The adsorption behaviours of Pt adatom on pristine and defective bilayer graphene

The structural stability and electronic property of metal Pt atom anchors on two typical substrates (including the pristine and defective bilayer graphene, PBG and DBG) are studied using the first-principles calculations. For the PBG sheets, the Pt atom at the bridge site of bottom layer has only one stable adsorption, which is more stable than other sites of the top layer. For the DBG sheets, the doped Pt below defective site has the larger adsorption energy than that of the upper one. Compared to the isolated graphene films, the Pt(111) substrate-supported graphene systems have effect on the adsorption energies of Pt adatom to some extent, but it does not affect the most preferable configurations. Moreover, the diffusion pathways and energy barriers of Pt adatom on PBG and DBG substrates are comparatively investigated. For the DBG sheets, the Pt dopant has smaller diffusion barrier on upper layer than that of the intercalation process through the defective site. Therefore, the Pt dopant prefers to diffuse on the top layer and then forms the metal impurity. This work provides valuable information on understanding the formation process and intercalation mechanism of metal adatom on graphene sheets.     

Theoretical investigation of manganese adsorption on graphene and graphane: A first-principles comparative study

Within the framework of spin-polarized generalized gradient approximation (σGGA) of the density functional theory (DFT) and pseudopotential method, the structural, magnetic, and electronic properties of graphene and graphane upon the adsorption of manganese atoms have been theoretically investigated. In contrast to the recent results (New J. Phys. 12, 063020 (2010)), Mn atom has been found to be adsorbed on a hollow-site configuration and no appreciable indication to substitute one of the C atoms of the graphene sheet. Unlike the recent results on Mn-doped graphane (Carbon 48, 3901 (2010)), the Mn adatom prefers to adsorb on the top of a carbon atom, forming a bridge with the uppermost hydrogen atoms. The magnetic moment of the Mn-doped graphene is found to be larger than that of the Mn-doped graphane. The structural parameters and electronic properties of both Mn-doped graphene and Mn-doped graphane are determined and compared with the available data.     

First-principles studies: Thiolated Au2Cr and Au6Cr clusters

The structural, energetic and magnetic properties of thiol-passivating Au₂Cr and Au₆Cr clusters are investigated by performing first-principles calculation based on density functional theory. We find that the adsorption of thiolate is energetically more favorable than thiol and that the thiolates favor “top” site adsorption on Cr atom in one methanethiolate adsorbed Au₂Cr cluster while they favor “bridge” site adsorption on top of the middle point of Cr–Au bonds in three methanethiolates adsorbed Au₂Cr cluster. In thiol-passivating Au₆Cr cluster, the thiol favor “top” site adsorption on top of atom Au while the thiolate favor “bridge” site adsorption on top of the middle point of Au–Au bonds. The energetics of the reactions indicates that these thiol-passivating Au₂Cr or Au₆Cr clusters can be used as hydrogen storage materials. There are large and positive spin populations on atom Cr. The spin populations of atoms Au, S and H are attributed to both the spin delocalization and the spin polarization mechanisms.     

缺陷对Pt在Graphene上吸附影响的研究

本文利用第一原理方法计算了空位缺陷和硼（B）掺杂时对Pt在graphene上吸附的影响.结果表明：Pt在graphene上吸附的稳定位置是Pt吸附在桥位;悬挂键的存在极大的增强了Pt在graphene空位处的吸附;B替位掺杂有利于Pt原子在杂质附近的吸附.     

缺陷对Pt在Graphene上吸附影响的研究

本文利用第一原理方法计算了空位缺陷和硼（B）掺杂时对Pt在graphene上吸附的影响.结果表明：Pt在graphene上吸附的稳定位置是Pt吸附在桥位；悬挂键的存在极大的增强了Pt在graphene空位处的吸附；B替位掺杂有利于Pt原子在杂质附近的吸附.     

