理想气体与范氏气体在任意准静态过程中的摩尔热容

导出了理想气体与范氏气体在任意准静态过程中的摩尔热容公式。     

Modeling chemical reactions on surfaces: The roles of chemical bonding and van der Waals interactions

Chemical reactions on surfaces play central roles in heterogeneous catalysis, and most reactions involve the formation and/or the cleavage of bonds. At present, density functional theory (DFT) has become the workhorse for computational investigation of reaction mechanisms, but its predictive power has been severely limited by the lack of appropriate exchange-correlation functionals. Here, we show that there are many cases where the chemical bonding and van der Waals (vdW) interactions both play a key role in chemical reactions on surfaces. After briefly introducing some DFT methods and basic theory in chemical reactions, we first demonstrate that DFT can help to understand the mechanisms of “classic” reactions that mainly dominated by covalent bonding and vdW forces, as exemplified in electrocatalytic reduction of CO₂ and the fabrication of 2D materials on metal substrates. We next show that DFT calculations can help to uncover the tautomerization reactions of molecules on metal surfaces, wherein the hydrogen bonding and vdW forces would largely affect the reaction process. More importantly, we show that in some cases, the vdW interactions can become the decisive effect that determines the adsorption configuration, energy hierarchy, and the potential-energy surface of chemical reactions, yielding distinct pathways and products. Additionally, we highlight the importance of more realistic conditions, such as surface defects, finite coverage, and temperature effects, in accurate modeling of chemical reactions. Finally, we summarize some challenges in modeling catalysis, which include many-body dispersive correction, strong correlation effect, and non-adiabatic approximations.     

Multiple surface conduction channels via topological insulator and amorphous insulator thin film multi-stacks

Multi-channel Bi₂Se₃ thin films were grown by combining molecular beam epitaxy and atomic layer deposition. High-resolution transmission electron microscope images showed that c-axis oriented Bi₂Se₃ grew on amorphous Al₂O₃ even after multiple stacking. While the surface morphology degraded for the upper layers, each layer was electrically similar. The electrical transport measurements showed that the weak anti-localization effect was quantitatively enhanced upon increasing the number of Bi₂Se₃ channels. Our results provide a promising approach to exploit diverse combinations of layered topological insulator films vertically stacked with amorphous insulator films.     

Efficient band structure engineering and visible-light response in ZrS2/GaS heterobilayer by electrical field or external strains

Via first-principle methods, the electronic structures and optical properties of 2D ZrS₂/GaS van der Waals heterostructure (vdWH) are studied. It is found that the band alignment changes from type-II to type-I under negative electrical field, and compressive strains. The transition points are -0.2 V/Å and -1%, respectively. The band gap changes efficiently under positive electrical field and compressive strains. The tensile strains increase the optical adsorption coefficients in ultraviolet regions, while the compressive strains increase the optical adsorption coefficients in visible region significantly.     

Surface chemistry and catalysis of oxide model catalysts from single crystals to nanocrystals

Fundamental understandings of surface chemistry and catalysis of solid catalysts are of great importance for the developments of efficient catalysts and corresponding catalytic processes, but have been remaining as a challenge due to the complex nature of heterogeneous catalysis. Model catalysts approach based on catalytic materials with uniform and well-defined surface structures is an effective strategy. Single crystals-based model catalysts have been successfully used for surface chemistry studies of solid catalysts, but encounter the so-called “materials gap” and “pressure gap” when applied for catalysis studies of solid catalysts. Recently catalytic nanocrystals with uniform and well-defined surface structures have emerged as a novel type of model catalysts whose surface chemistry and catalysis can be studied under the same operational reaction condition as working powder catalysts, and they are recognized as a novel type of model catalysts that can bridge the “materials gap” and “pressure gap” between single crystals-based model catalysts and powder catalysts. Herein we review recent progress of surface chemistry and catalysis of important oxide catalysts including CeO₂, TiO₂ and Cu₂O acquired by model catalysts from single crystals to nanocrystals with an aim at summarizing the commonalities and discussing the differences among model catalysts with complexities at different levels. Firstly, the complex nature of surface chemistry and catalysis of solid catalysts is briefly introduced. In the following sections, the model catalysts approach is described and surface chemistry and catalysis of CeO₂, TiO₂ and Cu₂O single crystal and nanocrystal model catalysts are reviewed. Finally, concluding remarks and future prospects are given on a comprehensive approach of model catalysts from single crystals to nanocrystals for the investigations of surface chemistry and catalysis of powder catalysts approaching the working conditions as closely as possible.     

