Thermal faceting of the rutile TiO2(001) surface

Temperature dependent faceting of rutile TiO₂ surfaces cut to the (001) plane has been reported [Tait and Kasowski, Phys. Rev. B20 (1979) 5178]. By comparing LEED data to beam positions calculated for various sets of facet planes, the facet planes have been identified. The first ordered structure observed on annealing ion bombarded surfaces is composed of {011} facets with the facet planes in a (2 × 1) reconstruction. The high temperature structure produced on annealing above 1300K is best described as {114} facets; however, there are deviations of the observed LEED pattern from that calculated for {114} facets, possibly because of the presence of related planes. LEED data have now been obtained on the behavior of (110), (100), (011), (114), and (001) surfaces in UHV. The observed stability of TiO₂ surfaces can be related to the Ti ion coordination numbers in the surface plane as derived from stoichiometric terminations of the rutile lattice.     

Field-ion microscope observation of ordering in the near-surface of Ni4Mo alloy using in situ annealing

Field-ion microscope observations were made on Ni₄Mo alloy to investigate surface effects on ordering during in situ annealing after quenching from high temperature α phase region. Surface ordering occurred preferentially at {200}_FCC and/or {111}_FCC facets (at 880–835°C). Surface layers with low degree of order ranging from ten to a few tens ångströms in thickness were formed (at 760–720°C). The degree of order in relatively large ordered domains decreased near the surface (at 825–810°C). In the interior of the specimens at a range of depths 100–300 Å from the surface, ordering behavior was essentially the same as that for bulk specimens (at 825–720°C). Homogeneously nucleated ordered domains coexisted with relatively large heterogeneously nucleated ones in the interior of the specimen (at 670°C). Certain relatively low index (FCC) planes faceted (at 880-720°C). Faceting originating from β structure (ordered structure) occurred on the surface (at 670°C). In addition, in situ formed deformation twin was observed (at 810–825°C).     

Facet formation in strained Si1−x Gex films

The surface morphology of epitaxial (001) Si_1−x Ge_x films, subject to biaxial strain, is studied by atomic force microscopy (AFM). Distinct facets are observed, oriented on {105}, {311}, and {518} crystal faces. The tiled arrangement of facets resembles a mosaic. We find that the growth sequence begins with the shallow {105} facets, followed by the appearance of steeper facets. After strain relaxation, the morphology coarsens and facets become less distinct. The existence of discrete facets produces a kinetic barrier to strain-induced roughening; and we show that increasing this barrier (by growing at reduced strain or reduced temperature) leads to a flatter surface morphology.     

Facet‐Dependent Effect of Well‐Defined CeO2 Nanocrystals on the Adsorption and Dephosphorylation of Phosphorylated Molecules

CeO₂ nanocrystals (CN) with different morphologies (i.e., cube, octahedron, and rod) are prepared and the facet‐dependent effect of these CeO₂ nanocrystals on the adsorption and dephosphorylation of phosphorylated molecules is investigated for the first time using the model p‐nitrophenyl disodium orthophorphate (p‐NPP). Due to their different surface atomic configurations, the {111} and {110} facets have much higher adsorption capacity and kinetic catalytic activities than {100} facets. All the CeO₂ nanocrystals can intensely promote the dephosphorylation reaction owing to the strong interaction between Ce cations and phosphoryl oxygens resulting in the cleavage of phosphoester bonds. As was expected, the above facet‐dependent effect can be verified by the practical application results of the CeO₂ nanocrystals on the capture and dephosphorylation of phosphopeptides. Thus, surface engineering could be a useful and feasible strategy for not only fundamentally understanding the interaction between crystal facets and molecules but also effectively developing high‐performance functional materials.     

