Characteristics and performance of layered two-dimensional materials under doping engineering.

In recent years, doping engineering, which is widely studied in theoretical and experimental research, is an effective means to regulate the crystal structure and physical properties of two-dimensional materials and expand their application potential. Based on different types of element dopings, different 2D materials show different properties and applications. In this paper, the characteristics and performance of rich layered 2D materials under different types of doped elements are comprehensively reviewed. Firstly, 2D materials are classified according to their crystal structures. Secondly, conventional experimental methods of charge doping and heterogeneous atom substitution doping are summarized. Finally, on the basis of various theoretical research results, the properties of several typical 2D material representatives under charge doping and different kinds of atom substitution doping as well as the inspiration and expansion of doping systems for the development of related fields are discussed. Through this review, researchers can fully understand and grasp the regulation rules of different doping engineering on the properties of layered 2D materials with different crystal structures. It provides theoretical guidance for further improving and optimizing the physical properties of 2D materials, improving and enriching the relevant experimental research and device application development.

Defect engineering the electronic and optoelectronic properties of heterostructure of MoSSe/PbS (111).

The structural, electronic and optical properties of MoSSe, PbS (111) and MoSSe/PbS (111) have been studied by the first-principles calculations, and the effect of VSon electronic and optical properties of MoSSe/PbS (111). When PbS (111) is stacked on MoSSe, an internal electric field and ohmic contact are formed at interlayer, and exhibited metal property. Compared with MoSSe and PbS (111) monolayer, MoSSe/PbS (111) heterostructure has higher absorption coefficients. Further analysis shows that this can be attributed to the orbital hybridization between the heterostructure layers. When VSis introduced, spin splitting occurs, making the spin-down channel below the Fermi level and inducing half-metallicity. What's more, Vs MoSSe/PbS (111) still performances better optical absorption coefficient. Based on these findings, the heterogeneous structures and defects not only affect the electronic properties, but also can be used as an effective method to regulate the electrical and optical properties, providing useful theoretical guidance for further experimental studies.

Approaching Elaborate Control of the Nano-Products of Carbothermal Reduction Reaction Through In Situ Identification.

Atomic understanding of a chemical reaction can realize the programmable design and synthesis of desired products with specific compositions and structures. Through directly monitoring the phase transition and tracking the dynamic evolution of atoms in a chemical reaction, in situ transmission electron microscopy (TEM) techniques offer the feasibility of revealing the reaction kinetics at the atomic level. Nevertheless, such investigation is quite challenging, especially for reactions involving multi-phase and complex interfaces, such as the widely adopted carbothermal reduction (CTR) reactions. Herein, in-situ TEM is applied to monitor the CTR of Co3 O4 nanocubes on reduced graphene oxide nanosheets. Together with the first-principle calculation, the migration route of Co atoms during the phase transition of the CTR reaction is revealed. Meanwhile, the interfacial edge-dislocations/stress-gradient is identified as a result of the atomistic diffusion, which in turn can affect the morphology variation of the reactants. Accordingly, controllable synthesis of Co-based nanostructure with a desirable phase and structure has been achieved. This work not only provides atomic kinetic insight into CTR reactions but also offers a novel strategy for the design and synthesis of functional nanostructures for emerging energy technologies.

Au Nanoparticle Modification Induces Charge-Transfer Channels to Enhance the Electrocatalytic Hydrogen Evolution Reaction of InSe Nanosheets.

Electrocatalytic water splitting for hydrogen production is an efficient, clean, and sustainable strategy to solve energy and environmental problems. As the important alternative materials for noble metals (Pt, Ir, etc.), two-dimensional (2D) materials have been widely applied for electrocatalysis, although the practical performance is restricted by low carrier mobility and slow reaction kinetics. Here, we adopt the strategy of Au nanoparticle modification to achieve the enhanced hydrogen evolution reaction (HER) performance of InSe nanosheets. Experimental results prove that the HER performance of InSe nanosheets is significantly enhanced under the modification of Au nanoparticles, and the overpotential (392 mV) and Tafel slope (59 mV/dec) are significantly reduced compared to sole InSe nanosheets (580 mV and 148.2 mV/dec). First-principles calculations have found that the InSe/Au system exhibits metallicity because the free electrons provided by the Au particles are injected into the InSe, thereby improving its conductivity. The difference charge density and localized charge density of InSe/Au show that Au nanoparticle loading can induce the formation of Au-Se electron-transfer channels with electrovalent bond characteristics, which effectively promotes the charge transfer. Meanwhile, the standard free-energy calculation of the HER process shows that the InSe/Au heterojunction has a H* adsorption/desorption Gibbs free energy [(|ΔGH*|) = 0.59 eV] closer to the optimal value. This study reveals the theoretical mechanism of metal modification to improve the performance of electrocatalytic HER and is expected to motivate the development of a new strategy for enhancing the catalytic activity of 2D semiconductor materials.

A graphene-Mo2C heterostructure for a highly responsive broadband photodetector.

Photodetectors based on intrinsic graphene can operate over a broad wavelength range with ultrafast response, but their responsivity is much lower than commercial silicon photodiodes. The combination of graphene with two-dimensional (2D) semiconductors may enhance the light absorption, but there is still a cutoff wavelength originating from the bandgap of semiconductors. Here, we report a highly responsive broadband photodetector based on the heterostructure of graphene and transition metal carbides (TMCs, more specifically Mo2C). The graphene-Mo2C heterostructure enhanced light absorption over a broad wavelength range from ultraviolet to infrared. In addition, there is very small resistance for photoexcited carriers in both graphene and Mo2C. Consequently, photodetectors based on the graphene-Mo2C heterostructure deliver a very high responsivity from visible to infrared telecommunication wavelengths.

