双层石墨烯掺杂Pd对CO和NO的气敏特性研究

采用基于密度泛函理论的第一性原理计算方法,研究了AA堆叠型双层石墨烯掺杂Pd原子(Pd/BG)后对气体分子CO和NO的气敏特性和吸附机理.结果表明,Pd原子的掺杂改变了双层石墨烯的电子性质和局部几何结构.Pd原子替代双层石墨烯的一个碳原子后,杂质原子突出层外区域(Po)和突入层间区域(Pi)都可以形成稳定结构,但是突出(Po)构型更有利于气体分子的吸附.对于Po构型,CO和NO吸附在Pd/BG上的最稳定结构是不同的,CO分子与石墨烯表面呈一定夹角,而NO分子近似垂直于石墨烯表面.Pd/BG对NO分子的吸附强于CO分子.气体分子在Po构型上属于化学吸附,而在Pi构型上属于物理吸附.Pd/BG吸附CO和NO气体分子后具有不同的电子性质.Pd/BG体系为半导体性质,在吸附CO气体分子后,转变为金属性,系统无磁性;而在吸附NO气体分子后变为金属性且具有较大磁矩.这种电子性质的变化能够阐明气体分子吸附的敏感程度.研究结果能够为石墨烯基的气体传感器或者探测器提供理论基础和实验指导.     

Randomly Distributed Vacancies Influence on Magnetic Properties of the Bilayer Thin Film

In this paper we are investigating the magnetic behavior of the double-layer thin film in the extended Heisenberg model, with long-range dipolar interaction, taking into account the influence of the randomly distributed vacancies on the magnetic properties of the system. We are studying the physical quantities of interest (magnetization, magnetic susceptibility and specific heat) via Monte Carlo technique, by applying the standard Metropolis algorithm. In this context, we investigate the critical temperature variation for different vacancies concentration levels, taking into account the uniform and the superficial distribution of the defects, respectively.      

锰掺杂锯齿型石墨烯纳米带电磁学特性研究

基于密度泛函理论的第一性原理,计算了锰原子单空位掺杂锯齿型石墨烯纳米带6种不同位置时的电磁学特性。结果表明:锰原子掺杂石墨烯纳米带的能带结构对掺杂位置十分敏感。随着锰掺杂位置的变化,掺杂石墨烯纳米带分别表现出半导体性和金属性特征。锰原子掺杂石墨烯纳米带改变了原本的磁性特征,掺杂位置不同,结构磁性特点也不相同,掺杂位置在4号位置时,纳米带实现了由反铁磁态的锯齿型石墨烯纳米带向铁磁性的转化。锰原子掺杂锯齿型石墨烯纳米带可以调制其磁性和能带特性,为石墨烯纳米带在电磁学领域应用提供一定的理论依据。     

High-Field Electronic Properties of Graphene

We have measured the energy gaps in single-layer and bilayer graphene by means of temperature dependent transport experiments in high magnetic fields up to 33 T. They follow the expected Landau level splitting when a finite level width is taken into account. The quantum Hall effect, hitherto only observed up to 30 K, remains visible up to 200 K in bilayers and even up to room temperature in single-layer graphene. Our experiments in single-layer graphene show that the lowest Landau level, shared equally between electrons and holes at zero energy, becomes extremely narrow in high magnetic fields. It is this narrowing, together with the large Landau level splitting in graphene that leads to an extremely robust localization and makes the quantum Hall effect visible up to room temperature. In high magnetic fields (B>20 T) we observe a strongly increasing resistance with decreasing temperature. These results are explained with field dependent splitting of the lowest Landau level of the order of a few Kelvin, as extracted from activated transport measurements.     

Electronic and Electrical Conductivity of AB and AA-Stacked Bilayer Graphene with Tunable Layer Separation

This humble work attempts to study the electronic and electrical conductivity characteristics of AB and AAstacked bilayer graphene (BLG) sheet, by using ab initio calculation. The electronic transport coefficient was calculated by using Boltzmann transport equations implanted in Boltztrap package at various temperatures from 80 to 380 K. First, this study will begin to experiment an interlayer spacing from 3.55 and 3.35 Å respectively for AA and AB-BLG. If the distance between the layers is more than 5.00 Å, the increase or decrease of energy does depend on the interlayer spacing so band gap is equal to zero. The electrical conductivity of AA and AB-BLG is compared to the experimental electrical conductivity of graphene monolayer under increasing spacing between layers to 4.00 Å. Band gap decreases with the increasing space while conductivity increases with increasing space. AA-BLG electrical conductivity shows a value near to the experimental electrical conductivity of graphene ribbon for 4.00 Å at 380 K. Nevertheless, the distance variation does not much affect the electronic and electrical characteristics of AB-BLG. In addition, the increase between the interlayer distances does not influence so much the electrical conductivity. Therefore, increasing the distance between interlayers decreases the electrical conductivity due to the increasing of band gap.     