Surface self-diffusion behavior of individual tungsten adatoms on rhombohedral clusters

The diffusion of single tungsten adatoms on the surfaces of rhombohedral clusters is studied by means of molecular dynamics and the embedded atom method. The energy barriers for the adatom diffusing across and along the step edge between a {110} facet and a neighboring {110} facet are calculated using the nudged elastic band method. We notice that the tungsten adatom diffusion across the step edge has a much higher barrier than that for face-centered cubic metal clusters. The result shows that diffusion from the {110} facet to a neighboring {110} facet could not take place at low temperatures. In addition, the calculated energy barrier for an adatom diffusing along the step edge is lower than that for an adatom on the flat (110) surface. The results show that the adatom could diffuse easily along the step edge, and could be trapped by the facet corner. Taking all of this evidence together, we infer that the {110} facet starts to grow from the facet corner, and then along the step edge, and finally toward the {110} facet center. So the tungsten rhombohedron can grow epitaxially along the {110} facet one facet at a time and the rhombohedron should be the stable structure for both large and small tungsten clusters.     

Enhanced piezoelectric-induced catalysis of SrTiO3 nanocrystal with well-defined facets under ultrasonic vibration

Facet engineering of nanocomposite has been confirmed to be an efficient strategy to accelerate their catalytic performances, but to improve their piezoelectric catalytic activities by facet engineering has been seldom reported. Herein, we developed a series of SrTiO₃ nanocrystals with exposed {0 0 1} facet, dominant {1 1 0} facet and co-exposed {0 0 1} and {1 1 0} facets, respectively, and firstly revealed its piezoelectric catalytic performance under ultrasonic vibration. Moreover, the relationship between piezoelectric-induced catalytic activity and facet-dependence of SrTiO₃ nanocrystal was disclosed for the first time. The SrTiO₃ nanocrystal with co-exposed {0 0 1} and {1 1 0} facets exhibited effectively enhanced piezoelectric catalytic activity by degrading Rhodamine B (RhB) under ultrasonic vibration, as compared to that of SrTiO₃ nanocrystals with exposed {0 0 1} facet and dominant {1 1 0} facet, respectively. In addition, trapping experiments and active species quantitative experiments confirmed that the co-exposed {0 0 1} and {1 1 0} facets were beneficial to produce O₂⁻ and OH with the generation rates of 8.3 and 132.2 μmol g⁻¹ h⁻¹, respectively. The OH radical played a dominant role in piezoelectric catalytic process. Finally, the piezoelectric catalysis mechanism of SrTiO₃ surface heterojunction was proposed based on a DFT study. This study presents an in-depth understanding of piezoelectric-induced catalytic of perovskite nanocrystals with exposed well-defined facets.     

Sectional area-dependent plasmonic shifting in the truncated process of silver nanoparticles: from cube to octahedron

A silver nanocube with sub-40 nm edge length was truncated by {111} planes and transformed into octahedron gradually. The extinction cross-section spectra corresponding to this process were studied by using the discrete dipole approximation (DDA) method. Non-monotonous shifting (blue shifts first and then red shifts) of the surface plasmon resonance (SPR) bands was observed. It was found that the sectional area of {111} facets could be a new and better factor to characterize the shape-dependent non-monotonous shifting of the SPR. The area of {111} facet increases while the SPR peak red shifts, whereas decreases while the SPR peak blue shifts. Similar results were also observed while an octahedron has been truncated into a smaller cube. The physical mechanism was illuminated by analyzing the local field distribution of the nanoparticles with different truncated ratios. The distance of the charge center was one of the most important reasons to affect the shift of SPR as the sectional area of {111} facet is changed. We believe the sectional area factor could be widely used to investigate the SPR shifting in other kinds of truncated process.     

Growth of nanorods and mesoscale stars prior to an orientation transition in thin Bi films on graphite

We report on the growth of unusual star shaped Bi islands and ordered arrays of nanorods on highly ordered pyrolitic graphite (HOPG) substrates. The rods and stars grow with {0 1 2}_Bi||{0 0 1}_HOPG and are preferentially aligned with the high symmetry directions of the substrate. As more Bi is deposited, the film undergoes a transition to the {0 0 1} orientation. These features are a result of a complex interplay between kinetics, thermodynamics, and the crystallography of the substrate and island material.     