Anchoring platinum on graphene using metallic adatoms: a first principles investigation

First principles calculations based on spin-polarized density functional theory were used to identify metallic adatoms that would strengthen the Pt(111)/graphene interface (with a low work of separation of 0.009 J m(-2)), when the adatom was placed between the Pt(111) and the graphene. It was shown that the strength of the Pt-adatom bond, which had a metallic character, increased with the amount of charge transferred from the adatom to the Pt. The carbon-adatom bond, on the other hand, had a mixed ionic and covalent character and was weaker than the Pt-adatom bond for each of the 25 elements considered. Consequently, the total Pt(111)/graphene interface strength and, hence, the anchoring effect of the adatom were controlled by the carbon-adatom bond strength. Metals with unfilled d orbitals increased the Pt/graphene interface strength to above 0.5 J m(-2). The carbon-adatom bond strength was proportional to the ratio between the charge transferred from the adatom to the graphene (ΔZ(C)) and the charge transferred to the Pt surface (ΔZ(Pt)); i.e., the ΔZ(C)/ΔZ(Pt) ratio defined the ability of an adatom to anchor Pt to graphene. For Ir, Os, Ru, Rh and Re, ΔZ(C)/ΔZ(Pt) > 1.0, making these elements the most effective adatoms for anchoring Pt to graphene.     

Structures of Pt clusters on graphene doped with nitrogen, boron, and silicon: a theoretical study

The structures of Pt clusters on nitrogen-,boron-,silicon-doped graphenes are theoretically studied using densityfunctional theory.These dopants(nitrogen,boron and silicon) each do not induce a local curvature in the graphene and the doped graphenes all retain their planar form.The formation energy of the silicon-graphene system is lower than those of the nitrogen-,boron-doped graphenes,indicating that the silicon atom is easier to incorporate into the graphene.All the substitutional impurities enhance the interaction between the Pt atom and the graphene.The adsorption energy of a Pt adsorbed on the silicon-doped graphene is much higher than those on the nitrogen-and boron-doped graphenes.The doped silicon atom can provide more charges to enhance the Pt-graphene interaction and the formation of Pt clusters each with a large size.The stable structures of Pt clusters on the doped-graphenes are dimeric,triangle and tetrahedron with the increase of the Pt coverage.Of all the studied structures,the tetrahedron is the most stable cluster which has the least influence on the planar surface of doped-graphene.     

单层GaSe表面Fe原子吸附体系电子自旋性质调控

Ⅲ族金属单硫化物因其优越的光电和自旋电子特性而备受关注,实现对其自旋性质的有效调控是发展器件应用的关键.本文采用密度泛函理论系统地研究了GaSe表面Fe原子吸附体系的几何构型及自旋电子特性.Fe/GaSe体系中Fe吸附原子与最近邻Ga,Se原子存在较强的轨道耦合效应,使体系呈现100%自旋极化的半金属性.其自旋极化贡献主要来源于Fe-3d电子的转移及Fe-3d,Se-4p和Ga-4p轨道杂化效应.对于Fe双原子吸附体系,两Fe原子之间的自旋局域导致原本从Fe转移至GaSe的自旋极化电荷量减少,从而费米能级附近的单自旋通道转变为双自旋通道,费米能级处的自旋极化率转变为0.研究结果揭示了Fe_n/GaSe吸附体系自旋极化特性的形成和转变机制,可为未来二维自旋纳米器件的设计与构建提供参考.     

Electronic and magnetic properties of copper-family-element atom adsorbed graphene nanoribbons with zigzag edges

We have investigated the electronic and magnetic properties of copper-family-element (CFE) atom adsorbed graphene nanoribbons (GNRs) with zigzag edges using first-principles calculations based on density functional theory. We found that CFE atoms energetically prefer to be adsorbed at the edges of nanoribbons. Charges are transferred between the CFE atom and carbon atoms at the edge, which reduce the local magnetic moment of carbon atoms in the vicinity of adsorption site and change the electronic structure of GNRs. As a result, Cu adsorbed zigzag GNR is a semiconductor with energy band gap of 0.88 eV in beta-spin and energy gap of 0.22 eV in alpha-spin, while Ag adsorbed zigzag GNR and Au adsorbed zigzag GNR are both half-metallic with the energy gaps of 0.68 eV and 0.63 eV in beta-spin, respectively. These results show that CFE atom adsorbed zigzag GNRs can be applied in nanoelectronics and spintronics.     

Adsorption of transition metal atoms (Co and Ni) on zigzag graphene nanoribbon

The geometry structures and electronic properties of zigzag graphene nanoribbon (ZGNR) with the adsorption of transition metal atoms (Co and Ni) are investigated by using the density functional theory. The calculated results show that the interaction between Ni atom and ZGNR are stronger than that between Co atom and ZGNR. It is found that the ZGNR with Co adatom adsorbing has more possibility to show the character from semiconducting to the half-metallic one than that of the ZGNR with Ni adatom adsorbing. It is hoped that it may be valuable for investigating the GNR-based electronic devices.     

