Direct visualization of structural defects in 2D semiconductors

Direct visualization of the structural defects in two-dimensional (2D) semiconductors at a large scale plays a significant role in understanding their electrical/optical/magnetic properties, but is challenging. Although traditional atomic resolution imaging techniques, such as transmission electron microscopy and scanning tunneling microscopy, can directly image the structural defects, they provide only local-scale information and require complex setups. Here, we develop a simple, non-invasive wet etching method to directly visualize the structural defects in 2D semiconductors at a large scale, including both point defects and grain boundaries. Utilizing this method, we extract successfully the defects density in several different types of monolayer molybdenum disulfide samples, providing key insights into the device functions. Furthermore, the etching method we developed is anisotropic and tunable, opening up opportunities to obtain exotic edge states on demand.     

单层MXene纳米片Ti2N电磁特性的过渡金属(Sc、V、Zr)掺杂效应

二维材料MXene纳米片由于具有较大的比表面积和较高的电子迁移率而受到广泛的关注。本文采用基于密度泛函理论的第一性原理计算,对单层MXene纳米片Ti₂N电磁特性的过渡金属(Sc、V、Zr)掺杂效应进行了系统研究。结果表明,所有过渡金属掺杂体系结合能均为负值,结构均稳定;其中Ti₂N-Sc体系的形成能为-2.242 eV,结构更易形成,且保持稳定;掺杂后Ti₂N-Sc、Ti₂N-Zr体系磁矩增大;此外,Ti₂N-Sc体系中保留了较高的自旋极化率,达到84.9%,可预测该体系在自旋电子学中具有潜在的应用价值。     

Sandwich-like Catalyst–Carbon–Catalyst Trilayer Structure as a Compact 2D Host for Highly Stable Lithium–Sulfur Batteries

Herein, we propose the construction of a sandwich-structured host filled with continuous 2D catalysis–conduction interfaces. This MoN-C-MoN trilayer architecture causes the strong conformal adsorption of S/Li₂S_x and its high-efficiency conversion on the two-sided nitride polar surfaces, which are supplied with high-flux electron transfer from the buried carbon interlayer. The 3D self-assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN-C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job-synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li₂S_x, and avoids thick and devitalized accumulation (electrode passivation) even after high-rate and long-term cycling.     

Synthesis of the Antimicrobial S‐Linked Glycopeptide,Glycocin F

The first total synthesis of glycocin F, a uniquely diglycosylated antimicrobial peptide bearing a rare S‐linked N‐acetylglucosamine (GlcNAc) moiety in addition to an O‐linked GlcNAc, has been accomplished using a native chemical ligation strategy. The synthetic and naturally occurring peptides were compared by HPLC, mass spectrometry, NMR and CD spectroscopy, and their stability towards chymotrypsin digestion and antimicrobial activity were measured. This is the first comprehensive structural and functional comparison of a naturally occurring glycocin with an active synthetic analogue.     

Simultaneous Induction of Axial and Planar Chirality in Arene–Chromium Complexes by Molybdenum‐Catalyzed Enantioselective Ring‐Closing Metathesis

The molybdenum‐catalyzed asymmetric ring‐closing metathesis of the various C_s‐symmetric (π‐arene)chromium substrates provides the corresponding bridged planar‐chiral (π‐arene)chromium complexes in excellent yields with up to >99 % ee. With a bulky and unsymmetrical substituent, such as N‐indolyl or 1‐naphthyl, at the 2‐positions of the η⁶‐1,3‐diisopropenylbenzene ligands, both biaryl‐based axial chirality and π‐arene‐based planar chirality are simultaneously induced in the products. The axial chirality is retained even after the removal of the dicarbonylchromium fragment, and the chiral biaryl/heterobiaryl compounds are obtained with complete retention of the enantiopurity.     

Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes

In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ₂ lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure.     

Molybdenum Complexes Supported by Mixed NHC/Phosphine Ligands: Activation of N2 and Reaction With P(OMe)3 to the First Meta‐Phosphite Complex

Molybdenum(0) dinitrogen complexes, supported by the mixed NHC/phosphine pincer ligand PCP, exhibit an extreme activation of the N₂ ligand due to a very π‐electron‐rich metal center. The low thermal stability of these compounds can be increased using phosphites instead of phosphines as coligands. Through an amalgam reduction of [MoCl₃(PCP)] in the presence of trimethyl phosphite and N₂ the highly activated and room‐temperature stable dinitrogen complex [Mo(N₂)(PCP)(P(OMe)₃)₂] is obtained. As a second product, the first transition metal complex containing the meta‐phosphite ligand P(O)(OMe) originates from this reaction.     

A post curing strategy toward the feasible covalent adaptable networks in polyacrylate latex films

The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers.     

Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.     

Hierarchical Hollow-Nanocube Ni−Co Skeleton@MoO3/MoS2 Hybrids for Improved-Performance Lithium-Ion Batteries

Improving the performance of anode materials for lithium-ion batteries (LIBs) is a hotly debated topic. Herein, hollow Ni−Co skeleton@MoS₂/MoO₃ nanocubes (NCM-NCs), with an average size of about 193 nm, have been synthesized through a facile hydrothermal reaction. Specifically, MoO₃/MoS₂ composites are grown on Ni−Co skeletons derived from nickel–cobalt Prussian blue analogue nanocubes (Ni−Co PBAs). The Ni−Co PBAs were synthesized through a precipitation method and utilized as self-templates that provided a larger specific surface area for the adhesion of MoO₃/MoS₂ composites. According to Raman spectroscopy results, as-obtained defect-rich MoS₂ is confirmed to be a metallic 1T-phase MoS₂. Furthermore, the average particle size of Ni−Co PBAs (≈43 nm) is only about one-tenth of the previously reported particle size (≈400 nm). If assessed as anodes of LIBs, the hollow NCM-NC hybrids deliver an excellent rate performance and superior cycling performance (with an initial discharge capacity of 1526.3 mAh g⁻¹ and up to 1720.6 mAh g⁻¹ after 317 cycles under a current density of 0.2 A g⁻¹). Meanwhile, ultralong cycling life is retained, even at high current densities (776.6 mAh g⁻¹ at 2 A g⁻¹ after 700 cycles and 584.8 mAh g⁻¹ at 5 A g⁻¹ after 800 cycles). Moreover, at a rate of 1 A g⁻¹, the average specific capacity is maintained at 661 mAh g⁻¹. Thus, the hierarchical hollow NCM-NC hybrids with excellent electrochemical performance are a promising anode material for LIBs.