Rh超薄膜在Mo(111)及W(111)上引起{110}小面再构的可能性

用第一性原理总能计算方法,计算了Mo和W表面吸附金属Rh薄膜前后[111],[110]方向的表面能.计算结果表明,清洁Mo和W的（111）面不会发生{111}小面再构,与实验观察一致,当Rh的覆盖厚度达到一物理单层后,Rh/Mo（111）仍不会形成{110}小面;面Rh/W（111）满足小面再构到{110}的热力学条件,在一定条件下可能形成{110}小面. 关键词：     

合成氨钌催化剂的晶体和形貌敏感性

哈伯-博施法合成氨反应是高温高压的耗能过程,因此降低该过程的能量消耗及开发温和条件下合成氨反应催化剂具有重要意义. 金属钌是合成氨反应中最有前途的催化剂之一,一直备受广泛关注. 确定金属钌催化剂的结构敏感性并提高其比质量活性是多相催化中亟待解决的重要问题. 氮气(N₂)活化是合成氨反应中的关键步骤. 本文通过第一性原理理论计算和微观动力学模拟方法系统研究了具有六方密排和面心立方晶体结构的钌催化剂上N₂活化过程和N₂解离反应速率. 理论计算研究表明,在六方密排Ru形貌中,{2130}晶面具有最高的N₂解离活性,其次是{0001}台阶面,它们比六方密排Ru其他表面上N₂解离反应速率高3个数量级以上;在面心立方Ru形貌中,{211}和{311}表面上N₂解离活性最高. 这些结果都表明台阶面/台阶位对氮气活化至关重要. 虽然六方密排Ru {2130}晶面具有最低的N₂解离能垒,然而由于面心立方Ru上可以暴露更高密度的活性位点,使得面心立方Ru比六方密排Ru具有更高的N₂转化速率. 本研究深入理解了N₂解离过程中,金属Ru 催化剂形貌和晶相结构敏感性,这为设计和优化高活性的合成氨Ru催化剂提供了理论基础.     

不同晶面银纳米晶高温熔化的各向异性

采用嵌入原子势, 使用分子动力学方法, 模拟研究了银纳米晶高温弛豫过程中的热稳定性和熔化机制, 并引入均方位移和稳定寿命来分析它的结构和形状的演化过程. 结果表明: 对于沿相互垂直{110}, {211}和{111}面切割形成的近正方体截面纳米晶, 高温弛豫熔化存在明显的各向异性行为; (112) 面热稳定性最低, 最易熔化, 其次是(110) 面, 热稳定性最高的是(111) 面, 最难熔化; 三个不同晶面的最外层和次外层原子的稳定寿命极短, 且三个不同晶面之间相差很小, 没有明显差异; 对于具有相同晶面指数的晶面, 第三层及其以内的稳定寿命较长, 且依次微量增长, 但不同晶面第三层及其以内的寿命相差明显.     

Ultrasound assisted deposition of highly stable self-assembled Bi2MoO6 nanoplates with selective crystal facet engineering as photoanode

The use of crystal facets of photocatalysts is well known as a promising strategy for the design of new photocatalysts with interesting physicochemical features for energy production applications. In this work, Bi₂MoO₆ thin films were synthesized by two methods, electrodeposition and sonoelectrodeposition. Preferential growth orientation depended on synthesis method. Results suggested that sonoelectrodeposition led to dominate the crystal facet {1 0 0} growth with self-assembled nanoplate morphologies while growth orientation in the {0 1 0} facet was dominant in electrodeposition in the absence of ultrasonic waves. As a highlight result, the {1 0 0} facet shows a smaller band gap, higher photocatalytic water splitting than the {0 1 0} facet. Efficient separation of charge pairs and long life time of photogenerated electrons was observed to be intrinsic features of the {1 0 0} facets. The higher charge transfer was confirmed by a higher photocurrent from linear sweep voltammetry and a smaller Nyquist radius arc. Ultrasound plays a key role in growth orientation and led to a production of homogeneous films with nanoplates which self-assembled together to form a flower-like structure. While in the absence of ultrasound the film has coral-like structure. Highly stable sonoelectrodeposited films exhibited incident photon-to-electron conversion efficiency (IPCE) of 22.4% at the specific wavelength of 500 nm. The sonoelectrodeposition method could act as a promising method for forming new films with specific crystal facet selection and developing as highly efficient photoanodes for PEC water splitting.     

