Monolayer molybdenum disulfide (MoS2) is a two-dimensional direct band gap semiconductor with unique mechanical, electronic, optical, and chemical properties that can be utilized for novel ...nanoelectronics and optoelectronics devices. The performance of these devices strongly depends on the quality and defect morphology of the MoS2 layers. Here we provide a systematic study of intrinsic structural defects in chemical vapor phase grown monolayer MoS2, including point defects, dislocations, grain boundaries, and edges, via direct atomic resolution imaging, and explore their energy landscape and electronic properties using first-principles calculations. A rich variety of point defects and dislocation cores, distinct from those present in graphene, were observed in MoS2. We discover that one-dimensional metallic wires can be created via two different types of 60° grain boundaries consisting of distinct 4-fold ring chains. A new type of edge reconstruction, representing a transition state during growth, was also identified, providing insights into the material growth mechanism. The atomic scale study of structural defects presented here brings new opportunities to tailor the properties of MoS2 via controlled synthesis and defect engineering.
The cathodic oxygen reduction reaction (ORR) is essential in the electrochemical energy conversion of fuel cells. Here, through the NH3 atmosphere annealing of a graphene oxide (GO) precursor ...containing trace amounts of Ru, we have synthesized atomically dispersed Ru on nitrogen-doped graphene that performs as an electrocatalyst for the ORR in acidic medium. The Ru/nitrogen-doped GO catalyst exhibits excellent four-electron ORR activity, offering onset and half-wave potentials of 0.89 and 0.75 V, respectively, vs a reversible hydrogen electrode (RHE) in 0.1 M HClO4, together with better durability and tolerance toward methanol and carbon monoxide poisoning than seen in commercial Pt/C catalysts. X-ray adsorption fine structure analysis and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy are performed and indicate that the chemical structure of Ru is predominantly composed of isolated Ru atoms coordinated with nitrogen atoms on the graphene substrate. Furthermore, a density function theory study of the ORR mechanism suggests that a Ru-oxo-N4 structure appears to be responsible for the ORR catalytic activity in the acidic medium. These findings provide a route for the design of efficient ORR single-atom catalysts.
Monolayer transition metal dichalcogenides (TMDs) have become essential two-dimensional materials for their perspectives in engineering next-generation electronics. For related applications, the ...controlled growth of large-area uniform monolayer TMDs is crucial, while it remains challenging. Herein, we report the direct synthesis of 6-inch uniform monolayer molybdenum disulfide on the solid soda-lime glass, through a designed face-to-face metal-precursor supply route in a facile chemical vapor deposition process. We find that the highly uniform monolayer film, with the composite domains possessing an edge length larger than 400 µm, can be achieved within a quite short time of 8 min. This highly efficient growth is proven to be facilitated by sodium catalysts that are homogenously distributed in glass, according to our experimental facts and density functional theory calculations. This work provides insights into the batch production of highly uniform TMD films on the functional glass substrate with the advantages of low cost, easily transferrable, and compatible with direct applications.
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Recent success in isolating and growing various two-dimensional (2D) materials with intriguing properties has pushed forward the search for new 2D nanostructures with novel ...properties. Current experimental trial-and-error methods face the fundamental challenges of low efficiency and a lack of clear guidelines. In contrast, based on state-of-the-art first-principles calculations and well-developed structural prediction algorithms, computational simulations can not only predict an increasing number of new 2D materials with desirable properties but also suggest their possible synthesis routes. Among them, many predictions, such as the growth of monolayer boron sheets (borophene), piezoelectricity in molybdenum disulfide (MoS2), ferroelectricity in tin telluride (SnTe), topological defects in transition metal dichalcogenides, Dirac cones in borophene, and high carrier mobility and mobility anisotropy in black phosphorene, have been verified by experiments, showing the accuracy of computational approaches, as well as their power in facilitating experimental exploration in 2D flatland. To date, the rapid expansion in theoretical work has generated a large number of very important results, but the overall picture of recent progress, current challenges, and future opportunities is rarely discussed. Accordingly, this review aims at providing information about current trends and future perspectives for 2D materials research. To achieve this, the review is organized as follows: (1) discussion of structural predictions in 2D materials using borophene as an example; (2) predictions of the electronic, optical, mechanical, and magnetic properties in various 2D materials; (3) discussion of the influence of defects on the structures and properties of 2D materials; and (4) evaluation of current progress in computational simulations and perspectives for future development.