PtCu二元金属催化剂抗CO中毒性能的理论研究

基于密度泛函第一性原理研究了M-graphene(M=Pt,Cu,PtCu;graphene:pristine,Stonewales,Single-vacancy graphene)催化剂的抗CO中毒能力.对于纯Pt和纯Cu吸附在石墨烯上时,Pt的吸附能力最强,吸附结构最稳定.当Pt中掺杂Cu后,PtCu二元金属催化剂在石墨烯上的吸附结构的稳定性进一步增强.通过对M-graphene-CO吸附结构的研究,发现以缺陷石墨烯为载体的金属催化剂的抗CO中毒能力优于以原始石墨烯为载体的同种金属催化剂,PtCu二元金属催化剂抗CO中毒能力明显好于纯Pt和纯Cu的抗毒性.因此,缺陷石墨烯载体以及掺杂Cu的PtCu二元金属催化剂,对于提高催化剂的稳定性和抗CO中毒能力起到了重要的作用.     

Interfacial properties of Ce<Subscript>0.75</Subscript>Zr<Subscript>0.25</Subscript>O<Subscript>2</Subscript> supported noble metals (Pd,Pt) from first principles

First-principles electronic structure calculations of noble metals (NM=Pd, Pt)/Ce_0.75Zr_0.25O₂ systems are presented. It is found that: the NM adatoms do not prefer to stay at the atop or the bridge sites of the cations (Ce and Zr), but prefer to be adsorbed at or around the anion sites. The most preferable adsorption sites for both the Pd and Pt adatoms are the O-bridge sites neighboring the Zr dopant. The Pt adatom show much stronger interaction with the Ce_0.75Zr_0.25O₂(111) surface than does the Pd adatom. The interactions of the NM/Ce_0.75Zr_0.25O₂(111) interfaces are stronger than those of the corresponding NM/ceria(111) interfaces. There are some metal induced gap states (MIGS) appeared in the gaps of the NM/Ce_0.75Zr_0.25O₂(111) interfaces, which are important to catalytic properties of the NM/Ce_0.75Zr_0.25O₂(111) catalysts.     

Metal adsorption on monolayer blue phosphorene: A first principles study

We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and $0.77{\text{μ}}_B/\text{impurity}$ atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.     

The growth and chemisorptive propertles of Ag and Au monolayers on platinum single crystal surfaces: An AES,TDS and LEED study

The growth and chemisorptive properties of monolayer films of Ag and Au deposited on both the Pt(111) and the stepped Pt(553) surfaces were studied using Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), and low energy electron diffraction (LEED). AES studies indicate that the growth of Au on Pt(111) and Pt(553) and Ag on Pt(111) proceeds via a Stranski-Krastanov mechanism, whereas the growth of Ag on the Pt(553) surface follows a Volmer-Weber mechanism. Au dissolves into the Pt crystal bulk at temperatures > 800 K, whereas Ag desorbs at temperatures > 900 K. TDS studies of Ag-covered Pt surfaces indicate that the AgPt bond (283 kJ mol^?1) is ～25 kJ mol^?1 stronger than the AgAg bond (254 kJ mol^?1). On the Pt(553) surface the Au atoms are uniformly distributed between terrace and step sites, but Ag preferentially segregates to the terraces. The decrease in CO adsorption on the Pt crystal surfaces is in direct proportion to the Ag or Au coverage. No CO adsorption could be detected for Ag or Au coverages above one monolayer at 300 K and 10^?8 Torr. The heat of adsorption of CO on Pt is unaltered by the presence of Ag or Au.     

单原子Pt吸附于不同原子暴露终端BiOBr{001}面的第一性原理研究

基于密度泛函理论(density functional theory, DFT)的第一性原理方法研究了暴露不同原子终端的BiOBr{001}表面以及单原子Pt吸附于BiOBr{001}-BiO不同位置的几何构型、电子结构、光学性质和电荷转移.计算结果表明:BiOBr{001}面BiO终端暴露可诱导产生表面态且价带和导带能级向低能方向移动,光氧化性增强,尤其导带下方出现的表面态能级有助于光生电子-空穴对的分离和迁移,光吸收显著增强,且BiOBr{001}面BiO终端的功函数远低于贵金属Pt,有利于电荷定向转移.其次,单原子Pt吸附于BiOBr{001}-BiO为基底的表面,在禁带中间诱导产生杂质能级, Pt吸附于穴位时吸附能最小,光响应能力最好且电荷转移量最大,吸附于顶位和桥位时,形成开放性的贫电子区域,因此可预测穴位为Pt原子的吸附位点,预示其良好的降解有机污染物效果, Pt吸附于BiOBr{001}-BiO的顶位和桥位,具有潜在的CO_2还原或固氮等领域应用.     