Low-temperature and ambient-pressure synthesis and shape evolution of nanocrystalline pure, La-doped and Gd-doped CeO2

Nanocrystalline cuboidal ceria has been synthesized by low-temperature hydrothermal reaction of cerium nitrate hexahydrate with hexamethylene tetramine. The particles have been doped with La and Gd by adding aqueous solution of the nitrate salts of the metals to the reaction mixture. The pure and doped particles are cubic in crystal structure and 10-25 nm in size. The pure and La-doped ceria are cuboidal in morphology, whereas the Gd-doped particles are irregular in shape. High-resolution TEM imaging and image simulation indicates that atomic level steps are present on the particle surfaces. The particles are faceted parallel to the {1 1 1} and {1 0 0} crystallographic planes and a continuous switching takes place between the two possible surface facets. It appears that the surface energies of the {1 1 1} and {1 0 0} facets are quite similar in magnitude and the interplay of surface energy determines the particle shape. Chemically sensitive imaging and spectroscopy shows that the dopants are homogeneously distributed within the particles and that the oxidation state of Ce is a mixture of +3 and +4. No preferential segregation either of the dopant or the oxidation state was observed. However, since the facet switching does depend on the chemistry of the dopant, there must be an affect on the atomic scale.     

Solid-on-solid model of overlayer-induced faceting

A solid-on-solid model is proposed to describe faceting of bcc(1 1 1) metal surface induced by a metal overlayer. It is shown that the first-order phase transition occurs between faceted {2 1 1} or {1 1 0} and disordered phases. The ordered phases consist of large 3-sided pyramids with {2 1 1} facets or {1 1 0} facets. It is shown that the high-temperature disordered phase has not planar bcc(1 1 1) structure but faceted disordered structure. Hysteresis effects were observed when the system was warmed above the transition temperature and then cooled down. Temperature dependence of LEED patterns for faceted and disordered phase are calculated in kinematic approximation.     

Zener polaron ordering variants induced by A-site ordering in half-doped manganites

We have studied the magnetism of the half-doped charge ordered manganite YBaMn2O6. A formation of ferromagnetic plaquettes of four Mn atoms in the charge ordered phase below T_{CO} approximately 480 K is inferred from high temperature magnetic susceptibility data and the magnetic structure, as determined by neutron powder diffraction at T=1.5 K. The results indicate that new fourfold Mn paramagnetic units form between T_{N}相似文献   

On the 2D-3D transition in epitaxial thin film growth

The theory is based on the fact that the equilibrium concentration of single atoms adsorbed on the surface of a monolayer island placed on a foreign substrate such that the substrate-deposit interaction is weaker than the deposit-deposit interaction is higher than the equilibrium concentration of atoms adsorbed on the surface of the same island now placed on a substrate of the same material. This higher adatom concentration leads to 2D nucleation on top of the monolayer island. The difference of the above equilibrium adatom concentrations appears as a driving force for the process of transformation of the initial monolayer island into a 3D island by detachment of atoms from the first monolayer island edges and their subsequent attachment to the edges of the second layer nucleus. The kinetics of this process are studied in detail, the following two cases being considered. The first case consists of breaking up and agglomeration of an initially continuous film into 3D crystals upon heating. The second case consists of change of the growth mode from layer to island mode during the vapour deposition when the substrate temperature increases. Expressions for the critical temperatures for these two phenomena to occur are derived. It is shown that they depend strongly on the substrate orientation, the critical temperature being higher for the 〈111〉 orientation in comparison with the 〈110〉 orientation, if substrate and deposit with a fcc lattice are considered. The theoretical results are compared with experimental data for deposition of Au on Mo{110}, Cu on W{110} and W{100} and Fe on Cu{111}.     