Electronic Structure and Magnetic Properties of Zinc-Blende Co-Doped GaN with N Vacancies

The electronic structure and magnetic properties of zinc-blende structure of (Ga,Co)N phase with N vacancy defects are investigated using the Korringa–Kohn–Rostoker (KKR) method combined with coherent potential approximation (CPA). The results show that (Ga,Co)N phase is ferromagnetically polarized with an enhancement of the polarization and that the electronic structure can be modified simply by changing the concentration of N vacancies. Moreover, the (Ga,Co)N with high density of N vacancies shows a drastic increase of the magnetic moment of cobalt in the parent GaN compound, to reach a maximum value of 1.7 μ_B/Co at 8 at.%, which is in good agreement with the experimental values reported in the literature.     

单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究

本研究采用基于密度泛函理论的第一性原理方法,在局域密度近似和广义梯度近似下,研究了单点缺陷下不同结构氧化石墨烯的电子结构和光学特性。研究结果表明:文中四种构型的氧化石墨烯为力学稳定结构,其中包含不饱和氧原子的氧化石墨烯结构在水裂解及制氢中具有重要应用潜力。能带及分波态密度计算结果表明,包含不饱和氧原子的构型为间接带隙半导体,其余构型均为直接带隙半导体,且掺杂类型和带隙值随结构不同而改变。氧化石墨烯的光学吸收表现为各向异性,且在垂直于平面方向上的吸收边蓝移到近紫外可见光区。包含sp3杂化形式的结构光学吸收系数比包含sp2杂化的结构高,说明碳氧双键和悬挂键的存在对吸收光谱有重要影响。     

Influences of Cd-Substitution and Intrinsic Vacancies on the Electronic Structures and Optical Properties of ZnO Nanotubes

The electronic structures and optical properties of the defect-free armchair and zigzag ZnO nanotubes (NTs) as well as ZnO NTs containing defects have been investigated using the first-principles projector augmented wave potential within density functional theory framework. Simultaneously, the relevant properties for the corresponding ZnO sheets are also exhibited for comparison. Attributing to the influence of curvature, the band gaps of the defect-free, Cd substitutional, and O deficient ZnO NTs are decreased, as compared with the corresponding sheets. Moreover, for both ZnO sheets and ZnO NTs, the band gap of the substitutional Cd case is smaller than that of the defect-free case, by contraries, O vacancy case is larger. In particular, the Zn vacancy could introduce magnetism in both ZnO sheet and ZnO NTs. Curvature-induced drifting of the conduction bands towards the Femi level allows the electronic excitations from the valence band to conduction band at ??-point through optical absorption in the visible region. The near-band-edge emission of the Cd-doped ZnO NTs shows a slight red shift, while the presence of the O vacancy contributes strongly to optical absorption in the visible region. This finding is useful for the design of new generation of materials with improved solar radiation absorption.     

Strain Modulation of Electronic and Heat Transport Properties of Bilayer Boronitrene

Strain engineering has been proven as an effective approach to modify electronic and thermal properties of materials. Recently, strain effects on two-dimensional materials have become important relevant topics in this field. We performed density functional theory studies on the electronic and heat transport properties of bilayer boronitrene samples under an isotropic strain. We demonstrate that the strain will reduce the band gap width but keep the band gap type robust and direct. The strain will enhance the thermal conductivity of the system because of the increase in specific heat. The thermal conductivity was studied as a function of the phonon mean-free path.     

SW缺陷石墨烯铝原子吸附能的第一性原理研究

基于密度泛函理论（DFT）和广义梯度近似（GGA）,对SW（Stone--Wales）陷石墨烯的结构和吸附能进行了研究,计算了石墨烯吸附Al原子前后的能带结构,态密度和吸附能,计算结果表明,掺杂SW缺陷有利于石墨烯和具有自由电子的金属原子的吸附结合,与未掺杂时对比,掺杂SW缺陷可显著提高石墨烯片的吸附能。     

Control of Local Electronic Structure of Pd Single Atom Catalyst by Adsorbate Induction

Aiming at regulating and controlling the localized electronic states while maintaining the metal atoms in the isolation form, an in situ adsorbate induced strategy is proposed at a programmed temperature to activate Zr-based metal–organic framework (MOF) supported single Pd atom catalyst. It is discovered that in situ treatment environments trigger the change of lattice parameters in MOF materials by reaction heat effect, observed by in situ X-ray diffraction, spherical aberration-corrected electron microscope, and X-ray adsorption fine structure (XAFS). The as-obtained electron-deficient Pd single atoms are critical to the high intrinsic activity (turnover frequency of 0.132 s^?1) and selectivity of 93% with the long-term stability in the semihydrogenation of acetylene, which can be comparable to the state-of-the-art Pd catalysts. This superior catalytic behavior correlates with the reduced C₂H₄ desorption energy and the activation barriers for the hydrogenation, confirmed by density functional theory calculation.     