氮原子修饰点缺陷石墨烯结构和性质的理论研究

氮原子掺杂石墨烯对基于石墨烯的器件和催化研究具有重要的应用价值.本文采用基于密度泛函理论的计算方法,研究了氮原子修饰的C-Bridge(碳原子吸附在石墨烯碳碳键桥位)、C-Top(碳原子吸附在石墨烯一个碳原子上方)和C7557(碳原子对吸附在石墨烯碳环上方)三种不同点缺陷类型的石墨烯物理性质.讨论不同缺陷石墨烯结构在用氮原子进行修饰前后体系的稳定性、电子结构等;计算得到了缺陷处原子的分波态密度(PDOS)图,分析了原子间的相互作用;模拟出氮原子修饰后缺陷石墨烯恒流模式的STM图像,以便和实验上得出的图像进行对比.计算结果表明,对于所选取的三种不同缺陷,氮原子能够较稳定地吸附在缺陷表面.C-Bridge和C-Top缺陷结构本身具有磁矩,经氮原子修饰后结构磁矩消失.与之相反,C7557缺陷结构本身没有磁矩,经氮原子修饰后缺陷体系带有磁矩.另外,C-Bridge和CTop两种不同缺陷结构石墨烯经过氮原子修饰后,体系几何结构变得完全一样.     

Ab-initio study of the coadsorption of Li and H on Pt(001), Pt(110) and Pt(111) surfaces

The coadsorption of Li and H atoms on Pt(001), Pt(110) and Pt(111) surfaces is studied using density functional theory with generalised gradient approximation. In all calculations Li, H and the two topmost layers of the metal were allowed to relax. At coverage of 0.25 mono-layer in a p(2×2) unit cell, lithium adsorption at the hollow site for the three surfaces is favoured over top and bridge sites. The most favoured adsorption sites for H atom on the Pt(001) and Pt(110) surfaces are the top and bridge sites, while on Pt(111) surface the fcc site appears to be slightly favoured over the hcp site. The coadsorption of Li and atomic hydrogen shows that the interaction between the two adsorbates is stabilising when they are far from each other. The analysis of Li, H and Pt local density of states shows that Li strongly interacts with the Pt surfaces.     

Theoretical investigation of structures and energetics of sodium adatom and its dimer on graphene: DFT study

Extensive ab initio calculations have been performed to study the energetics of a sodium (Na) atom and its dimer adsorbed on graphene using the SIESTA package Soler et al. (2002) [1] which works within a DFT(density functional theory)–GGA (generalized gradient approximation) pseudopotential framework. The adsorption energy, geometry, charge transfer, ionization potential and density of states (DOS), partial density states (PDOS) of adatom/dimer-graphene system have been calculated. After considering various sites for adsorption of Na on graphene, the center of a hexagonal ring of carbon atoms is found to be the preferred site of adsorption while the Na₂ dimer prefers to rest parallel to the graphene sheet. We find insignificant energy differences among adsorption configurations involving different possible sites in parallel orientation, which implies high mobility of the dimer on the graphene sheet. We also notice only a slight distortion of the graphene sheet perpendicular to its plane upon adatom adsorption. However, some lateral displacements seen are more perceptible.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

金掺杂锯齿型石墨烯纳米带的电磁学特性研究

本文采用基于密度泛函理论的第一性原理计算了金原子填充锯齿型石墨烯纳米带 (ZGNRs)中双空位结构的电磁学特性. 计算结果表明: 边缘位置是金原子的最稳定掺杂位置, 杂质原子的引入导致掺杂边缘的磁性被抑制, 不过掺杂率足够大时, 掺杂边缘的磁性反而恢复了. 金掺杂纳米带的能带结构对掺杂率敏感: 随着掺杂率的增大, 掺杂纳米带分别表现半导体特性、半金属特性以及金属特性. 本文的计算表明金原子掺杂可以调制ZGNR的磁性以及能带特性, 为后续实验起指导作用, 有利于推动石墨烯材料在自旋电子学方面的应用.