Investigation into the kinetics of ordering of the Au4Zn alloy

The kinetics of ordering of the Au₄Zn alloy is investigated using X-ray diffractometry. It is established that the ordering and growth of domains inside the ordered phase are multistage processes. These processes are characterized by nucleation and growth of the ordered phase. The kinetics of growth of domains involves the nucleation and growth stages, as well as stages in which the crystal lattice axes have preferred or equally probable directions. The stages are more pronounced at low annealing temperatures. The duration of particular stages of the evolution of antiphase domains and their sizes depend on the annealing temperature.     

New two-fold integration transformation for the Wigner operator in phase space quantum mechanics and its relation to operator ordering

Using the Weyl ordering of operators expansion formula (Hong-Yi Fan, \emph{ J. Phys.} A {\bf 25} (1992) 3443) this paper finds a kind of two-fold integration transformation about the Wigner operator $\varDelta \left( q',p'\right) $ ($\mathrm{q}$-number transform) in phase space quantum mechanics, $\iint_{-\infty}^{\infty}\frac{{\rm d}p'{\rm d}q'}{\pi }\varDelta \left( q',p'\right) \e^{-2\i\left( p-p'\right) \left( q-q'\right) }=\delta \left( p-P\right) \delta \left( q-Q\right),$ and its inverse% $ \iint_{-\infty}^{\infty}{\rm d}q{\rm d}p\delta \left( p-P\right) \delta \left( q-Q\right) \e^{2\i\left( p-p'\right) \left( q-q'\right) }=\varDelta \left( q',p'\right),$ where $Q,$ $P$ are the coordinate and momentum operators, respectively. We apply it to study mutual converting formulae among $Q$--$P$ ordering, $P$--$Q$ ordering and Weyl ordering of operators. In this way, the contents of phase space quantum mechanics can be enriched. The formula of the Weyl ordering of operators expansion and the technique of integration within the Weyl ordered product of operators are used in this discussion.     

Grain-boundary faceting at a = 3, [110]/{112} grain boundary in a cubic zirconia bicrystal

The atomic structure of a = 3, [110]/{112} grain boundary in a yttria-stabilized cubic zirconia bicrystal has been investigated by high-resolution transmission electron microscopy (HRTEM). It was found that the grain boundary migrated to form periodic facets, although the bicrystal was initially joined so as to have the symmetric boundary plane of {112}. The faceted boundary planes were indexed as {111}/{115}. The structure of the {111}/{115} grain boundary was composed of an alternate array of two types of structure unit: {112}- and {111}-type structure units. HRTEM observations combined with lattice statics calculations verified that both crystals were relatively shifted by (α/4)[110] along the rotation axis to form a stable grain-boundary structure. A weak-beam dark-field image revealed that there was a periodic array of dislocations along the grain boundary. The grain-boundary dislocations were considered to be introduced by the slight misorientation from the perfect = 3 orientation. The fact that the periodicity of the facets corresponded to that of the grain-boundary dislocations must indicate that the introduction of the grain-boundary dislocations is closely related to the periodicity of the facets. An atomic flipping model has been proposed for the facet growth from the initial = 3, {112} grain boundary.     

铂修饰的{001}面暴露的二氧化钛纳米片阵列的制备和光催化性能

采用有机溶剂热法在FTO衬底上制备{001}面暴露的单晶锐钛矿相TiO₂纳米片阵列,通过FESEM和XRD研究样品的形貌和晶体结构. 与水热法制备的纳米片阵列相比,有机溶剂热法制备的样品取向性更好. 采用光沉积方法在纳米片阵列上沉积Pt,所得到的Pt纳米颗粒粒径更为均匀,并且更容易沉积在{001}面上. 所负载的Pt 纳米颗粒增强了TiO₂纳米片的光吸收性能,同时大大减弱了光致发光强度. 在光催化性能测试中,具有最优负载量的样品催化性能提高了一倍. 与传统的Pt负载相比,{001}面的最优负载量显得相当小,这可能源于高活性{001}面的原子结构.