Lewis Base-Catalyzed Trifluoromethylsulfinylation of Allylic Alcohols: Stability-Oriented Divergent Synthesis.

A novel strategy is demonstrated for Lewis base-activated trifluoromethylsulfinylation of allylic alcohols. Controllable synthesis of structurally varied allylic trifluoromethanesulfones via sigmatropic rearrangements was performed, and trifluoromethanesulfinate esters were achieved. This metal-free, catalytic divergent transformation features good functional group tolerance and late-stage modification of bioactive molecules. Mechanistic studies suggested that Lewis bases interact with N-(trifluoromethylsulfinyl)phthalimide to generate an ion pair adduct followed by O-trifluoromethylsulfinylation with allylic alcohols.

PNP-type ligands enabled copper-catalyzed N-formylation of amines with CO2 in the presence of silanes.

The sustainable catalytic transformation of carbon dioxide into valuable fine chemicals with high efficiency is a global challenge as although CO2 is an abundant, nontoxic, and sustainable carbon feedstock it is also the most important factor behind the Greenhouse Effect. We describe herein a PNP-type ligand-enabled copper-catalyzed N-formylation of amines utilizing CO2 as the building block in the presence of hydrosilane as the reductant. Our current protocol featured newly synthesized PNP-type ligands with broad substrate scope under mild reaction conditions.

C-H Fluoroalkylsulfinylation/Intramolecular Rearrangement for Precise Synthesis of Fluoroalkyl Sulfoxides.

An efficient methodology to access various fluoroalkyl sulfoxides bearing ortho/para-functionalized amine scaffolds from arylhydroxylamines is described. The transformation was featured with new electrophilic trifluoromethylthiolated reagents, good functional group tolerance, and late-stage modification of complex bioactive scaffolds, providing a rapid access to prepare numerous trifluoromethyl- and difluoromethyl-substituted sulfoxides. Mechanism studies and density functional theory calculations suggest this reaction goes through a nucleophilic trifluoromethylthiolation of arylhydroxylamine and subsequent internal 2,3-sigmatropic rearrangement involving a sulfur and oxygen transfer process.

Size-dependent strain-engineered nanostructures in MoS2monolayer investigated by atomic force microscopy.

The strain has been employed for controlled modification of electronical and mechanical properties of two-dimensional (2D) materials. However, the thermal strain-engineered behaviors of the CVD-grown MoS2have not been systematically explored. Here, we investigated the strain-induced structure and properties of CVD-grown triangular MoS2flakes by several advanced atomic force microscopy. Two different kinds of flakes with sharp-corner or vein-like nanostructures are experimentally discovered due to the size-dependent strain behaviors. The critical size of these two kinds of flakes can be roughly estimated at âˆ¼17µm. Within the small flakes, the sharp-corner regions show specific strain-modified properties due to the suffering of large tensile strain. While in the large MoS2flakes, the complicated vein-like nanoripple structures were formed due to the interface slipping process under the larger tensile strain. Our work not only demonstrates the size-specific strain behaviors of MoS2flakes but also sheds light on the artificial design and preparation of strain-engineered nanostructures for the devices based on the 2D materials.

The Ag-promoted α-C-H arylation of alcohols.

We herein report the functionalization of α-C-H in alcohols through cross-dehydrogenative coupling reactions. Selectfluor was used as a mild oxidant. In situ-generated HF participated in the reaction and no external strong acid was necessary. A variety of heteroaryl-substituted alcohols were achieved with good yields and with good functional group tolerance.

Nanoscale charge transfer and diffusion at the MoS2/SiO2 interface by atomic force microscopy: contact injection versus triboelectrification.

Understanding the process of charge generation, transfer, and diffusion between two-dimensional (2D) materials and their supporting substrates is very important for potential applications of 2D materials. Compared with the systematic studies of triboelectric charging in a bulk sample, a fundamental understanding of the triboelectrification of the 2D material/insulator system is rather limited. Here, the charge transfer and diffusion of both the SiO2 surface and MoS2/SiO2 interface through contact electrification and frictional electrification are investigated systematically in situ by scanning Kelvin probe microscopy and dual-harmonic electrostatic force microscopy. Different from the simple static charge transfer between SiO2 and the PtSi alloy atomic force microscope (AFM) tip, the charge transfer between the tip and the MoS2/SiO2 system is complicated. Triboelectric charges, generated by contact or frictional electrification with the AFM tip, are trapped at the MoS2/SiO2 interface and act as floating gates. The local charge discharge processes can be obtained by monitoring the surface potential. The charge decay time (τ) of the MoS2/SiO2 interface is one (or two) orders of magnitude larger than the decay time τ of the SiO2 surface. This work facilitates an understanding of the triboelectric and de-electrification of the interface between 2D materials and substrates. In addition to the charge transfer and diffusion, we demonstrate the nanopatterns of surface and interfacial charges, which have great potential for the application of self-assembly of charged nanostructures.

