Controllable Synthesis and Charge Density Wave Phase Transitions of Two-Dimensional 1T-TaS2 Crystals.

1T-TaS2 has attracted much attention recently due to its abundant charge density wave phases. In this work, high-quality two-dimensional 1T-TaS2 crystals were successfully synthesized by a chemical vapor deposition method with controllable layer numbers, confirmed by the structural characterization. Based on the as-grown samples, their thickness-dependency nearly commensurate charge density wave/commensurate charge density wave phase transitions was revealed by the combination of the temperature-dependent resistance measurements and Raman spectra. The phase transition temperature increased with increasing thickness, but no apparent phase transition was found on the 2~3 nm thick crystals from temperature-dependent Raman spectra. The transition hysteresis loops due to temperature-dependent resistance changes of 1T-TaS2 can be used for memory devices and oscillators, making 1T-TaS2 a promising material for various electronic applications.

Electronic Properties and Carrier Dynamics at the Alloy Interfaces of WS2x Se2-2x Spiral Nanosheets.

Electronic properties at the interfaces between different-composition domains of 2D-alloys are key for their optical, electronic, and optoelectronic applications. Understanding the interfacial electronic structures and carrier dynamics is essential for designing and fabricating devices that use these alloys. Here, WS2x Se2-2x spiral nanosheets are prepared using the physical vapor deposition method, and the nonlinear optical and electronic properties, as well as the carrier dynamics at the interfaces between the WS and WSe domains, are studied. Second-harmonic generation tests demonstrate that these nanosheets exhibit a very strong layer-dependent nonlinear optical effect. Atomic-resolution scanning tunneling microscopy (STM) and spectroscopy (STS) measurements reveal that S and Se atoms are non-uniformly distributed, forming WS domains, WSe domains, and defect-related areas. Atomic STM images and STS maps reveal enhanced local density of states by electron scattering at the WS/WSe interfaces, providing a detailed nanoscale interpretation of the S/Se-ratio-dependent lifetimes observed in pump-probe spectroscopy measurements. This work provides valuable interfacial characterization of 2D-alloy materials, using state-of-the-art methods with high temporal and spatial resolutions. The obtained insights are likely to be useful for prospective applications.

Spatially Dependent Electronic Structures and Excitons in a Marginally Twisted Moiré Superlattice of Spiral WS2.

Twisted two-dimensional transition metal dichalcogenide (TMD) moiré superlattices provide an additional degree of freedom to engineer electronic and optical properties. Nevertheless, controllable synthesis of marginally twisted homo TMD moiré superlattices is still a challenge. Here, physical vapor deposition grown spiral WS2 nanosheets are demonstrated to be a marginally twisted moiré superlattice using scanning tunneling microscopy and spectroscopy. Periodic moiré superlattices are found on the third layer (3L) and 4L of the spiral WS2 nanosheet owing to the marginally twisted alignment between two neighboring layers, resulting in a highly localized flat band near the valence band maximum. Their bandgap depends on atomic stacking configurations, which gives a good interpretation for split moiré excitons using photoluminescence at 77 K. This work can benefit the development of twisted homo TMD moiré superlattices and could promote the profound research of twisted TMDs in the prospective field, such as strongly correlated physics and twistronics.

Epitaxy of NiTe2 on WS2 for the p-Type Schottky Contact and Increased Photoresponse.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have great potential applications in the electronic and optoelectronic devices. Nevertheless, due to the difficulty in the efficient doping of atomic-thickness TMDCs or Fermi level pinning (FLP) effects at the metal/semiconductor interface, most TMDC devices exhibit the n-type conduction polarity, which significantly limits their functional applications based on the p-n junction. Here, 2D semi-metal NiTe2 nanosheets were epitaxially grown on the WS2 monolayer by a two-step chemical vapor deposition route. The microstructure and optical characterizations confirm that the vertically stacked NiTe2/WS2 heterostructures are formed by van der Waals epitaxy. Interestingly, p-type WS2 field-effect transistors can be obtained with the hole mobility of ∼4.22 cm2/V·s, when the epitaxial NiTe2 sheets act as the source/drain electrodes. This is attributed to the decreased FLP effect and hence the low potential barrier for holes at the van der Waals contacts. Furthermore, the photodetectors based on the heterostructures show a 2 orders of magnitude increase in the switch ratio, responsivity, and detectivity and a 1 order of magnitude increase in the rise and decay speeds relative to those based on pristine WS2. This work paves the way to realize the p-type contact for monolayer WS2 with significantly enhanced optoelectronic performance.

Converting Poisonous Sulfate Species to an Active Promoter on TiO2 Predecorated MnOx Catalysts for the NH3-SCR Reaction.

