α钛富氧层增厚动力学模型

为了实现在工业化生产中对α钛富氧层厚度预测和控制,通过实验研究α钛富氧层在高温空气环境中的形成及增厚过程,讨论热处理温度和时间的影响作用,建立高温(750~850℃)空气环境下关于温度、时间的富氧层增厚动力学模型。结果表明:当恒温热处理温度为750~850℃时,α钛富氧层厚度x与保温时间t0.5呈正比例关系,且升高热处理温度可显著提高富氧层增厚速度。在此温度范围内,氧原子的扩散激活能约为203473 J/mol,计算曲线与实验数据吻合性较好。结合文献中已有的扩散系数方程和实验测得的富氧层厚度数据,推导得到5个富氧层增厚动力学方程,其中3个方程的计算曲线与实验数据吻合性较好,可为实际生产中预估富氧层厚度提供理论支持。     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.     

The Electron–Phonon Interaction of Low-Dimensional and Multi-Dimensional Materials from He Atom Scattering

Atom scattering is becoming recognized as a sensitive probe of the electron–phonon interaction parameter λ at metal and metal-overlayer surfaces. Here, the theory is developed, linking λ to the thermal attenuation of atom scattering spectra (in particular, the Debye–Waller factor), to conducting materials of different dimensions, from quasi-1D systems such as W(110):H(1 × 1) and Bi(114), to quasi-2D layered chalcogenides, and high-dimensional surfaces such as quasicrystalline 2ML-Ba(0001)/Cu(001) and d-AlNiCo(00001). Values of λ obtained using He atoms compare favorably with known values for the bulk materials. The corresponding analysis indicates in addition, the number of layers contributing to the electron–phonon interaction, which is measured in an atom surface collision.     

Single transition metal atom catalysts on Ti2CN2 for efficient CO2 reduction reaction

Electrochemical CO₂ reduction reaction (CO₂RR) is an efficient way in the utilization of CO₂. In this work, single transition-metal (TM) atom (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) anchored on two-dimensional (2D) Ti₂CN₂ are designed for CO₂RR using density-functional-theory (DFT) calculation. We show that Ti₂CN₂ serves as an excellent substrate to support single atom catalysts (SACs), compared to Ti₂CO₂ and Ti₂CF₂. We find that the Sc, Ti and V supported on Ti₂CN₂ show high catalytic activities to produce CO with a low overpotential of 0.37, 0.27, and 0.23 eV, respectively. Differently, the Mn and Fe on Ti₂CN₂ are catalytically active for the production of HCOOH with a low overpotential of 0.32 and 0.43 eV, respectively. We further show that the negatively charged TM-Ti₂CN₂ can capture and activate CO₂ more effectively, and the catalytic activity and selectivity can be significantly tuned by injecting extra electrons.     

Anchoring single Pt atoms on hollow Ag3VO4 spheres for improved activity towards photocatalytic H2 evolution reaction

The high cost of noble metal catalysts has been a great bottleneck for the catalyst industry. Using the noble metal at a single-atom level for catalytic applications could dramatically decrease the cost. The impacts of single Pt atoms on the photocatalytic performance of Ag₃VO₄ have been investigated and reported. In this report, single Pt atoms were anchored on the surface of Ag₃VO₄ (AVO) as a cocatalyst, and the resultant composite photocatalyst has been studied for photocatalytic H₂ production from water driven by visible light. The as-prepared AVO particles are hollow nanospheres in the monoclinic phase with a bandgap of 2.20 eV. The light absorption edge of AVO/Pt is slightly red-shifted compared to that of the pristine AVO, indicating more visible light absorption of AVO/Pt. The XPS peaks of Ag, V, and Pt exhibit a significant shift after AVO and Pt get into contact, suggesting the strong interaction between the surface Ag and V atoms, and single Pt atoms. After 3-h illumination, the photocatalytic H₂ evolution amount from AVO/Pt is improved up to 1400 μmol, which is 2.8 times that on the bare AVO. Such efficient photocatalytic H₂ evolution on AVO/Pt is still maintained after five reaction cycles. The better photocatalytic performance of AVO/Pt has been attributed to the more efficient visible light utilization and the lower interfacial charge transfer resistance, as demonstrated in the DRS and EIS spectra. The presence of the surface Pt atoms also leads to a higher amount of reactive radicals, which could efficiently promote the surface redox reactions.     

Development of a fast atom beam gun for surface-activated bonding

Surface-activated bonding (SAB), also called room-temperature bonding, is used in three-dimensional integration technology for semiconductor devices. An Ar fast atom beam (FAB) is used for SAB. However, conventional FAB guns must be replaced after hundreds of minutes of irradiation because carbon abrasion powders are generated by Ar ions sputtering in the gun. Therefore, this study develops a novel FAB gun with improved lifetime. The proposed FAB gun applies magnetic fields to guide Ar ions to reduce sputtering in the gun and improve irradiation efficiency. The proposed FAB gun indicates the possibility of improving gun lifetime.     

硼含量对有序态Ni3Fe合金中氢扩散的影响

采用阴极充氢和真空拉伸方法,研究了硼含量对氢原子在有序态Ni_3Fe合金中扩散的影响。结果表明,当合金中硼含量C_B≤0.06%(质量分数)时,氢原子在有序态Ni_3Fe合金中的扩散系数随C_B的增加而逐渐降低,而扩散激活能逐渐增大。当C_B0.06%后,氢原子的扩散系数随C_B的增加而变化很小,而扩散激活能略有减小。原子探针层析方法证实了硼原子在有序态Ni_3Fe合金中晶界处发生偏聚。对比研究硼含量对有序态Ni_3Fe合金中氢扩散系数及对合金在氢气环境中氢脆因子的作用,确认硼原子降低有序态Ni_3Fe合金在氢气环境中的氢脆敏感性的机理,是硼原子降低了氢原子在合金中的沿晶扩散系数。     

Quantification of grain boundary defect chemistry in a mixed proton-electron conducting oxide composite

Dual phase oxide membranes have shown promising hydrogen permeation fluxes in syngas applications due to their high mixed proton electron conduction (MPEC). However, the conductivity of grain boundaries can be many orders of magnitude lower than that of the bulk and so limits the total conductivity and hydrogen permeation. In this study, the three-dimensional nanoscale oxygen and cation distributions around grain and phase boundaries in a BaCe_0.8Y_0.2O_3-δ-Ce_0.8Y_0.2O_2-δ (BCY-YDC) membrane were quantified by atom probe tomography (APT) and related to average grain boundary conductivity measured by electrochemical impedance spectroscopy (EIS). Segregation varied among the general high-angle grain boundaries analyzed, but no trend from orientation analysis was determined. Correlative APT and electron energy loss spectroscopy (EELS) of one YDC grain boundary revealed composition and cerium valence information, respectively, allowing for the determination of vacancies at the grain boundary. While a specific MPEC membrane is characterized, the results are relevant to proton and electron conduction in a number of technologically important ceramics.