Analytical thermodynamical properties of a two-dimensional electron gas in a magnetic field

Analytical expressions for the thermodynamical properties of a two-dimensional electron gas in a perpendicular magnetic field are derived.This is accomplished by first deriving the general expression for the thermodynamical potential,and then employing this result to obtain the corresponding expression for the two-dimensional gas.The chemical potential and magnetization are studied as a function of temperature and magnetic field,and shown to be in agreement with prior work.It is also shown that the results are close to those obtained by assuming a Gaussian density of states for the Landau levels.     

Ultrafast interlayer photocarrier transfer in graphene–MoSe_2 van der Waals heterostructure

We report the fabrication and photocarrier dynamics in graphene–MoSe_2 heterostructures. The samples were fabricated by mechanical exfoliation and manual stacking techniques. Ultrafast laser measurements were performed on the heterostructure and MoSe_2 monolayer samples. By comparing the results, we conclude that photocarriers injected in MoSe_2 of the heterostructure transfer to graphene on an ultrafast time scale. The carriers in graphene alter the optical absorption coefficient of MoSe_2. These results illustrate the potential applications of this material in optoelectronic devices.     

van der Waals gap-inserted light-emitting p–n heterojunction of ZnO nanorods/graphene/p-GaN film

We report on the electroluminescent (EL) and electrical characteristics of graphene-inserted ZnO nanorods (NRs)/p-GaN heterojunction diode. In a comparative study, ZnO NRs/p-GaN and ZnO NRs/graphene/p-GaN heterojunctions exhibit white and yellow EL emissions, respectively, at reverse bias (rb) voltages. The different EL colors are results of different dichromatic EL peak intensity ratios between 2.25 and 2.8 eV light emissions which are originated from ZnO and p-GaN sides, respectively. The 2.25 eV EL is predominant in both the heterojunctions, because of recombination by numerous electrons tunneled from p-GaN to ZnO across the thin barriers of the staggered broken gap with a large band offset in ZnO/p-GaN and the van der Waals (vdW) gap formed by graphene insertion at ZnO NRs/p-GaN. However, as for the 2.8 eV EL intensity, ZnO NRs/graphene/p-GaN hardly shows the EL emission, whereas ZnO NRs/p-GaN exhibits the substantially strong EL peak. We discuss that the significantly reduced 2.8 eV EL emission of ZnO NRs/graphene/p-GaN is a result of decreased depletion layer thickness at p-GaN side where the recombination events occur for 2.8 eV EL before the reverse bias-driven tunneling because the insertion of graphene (or vdW gap barrier) inhibits the carrier diffusion whose amount determines the depletion thickness when forming the heterojunctions. This study opens a way of suppressing (or enhancing) the specific EL wavelength for the dichromatic EL-emitting heterojunctions simply by inserting atom-thick vdW layer.     

Characteristics of a type-II n-MoS2/p-Ge van der Waals heterojunction

A few-atomic-layer molybdenum disulfide (MoS₂) film on Si/SiO₂ substrates grown by metal-organic chemical vapor deposition was investigated. The few-atomic-layer MoS₂ film was subsequently transferred onto a (100) p-Ge substrate to build a van der Waals n-p heterojunction. The as-grown few-atomic-layer MoS₂ film and the MoS₂/Ge heterostructure were characterized atomic force microscopy, spectroscopic ellipsometry, high-resolution scanning transmission electron microscopy, Raman spectroscopy analyses, photoluminescence (PL) measurements at room temperature (RT, 300 K), and type-II band alignment of the heterostructure determined by ultraviolet photoelectron spectroscopy. The RT-PL measurements showed dominant peaks at 1.96 and 1.8 eV for the as-grown MoS₂ and red-shifted PL peaks for that transferred onto Ge. We examined the electrical characteristics of the few-atomic-layer MoS₂ by forming a type-II band alignment van der Waals heterojunction with a highly doped p-Ge. The heterojunction solar cell exhibited an open-circuit voltage of 0.15 V and a short-circuit current density of 45.26 μA/cm². The external quantum efficiency measurements showed a spectral response up to approximately 500 nm owing to the absorption by the few-atomic-layer MoS₂ film.