes with varying colour contrasts associated with the number of layers and resonant Raman peaks. We demonstrated the I-V characteristics of the back-gated few-layer (3.8 nm) HfS2 transistor with the robust current saturation. The on/off ratio was more than 10(4) and the maximum drain current of 0.2 μA/μm was observed. Moreover, using the electric double-layer gate structure with LiClO4:PEO electrolyte, the drain current of the HfS2 transistor significantly increased to 0.75 mA/μm and the mobility was estimated to be 45 cm(2)/V·s at least. This improved current seemed to indicate superior intrinsic properties of HfS2. These results provides the basic information for the experimental researches of electron devices based on HfS2.

| S-EPMC4772098 | biostudies-literature

Layer-by-Layer Insight into Electrostatic Charge Distribution of Few-Layer Graphene.

Project description:In few-layer graphene (FLG) systems on a dielectric substrate such as SiO2, the addition of each extra layer of graphene can drastically alter their electronic and structural properties. Here, we map the charge distribution among the individual layers of finite-size FLG systems using a novel spatial discrete model that describes both electrostatic interlayer screening and fringe field effects. Our results reveal that the charge density in the region very close to the edges is screened out an order of magnitude more weakly than that across the central region of the layers. Our discrete model suggests that the interlayer charge screening length in 1-8 layer thick graphene systems depends mostly on the overall gate/molecular doping level rather than on temperature, in particular at an induced charge density >5 × 1012 cm-2, and can reliably be determined to be larger than half the interlayer spacing but shorter than the bilayer thickness. Our model can be used for designing FLG-based devices, and offers a simple rule regarding the charge distribution in FLG: approximately 70%, 20%, 6% and 3% (99% overall) of the total induced charge density reside within the four innermost layers, implying that the gate-induced electric field is not definitely felt by >4th layer.

| S-EPMC5318858 | biostudies-literature

Alkenes as Chelating Groups in Diastereoselective Additions of Organometallics to Ketones.

Project description:Alkenes have been discovered to be chelating groups to Zn(II), enforcing highly stereoselective additions of organozincs to ?,?-unsaturated ketones. 1H NMR studies and DFT calculations provide support for this surprising chelation mode. The results expand the range of coordinating groups for chelation-controlled carbonyl additions from heteroatom Lewis bases to simple C-C double bonds, broadening the 60 year old paradigm.

| S-EPMC4195513 | biostudies-literature

Few-Layer Antimonene by Liquid-Phase Exfoliation.

Project description:We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few-layer antimonene by liquid-phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few-layer antimonene suitable for on-surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high-quality few-layer antimonene nanosheets with large lateral dimensions. These nanolayers are extremely stable under ambient conditions. Their Raman signals are strongly thickness-dependent, which was rationalized by means of density functional theory calculations.

| S-EPMC5113666 | biostudies-literature

ARPES Signatures of Few-Layer Twistronic Graphenes.

Project description:Diverse emergent correlated electron phenomena have been observed in twisted-graphene layers. Many electronic structure predictions have been reported exploring this new field, but with few momentum-resolved electronic structure measurements to test them. We use angle-resolved photoemission spectroscopy to study the twist-dependent (1° < θ < 8°) band structure of twisted-bilayer, monolayer-on-bilayer, and double-bilayer graphene (tDBG). Direct comparison is made between experiment and theory, using a hybrid k·p model for interlayer coupling. Quantitative agreement is found across twist angles, stacking geometries, and back-gate voltages, validating the models and revealing field-induced gaps in twisted graphenes. However, for tDBG at θ = 1.5 ± 0.2°, close to the magic angle θ = 1.3°, a flat band is found near the Fermi level with measured bandwidth Ew = 31 ± 5 meV. An analysis of the gap between the flat band and the next valence band shows deviations between experiment (Δh = 46 ± 5 meV) and theory (Δh = 5 meV), indicative of lattice relaxation in this regime.

| S-EPMC10273478 | biostudies-literature

Infrared fingerprints of few-layer black phosphorus.

Project description:Black phosphorus is an infrared layered material. Its bandgap complements other widely studied two-dimensional materials: zero-gap graphene and visible/near-infrared gap transition metal dichalcogenides. Although highly desirable, a comprehensive infrared characterization is still lacking. Here we report a systematic infrared study of mechanically exfoliated few-layer black phosphorus, with thickness ranging from 2 to 15 layers and photon energy spanning from 0.25 to 1.36 eV. Each few-layer black phosphorus exhibits a thickness-dependent unique infrared spectrum with a series of absorption resonances, which reveals the underlying electronic structure evolution and serves as its infrared fingerprints. Surprisingly, unexpected absorption features, which are associated with the forbidden optical transitions, have been observed. Furthermore, we unambiguously demonstrate that controllable uniaxial strain can be used as a convenient and effective approach to tune the electronic structure of few-layer black phosphorus. Our study paves the way for black phosphorus applications in infrared photonics and optoelectronics.

| S-EPMC5227111 | biostudies-literature

Base-Promoted Radical Azofluoromethylation of Unactivated Alkenes.

Project description:The base-induced reaction of aryl diazonium salts with commercially available CF3SO2Na/CF2HSO2Na allows for the generation of the corresponding diazene radicals along with fluoromethyl radicals. The addition of fluoromethyl radicals to alkenes with subsequent diazene trapping provides the azofluoromethylation products in good to excellent yields. This metal-free method under mild reaction conditions has broad functional group compatibility and is applicable in the late-stage modification of various natural products and bioactive molecules.

| S-EPMC7328341 | biostudies-literature

Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

Project description:This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

| S-EPMC2531155 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data