The electronic and magnetic properties of h-BN/MoS2 heterostructures intercalated with 3d transition metal atoms.

We performed density functional theory calculations to investigate the electronic and magnetic properties of h-BN/MoS2 heterostructures intercalated with 3d transition-metal (TM) atoms, including V, Cr, Mn, Fe, Co, and Ni atoms. It was found that metal and magnetic semiconductor characteristics are induced in the h-BN/MoS2 heterostructures after intercalating TMs. In addition, the results demonstrate that h-BN sheets could promote charge transfer between the TMs and the heterogeneous structure. Specifically, the h-BN/MoS2 heterostructure transforms from an indirect semiconductor to a metal after intercalating V or Cr atoms in the interlayers. For Mn, Fe, and Co atoms, the bandgaps of the intercalated heterojunction systems become smaller when the spin polarization is 100% at the highest occupied molecular orbital level. However, the system intercalated with Ni atoms exhibits no spin polarization and non-magnetic character. Strong covalent-bonding interactions emerged between the intercalated TMs and the nearest S atom of the h-BN/MoS2 heterostructure. In addition, the magnetic moments of the TM atoms show a decreasing trend for all the interstitial intercalated heterostructures compared with their free-standing states. These results reveal that h-BN/MoS2 heterostructures with intercalated TMs are promising candidates for application in multifarious spintronic devices.

Recent advances of monoelemental 2D materials for photocatalytic applications.

As a sustainable environmental governance strategy and energy conversion method, photocatalysis has considered to have great potential in this field due to its excellent optical properties and has become one of the most attractive technologies today. Among 2D materials, the emerging two-dimensional (2D) monoelemental materials mainly distributed in the -IIIA, -IVA, -VA and -VIA groups and show excellent performance in solar energy conversion due to their graphene-like 2D atomic structure and unique properties, thereby drawing increasing attention. This review briefly summarizes the preparation processes and fundamental properties of 2D single-element nanomaterials, as well as various modification strategies and adjustment mechanisms to enhance their photocatalytic properties. In particular, this article comprehensively discusses the related practical applications of 2D single-element materials in the field of photocatalysis, including photocatalytic degradation for contaminants removal, photocatalytic pathogen inactivation, photocatalytic fouling control and photocatalytic energy conversion. This review will provide some new opportunities for the rational design of other excellent photocatalysts based on 2D monoelemental materials, as well as present tremendous novel ideas for 2D monoelemental materials in other environmental conservation and energy-related applications, such as supercapacitors, electrocatalysis, solar cells, and so on.

Band offsets engineering in asymmetric Janus bilayer transition-metal dichalcogenides.

Using the first-principles calculation, we systematically studied the electronic properties of the bilayer transition metal dichalcogenides (TMDs) MX2 (M = Mo, W; X = S, Se, Te) with replacing one, two, three or four layers of X atoms as Y atoms (X ≠ Y = S, Se, Te). By comparison, it is found that when the inner two layers of chalcogenide atoms are different, the system has both valence band offset (VBO) and conduction band offset (CBO). Among them, values of the band offsets reach maxima when the inner one layer of X atoms is replaced by Y atoms, namely forming the asymmetric Janus bilayer XMX/YMX. We take SMoS/SeMoS as an example to analyze the formation of the band offsets and the improvement of optoelectronic properties. Importantly, it is also found that both external electric field and biaxial strain can regulate electronic structures of asymmetric Janus bilayer TMDs with noticeable modulation of the values of band offsets. When the external electric field changes from negative to positive continually, CBO decreases and VBO increases. While when the biaxial strain changes from compression to stretch continually, CBO increases and VBO decreases. These findings enrich the study of bilayer TMDs that can be used as optoelectronic, nanoelectronic and valleytronic devices.

First principles study of semihydrogenated graphene and topological insulator heterojunction.

Based on first principles calculations, we study the electronic properties of heterostructures formed by a 2D ferromagnetic insulator semihydrogenated graphene (SG) and topological insulator Bi2Se3 thin films of a few quintuple layers (QLs). It is found that the unsaturated C atoms in SG form bonds with Se atoms in Bi2Se3 thin film and the top surface states (at the interface) are strongly hybridized with SG. Due to breaking of time-reversal symmetry, the surface states open gaps of 40 meV and 150 meV for SG/3QL-Bi2Se3 and SG/5QL-Bi2Se3 heterostructures, respectively. Furthermore, a giant Rashba spin splitting is found induced by the SG layer.

Transition metal atoms absorbed on MoS2/h-BN heterostructure: stable geometries, band structures and magnetic properties.

We have studied the stable geometries, band structures and magnetic properties of transition-metal (V, Cr, Mn, Fe, Co and Ni) atoms absorbed on MoS2/h-BN heterostructure systems by first-principles calculations. By comparing the adsorption energies, we find that the adsorbed transition metal (TM) atoms prefer to stay on the top of Mo atoms. The results of the band structure without spin-orbit coupling (SOC) interaction indicate that the Cr-absorbed systems behave in a similar manner to metals, and the Co-absorbed system exhibits a half-metallic state. We also deduce that the V-, Mn-, Fe-absorbed systems are semiconductors with 100% spin polarization at the HOMO level. The Ni-absorbed system is a nonmagnetic semiconductor. In contrast, the Co-absorbed system exhibits metallic state, and the bandgap of V-absorbed system decreases slightly according to the SOC calculations. In addition, the magnetic moments of all the six TM atoms absorbed on the MoS2/h-BN heterostructure systems decrease when compared with those of their free-standing states.