Search

Wedemonstrate how substrate interfacial chemistry can be utilizedto tailor the physical properties of single-crystalline molybdenumdisulfide (MoS2) atomic-layers. Semiconducting, two-dimensionalMoS2possesses unique properties that are promising forfuture optical and electrical applications for which the ability totune its physical properties is essential. We use self-assembled monolayerswith a variety of end termination chemistries to functionalize substratesand systematically study their influence on the physical propertiesof MoS2. Using electrical transport measurements, temperature-dependentphotoluminescence spectroscopy, and empirical and first-principlescalculations, we explore the possible mechanisms involved. Our datashows that combined interface-related effects of charge transfer,built-in molecular polarities, varied densities of defects, and remoteinterfacial phonons strongly modify the electrical and optical propertiesof MoS2. These findings can be used to effectively enhanceor modulate the conductivity, field-effect mobility, and photoluminescencein MoS2monolayers, illustrating an approach for localand universal property modulations in two-dimensional atomic-layers. [ABSTRACT FROM AUTHOR]

Transition metal dichalcogenide monolayers exhibit ultrahigh surface sensitivity since they expose all atoms to the surface and thereby influence their optoelectronic properties. Here, we report an intriguing lightening of the photoluminescence (PL) from the edge to the interior over time in the WS 2 monolayers grown by physical vapor deposition method, with the whole monolayer brightened eventually. Comprehensive optical studies reveal that the PL enhancement arises from the p doping induced by oxygen adsorption. First-principles calculations unveil that the dissociation of chemisorbed oxygen molecule plays a significant role; i.e., the dissociation at one site can largely promote the dissociation at a nearby site, facilitating the photoluminescence lightening. In addition, we further manipulate such PL brightening rate by controlling the oxygen concentration and the temperature. The presented results uncover the extraordinary surface chemistry and related mechanism in WS 2 monolayers, which deepens our insight into their unique PL evolution behavior.

Two-dimensional (2D) MXene-loaded single-atom (SA) catalysts have drawn increasing attention. SAs immobilized on oxygen vacancies (O V ) of MXene are predicted to have excellent catalytic performance; however, they have not yet been realized experimentally. Here Pt SAs immobilized on the O V of monolayer Ti 3 C 2 T x flakes are constructed by a rapid thermal shock technique under a H 2 atmosphere. The resultant Ti 3 C 2 T x -Pt SA catalyst exhibits excellent hydrogen evolution reaction (HER) performance, including a small overpotential of 38 mV at 10 mA cm -2 , a high mass activity of 23.21 A mg Pt -1 , and a large turnover frequency of 23.45 s -1 at an overpotential of 100 mV. Furthermore, density functional theory calculations demonstrate that anchoring the Pt SA on the O V of Ti 3 C 2 T x helps to decrease the binding energy and the hybridization strength between H atoms and the supports, contributing to rapid hydrogen adsorption-desorption kinetics and high activity for the HER.

Despite recent advances in layered ferromagnets, ferromagnetic interactions in these materials are rather weak. Here, we report pressure-enhanced ferromagnetism in layered CrSiTe 3 flakes revealed by high-pressure magnetic circular dichroism measurements. Below ∼3 GPa, CrSiTe 3 undergoes a paramagnetic-to-ferromagnetic phase transition at ∼32 K, and the field-induced spin-flip in the ferromagnetic phase produces nearly zero hysteresis loops, demonstrating soft ferromagnetism. Above ∼4 GPa, a soft-to-hard ferromagnetic transition occurs, signaled by rectangular-shaped hysteresis loops with finite coercivity and remanent magnetization. Interestingly, as pressure increases, the Curie temperature and coercivity dramatically increase up to ∼138 K and 0.17 T at 7.8 GPa, respectively, in contrast to ∼36 K and 0.02 T at 4.6 GPa. It indicates a remarkable influence of pressure on exchange interactions, which is consistent with DFT calculations. The effective interaction between magnetic couplings and external pressure offers new opportunities in pursuit of high-temperature layered ferromagnets.

The practical recycling of carbon dioxide (CO2) by the electrochemical reduction route requires an active, stable, and affordable catalyst system. Although noble metals such as gold and silver have been demonstrated to reduce CO2 into carbon monoxide (CO) efficiently, they suffer from poor durability and scarcity. Here we report three-dimensional (3D) graphene foam incorporated with nitrogen defects as a metal-free catalyst for CO2 reduction. The nitrogen-doped 3D graphene foam requires negligible onset overpotential (-0.19 V) for CO formation, and it exhibits superior activity over Au and Ag, achieving similar maximum Faradaic efficiency for CO production (∼85%) at a lower overpotential (-0.47 V) and better stability for at least 5 h. The dependence of catalytic activity on N-defect structures is unraveled by systematic experimental investigations. Indeed, the density functional theory calculations confirm pyridinic N as the most active site for CO2 reduction, consistent with experimental results.

Guided by the principles of dislocation theory, we use the first-principles calculations to determine the structure and properties of dislocations and grain boundaries (GB) in single-layer transition metal disulfides MS(2) (M = Mo or W). In sharp contrast to other two-dimensional materials (truly planar graphene and h-BN), here the edge dislocations extend in third dimension, forming concave dreidel-shaped polyhedra. They include different number of homoelemental bonds and, by reacting with vacancies, interstitials, and atom substitutions, yield families of the derivative cores for each Burgers vector. The overall structures of GB are controlled by both local-chemical and far-field mechanical energies and display different combinations of dislocation cores. Further, we find two distinct electronic behaviors of GB. Typically, their localized deep-level states act as sinks for carriers but at large 60°-tilt the GB become metallic. The analysis shows how the versatile GB in MS(2) (if carefully engineered) should enable new developments for electronic and opto-electronic applications.