On-Surface Synthesis of Graphene Nanoribbons Catalyzed by Ni Atoms.

Nanometer-wide graphene nanoribbons can be synthesized from halogen aromatics through multistep on-surface reactions, but the catalytic role of extrinsic transition-metal atoms in these reactions are still to be explored. Here by low-temperature scanning tunneling microscopy, we investigated the on-surface synthesis of graphene nanoribbons from 10,10'-dibromo-9,9'-bianthryl precursors in the presence of Ni atoms. Ni atoms not only act as catalysts in debromination and lead to the formation of an organometallic intermediate at 300 K, but also prompt the fusion reaction between graphene nanoribbons at 673 K. Our work demonstrates a more efficient way to fabricate fused graphene nanoribbons.

Degradation of bisphenol A by electro-enhanced heterogeneous activation of peroxydisulfate using Mn-Zn ferrite from spent alkaline Zn-Mn batteries.

Mn-Zn ferrite (Mn0.6Zn0.4Fe2O4) was prepared by a gel method using spent alkaline Zn-Mn batteries as raw materials and employed as catalyst to degrade bisphenol A (BPA) by electro-enhanced heterogeneous activation of peroxydisulfate (PDS). The effects of initial pH, current density, PDS concentration, and Mn-Zn ferrite dosage on BPA removal were investigated. The formation of reactive radicals was verified by electron paramagnetic resonance (EPR) spectroscopy. The results of radical quenching experiments indicate that surface-bound sulfate and hydroxyl radicals played an important role in BPA removal. The stability of Mn0.6Zn0.4Fe2O4 catalyst was investigated by cycling experiments, which indicates Mn0.6Zn0.4Fe2O4 is stable and can be reused. This work also provides an alternative way for the reutilization of spent alkaline Zn-Mn batteries.

Epitaxial Growth and Band Structure of Te Film on Graphene.

Tellurium (Te) films with monolayer and few-layer thickness are obtained by molecular beam epitaxy on a graphene/6H-SiC(0001) substrate and investigated by in situ scanning tunneling microscopy and spectroscopy (STM/STS). We reveal that the Te films are composed of parallel-arranged helical Te chains flat-lying on the graphene surface, exposing the (1 × 1) facet of (101̅0) of the bulk crystal. The band gap of Te films increases monotonically with decreasing thickness, reaching the near-infrared band for the monolayer Te. An explicit band bending at the edge between the monolayer Te and graphene substrate is visualized. With the thickness controlled in the atomic scale, Te films show potential applications of electronics and optoelectronics.

Oxidation of organic contaminant in a self-driven electro/natural maghemite/peroxydisulfate system: Efficiency and mechanism.

Electro-assisted iron-mediated persulfate (PS) activation process has been successfully employed to oxidize organic contaminant. However, a majority of iron-based catalysts used for PS activation was synthesized through complicated or demanding procedures and may have potential risks on environment during the preparation process. Herein, natural maghemite (NM) which is abundant on the earth was employed to activate peroxydisulfate (PDS) in an electrolytic cell. The voltage was provided by microbial fuel cell (MFC) instead of external power as reported in the previous studies, so as to establish a self-driven electro/natural maghemite/PDS system (MFC/NM/PDS) for the oxidation of acid orange 7 (AO7). The results showed that above 90% removal efficiency of AO7 was achieved in a wide range of pH (3.0-9.0) after 100min reaction. Singlet oxygen was identified for the first time during PDS activation and surface bound sulfate radicals served as the dominant active species responsible for AO7 oxidation. The underlying mechanism of AO7 elimination in the MFC/NM/PDS system was elucidated through quenching tests, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) techniques. The variation of TOC and cytotoxicity to Escherichia coli was explored. The intermediate products formed were identified using LC-TOF-MS technique and a possible pathway of AO7 degradation was proposed.