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC

The effects of Pb intercalation on the structural and electronic properties of epitaxial single‐layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X‐ray photoelectron spectroscopy, and angle‐resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π‐bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of Pb? Si chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole‐doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene‐capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.     

Effect of Vacancies on the Electronic Structure and Bonding of Zirconium Nitride

The electronic structure and bonding configuration of cubic (B1 type) Zr- and N-deficient zirconium nitride phases were investigated using self-consistent linearized muffin-tin-orbital calculations in the atomic-sphere approximation for a supercell containing eight atoms. Interatomic interactions were analyzed in terms of the crystalline orbital overlap population calculated by the semiempirical tight-binding method. The results are compared with earlier calculations and available experimental data on the electronic structure of nonstoichiometric ZrN.     

Structural Stability, Electronic and Magnetic Properties of Cu Adsorption on Defected Graphene: A First Principles Study

Structural stabilities, electronic structures, and magnetic properties of Cu atom adsorption on pure, B(N)-doped and single-vacancy graphene have been studied using the first-principle method. It was found that the electronic property of graphene can be tuned by B or N doping. B-doped and N-doped graphene turned into a p-type and n-type semiconductor with a band gap of 0.2 eV, respectively. Total energy calculation results demonstrated the most stable site for the Cu atom adsorption on pure, B-doped and N-doped graphene is the top, bridge, and hollow site, respectively. B doping and vacancy both enhance the adsorption capacity for the Cu atom, while N doping weakens the capacity. Furthermore, B and N atoms do not induce magnetism in graphene, while the magnetic moment is induced when Cu is adsorbed on the graphene sheet, which is mainly caused by the unsaturated s-electrons of the Cu atom.     

Pd Single‐Atom Catalysts on Nitrogen‐Doped Graphene for the Highly Selective Photothermal Hydrogenation of Acetylene to Ethylene

The selective hydrogenation of acetylene to ethylene in an ethylene‐rich gas stream is an important process in the chemical industry. Pd‐based catalysts are widely used in this reaction due to their excellent hydrogenation activity, though their selectivity for acetylene hydrogenation and durability need improvement. Herein, the successful synthesis of atomically dispersed Pd single‐atom catalysts on nitrogen‐doped graphene (Pd₁/N‐graphene) by a freeze‐drying‐assisted method is reported. The Pd₁/N‐graphene catalyst exhibits outstanding activity and selectivity for the hydrogenation of C₂H₂ with H₂ in the presence of excess C₂H₄ under photothermal heating (UV and visible‐light irradiation from a Xe lamp), achieving 99% conversion of acetylene and 93.5% selectivity to ethylene at 125 °C. This remarkable catalytic performance is attributed to the high concentration of Pd active sites on the catalyst surface and the weak adsorption energy of ethylene on isolated Pd atoms, which prevents C₂H₄ hydrogenation. Importantly, the Pd₁/N‐graphene catalyst exhibits excellent durability at the optimal reaction temperature of 125 °C, which is explained by the strong local coordination of Pd atoms by nitrogen atoms, which suppresses the Pd aggregation. The results presented here encourage the wider pursuit of solar‐driven photothermal catalyst systems based on single‐atom active sites for selective hydrogenation reactions.     

Electronic properties of Bilayer Fullerene onions

HOMO–LUMO gaps of the bilayer fullerene onions were investigated. For this purpose, HOMO and LUMO energies for the isolated fullerenes were calculated using the parameterization of the tight binding method with the Harrison–Goodwin modification. Then, by the consideration of the van der Waals interaction, the thermodynamical stability of possible combinations of the fullerene molecules was verified and the unstable forms were excluded. Next, the difference of the Fermi levels of the outer and inner shells was calculated by the consideration of the hybridization of the orbitals by using the geometric parameters. The results were obtained by the combination of these calculations.     

温度对堆叠双层石墨烯层间耦合的影响

将不同层数堆叠和化学气相沉积法（CVD）生长的石墨烯在室温下进行拉曼光谱表征分析其层间耦合状态,并分析了不同温度下堆叠和CVD生长的双层石墨烯温度对其层间耦合的影响。研究结果表明:室温下CVD生长双层石墨烯和堆叠双层石墨烯的层间耦合状态截然不同;在25～250 ℃范围内,层间没有耦合作用或存在弱耦合作用的堆叠双层石墨烯的G峰峰位温度系数小于存在电子耦合的CVD生长双层石墨烯;超过250 ℃后,堆叠双层石墨烯G峰峰位温度系数变为正值,层与层之间可能产生了耦合,性质发生改变;在25～400 ℃ 范围内两种材料的2D峰半峰宽和G峰/2D峰强度比变化趋势几乎相同,但堆叠双层石墨烯波动大,对温度更敏感。