Layer-by-layer stacking or lateral interfacing of atomic monolayers has opened up unprecedented opportunities to engineer two-dimensional heteromaterials. Fabrication of such artificial ...heterostructures with atomically clean and sharp interfaces, however, is challenging. Here, we report a one-step growth strategy for the creation of high-quality vertically stacked as well as in-plane interconnected heterostructures of WS2/MoS2 via control of the growth temperature. Vertically stacked bilayers with WS2 epitaxially grown on top of the MoS2 monolayer are formed with preferred stacking order at high temperature. A strong interlayer excitonic transition is observed due to the type II band alignment and to the clean interface of these bilayers. Vapour growth at low temperature, on the other hand, leads to lateral epitaxy of WS2 on MoS2 edges, creating seamless and atomically sharp in-plane heterostructures that generate strong localized photoluminescence enhancement and intrinsic p-n junctions. The fabrication of heterostructures from monolayers, using simple and scalable growth, paves the way for the creation of unprecedented two-dimensional materials with exciting properties.
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.
The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen ...to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (−0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed COOH and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.
Modulating electronic structure of monolayer transition metal dichalcogenides (TMDCs) is important for many applications, and doping is an effective way toward this goal, yet is challenging to ...control. Here, the in situ substitutional doping of niobium (Nb) into TMDCs with tunable concentrations during chemical vapor deposition is reported. Taking monolayer WS2 as an example, doping Nb into its lattice leads to bandgap changes in the range of 1.98–1.65 eV. Noteworthy, electrical transport measurements and density functional theory calculations show that the 4d electron orbitals of the Nb dopants contribute to the density of states of Nb‐doped WS2 around the Fermi level, resulting in an n‐ to p‐type conversion. Nb‐doping also reduces the energy barrier of hydrogen absorption in WS2, leading to an improved electrocatalytic hydrogen evolution performance. These results highlight the effectiveness of controlled doping in modulating the electronic structure of TMDCs and their use in electronic related applications.
Substitutional doping is an important approach to modulate the electronic structure of 2D transition metal dichalcogenides (TMDCs). Using in situ substitutional doping during the chemical vapor deposition process, Nb‐doped TMDCs are grown with variable doping concentrations. The doping modulates the electronic structure of TMDCs and results in the realization of p‐type transport behavior and improved hydrogen evolution reaction performance.
As one of the CO2 capture and utilization technologies, Li-CO2 batteries have attracted special interest in the application of carbon neutral. However, the design and fabrication of a low-cost ...high-efficiency cathode catalyst for reversible Li2CO3 formation and decomposition remains challenging. Here, guided by theoretical calculations, CO2 was utilized to activate the catalytic activity of conventional nitrogen-doped graphene, in which pyridinic-N and pyrrolic-N have a high total content (72.65%) and have a high catalytic activity in both CO2 reduction and evolution reactions, thus activating the reversible conversion of Li2CO3 formation and decomposition. As a result, the designed cathode has a low voltage gap of 2.13 V at 1200 mA g–1 and long-life cycling stability with a small increase in the voltage gap of 0.12 V after 170 cycles at 500 mA g–1. Our work suggests a way to design metal-free catalysts with high activity that can be used to activate the performance of Li-CO2 batteries.
Abstract
Moiré superlattices of van der Waals heterostructures provide a powerful way to engineer electronic structures of two-dimensional materials. Many novel quantum phenomena have emerged in ...graphene and transition metal dichalcogenide moiré systems. Twisted phosphorene offers another attractive system to explore moiré physics because phosphorene features an anisotropic rectangular lattice, different from isotropic hexagonal lattices previously reported. Here we report emerging anisotropic moiré optical transitions in twisted monolayer/bilayer phosphorenes. The optical resonances in phosphorene moiré superlattice depend sensitively on twist angle and are completely different from those in the constitute monolayer and bilayer phosphorene even for a twist angle as large as 19°. Our calculations reveal that the Γ-point direct bandgap and the rectangular lattice of phosphorene give rise to the remarkably strong moiré physics in large-twist-angle phosphorene heterostructures. This work highlights fresh opportunities to explore moiré physics in phosphorene and other van der Waals heterostructures with different lattice configurations.
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