MnOx-based catalysts possess excellent low-temperature NH3 selective catalytic reduction (NH3-SCR) activity, but the poor SO2/sulfate poisoning resistance and the narrow active-temperature window limit their application for NOx removal. Herein, TiO2 nanoparticles and sulfate were successively introduced into MnOx-based catalysts to modulate the NH3-SCR activity, and the active-temperature window (NO conversion above 80%, T80) was significantly broadened to 100-350 °C (SO42--TiO2@MnOx) compared to that of the pristine MnOx catalyst (ca. T80: 100-268 °C). Combined with advanced characterizations and control experiments, it was clearly shown that the poisonous effects of sulfate on the MnOx catalyst could be efficiently inhibited in the presence of TiO2 species due to the interaction between sulfate and TiO2 to form a solid superacid (SO42--TiO2) species as NH3 adsorption sites for the low-temperature process. Furthermore, such solid superacid (SO42--TiO2) species could weaken the redox ability to inhibit the excessive oxidation of NH3 and thus enhance the high-temperature activity significantly. This work not only puts forward the TiO2 predecoration strategy that converts sulfate to a promoter to broaden the active temperature window but also experimentally proves that the requirement of redox ability and acidity in the MnOx-based NH3-SCR catalyst was dependent on the reaction temperature range.

Enhanced Optoelectronic Performance of CVD-Grown Metal-Semiconductor NiTe2/MoS2 Heterostructures.

Van der Waals (vdW) heterostructures are the fundamental blocks for two-dimensional (2D) electronic and optoelectronic devices. In this work, a high-quality 2D metal-semiconductor NiTe2/MoS2 heterostructure is prepared by a two-step chemical vapor deposition (CVD) growth. The back-gated field-effect transistors (FETs) and photodetectors based on the heterostructure show enhanced electronic and optoelectronic performance than that of a pristine MoS2 monolayer, owing to the better heterointerface in the former device. Especially, this photodetector based on the metal-semiconductor heterostructure shows 3 orders faster rise time and decay time than that of the pristine MoS2 under the same fabrication procedure. The enhancement of electronic behavior and optoelectronic response by the epitaxial growth of metallic vdW layered materials can provide a new method to improve the performance of optoelectronic devices.

Improved Catalytic Performance of Ethane Dehydrogenation in the Presence of CO2 over Zr-Promoted Cr/SiO2.

The Zr-, Ce-, Sr-, and Sn-promoted Cr/SiO2 catalysts were prepared by the incipient wetness impregnation method, then characterized by N2 adsorption/desorption, X-ray diffraction, X-ray photoelectron spectroscopy, H2-TPR, CO2-TPD, UV-vis, high-angle annular dark-field imaging-scanning transmission electron microscopy-energy dispersive X-ray spectroscopy elemental mapping, Raman, and thermogravimetric techniques to study the structural evolution under the preparation/reaction conditions, and applied to catalyze ethane oxidative dehydrogenation with CO2. The results suggested that the Cr6+ species were indispensable for activating the dehydrogenation reaction thanks to the oxidation-reduction cycle between Cr6+ and Cr3+. The type of the promotor also affected significantly the ability of replenishing the lattice oxygen through the disassociation of CO2, leading to the different catalytic performances. The Zr-promoted sample had the best performance in converting the reactants as well as the catalytic stability.

Self-Propagated Flaming Synthesis of Highly Active Layered CuO-δ-MnO2 Hybrid Composites for Catalytic Total Oxidation of Toluene Pollutant.

A new self-propagated flaming (SPF) technique was applied to the synthesis of highly active layered CuO-δ-MnO2 hybrid composites, for the de-polluting catalytic total oxidation of gaseous toluene vapor. Other transition metal oxide-doped MnO2 hybrid composites were also successfully prepared and investigated, ensuring a feasible strategy for the fabrication of various layered MOx-δ-MnO2 (M═Co, Ni, or Zn) hybrids. By changing the molar ratio of the precursors (KMnO4 and acetate salt) and the type of transition metal oxide introduced, it is possible to control the crystal structure and reducibility of the sheetlike hybrid composites as well as the catalytic activity for the total oxidation of toluene. The catalyst sample (CuO-δ-MnO2) with a Mn/Cu molar ratio of 10:1 exhibited the highest catalytic performance, with a lower reaction temperature of 300 °C for complete toluene removal, which was comparable to the reaction temperature for total toluene conversion by the Pt-based catalyst. The SPF technique provides an approach for developing highly efficient catalysts for the complete removal of volatile organic compounds, by allowing the facile and energy-saving fabrication of large quantities of layered CuO-δ-MnO2 hybrids.