Y掺杂空位石墨烯对NO及CO气体表面吸附的第一性原理研究

摘　要：基于第一性原理的计算方法,建立了本征石墨烯、空位石墨烯及钇( Y)掺杂空位石墨烯模型,并计算了CO、NO在三类石墨烯表面的吸附过程. 从表面能、吸附结构、吸附能和态密度四个方面进行分析讨论,研究掺杂Y对CO、NO气体吸附性能的影响. 结果表明：CO、NO与本征石墨烯之间的吸附为弱的物理吸附,掺杂Y后增强了材料表面对CO、NO的吸附效果,最大吸附能分别为7.414eV、6.702eV,属于化学吸附;掺杂Y使空位石墨烯费米能级附近有了更多的活跃电子,其吸附NO后体系由半金属转变为金属特性,该特性能为开发更加优良的石墨烯气敏材料提供理论支持.     

Ferromagnetism induced by intrinsic defects and nitrogen substitution in SnO2 nanotube

The possibilities of magnetism induced by intrinsic defects and nitrogen substitution in (5,5) single-wall SnO₂ nanotube are investigated by ab initio calculations. The calculated results indicate that a stoichiometric SnO₂ nanotube is nonmagnetic. The tin (Sn) vacancy can induce the magnetic moments rather than oxygen vacancy, which is originated from the polarization of O 2p electrons. A couple of tin vacancies can lead to the ferromagnetic coupling. A nitrogen substitution for oxygen also produces magnetic moments. When substituting two nitrogen atoms, the characteristics of exchange coupling depend upon the distance of two nitrogen atoms. The longer distance of two nitrogen atoms prefers the ferromagnetic coupling, whereas the short distance leads to the antiferromagnetic coupling.     

A stochastic theory for clustering of quenched-in vacancies—2. A solvable model

The model introduced for clustering of quenched-in vacancies in the first part of this series of papers is considered. Using a generating function, the rate equations are converted into a first order partial differential equation for the generating function coupled to a differential equation for the rate of change of the concentration of single vacancy units. A decoupling scheme is effected which gives an exponentially decaying solution with a very short time constant for the concentration of single vacancy units. The differential equation for the generating function is solved for times larger than the time required for the concentration of single vacancy units to reach its asymptotic value. The distribution for the size of the clusters is obtained by inverting the solution thus obtained. Several results that follow are shown to be in reasonably good agreement with the experimental results.     

Durable Electrocatalytic Reduction of Nitrate to Ammonia over Defective Pseudobrookite Fe2TiO5 Nanofibers with Abundant Oxygen Vacancies

We propose the pseudobrookite Fe₂TiO₅ nanofiber with abundant oxygen vacancies as a new electrocatalyst to ambiently reduce nitrate to ammonia. Such catalyst achieves a large NH₃ yield of 0.73 mmol h⁻¹ mg⁻¹_cat. and a high Faradaic Efficiency (FE) of 87.6 % in phosphate buffer saline solution with 0.1 M NaNO₃, which is lifted to 1.36 mmol h⁻¹ mg⁻¹_cat. and 96.06 % at −0.9 V vs. RHE for nitrite conversion to ammonia in 0.1 M NaNO₂. It also shows excellent electrochemical durability and structural stability. Theoretical calculation reveals the enhanced conductivity of this catalyst and an extremely low free energy of −0.28 eV for nitrate adsorption at the presence of vacant oxygen.     

Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.     

Armchair型石墨纳米带的电子结构和输运性质

利用第一性原理的电子结构和输运性质计算方法, 研究了扶手椅(armchair)型单层石墨纳米带(具有锯齿边缘)的电子结构和输运性质及其边缘空位缺陷效应. 研究发现, 完整边缘的扶手椅型石墨纳米带是典型的金属性纳米带, 边缘空位缺陷的存在对扶手椅型纳米带能带结构有一定的影响,但并不彻底改变其金属性特征.     

ZnSe掺Cu与Zn空位缺陷的稳定性、电子结构与光学性质

采用基于密度泛函理论框架下的第一性原理平面波超软雁势方法, 对ZnSe闪锌矿结构本体、掺入p型杂质Cu(Zn_0.875Cu_0.125Se)及Zn空位(Zn_0.875Se)超晶胞进行结构优化处理. 计算并详细分析了缺陷体系的形成能和三种体系下ZnSe材料的态密度、能带结构、集居数、介电和吸收光谱. 结果表明: 在Zn空位与Cu掺杂ZnSe体系中, 由于空位及杂质能级的引入, 禁带宽度有所减小, 吸收光谱产生红移; 单空位缺陷结构不易形成, Zn_0.875Se结构不稳定, Cu掺杂ZnSe结构相对更稳定.     

The properties and structures of the mono- and the di- vacancy in Cu crystal

The structures and energies of formation and migration of the mono- and di-vacancy in Cu crystal have been described and calculated with modified analytical embedded atom method (MAEAM). The lattice relaxation is considered with molecular dynamics (MD) method at T=0 K. The results show the FN di-vacancy is the most stable and likely occurs in practice from the energy minimization. Compared with the mono-vacancy, the formation energy of the FN di-vacancy is higher than that of a mono-vacancy, but lower than that of two isolated mono-vacancy. The preferred migration mechanism of the FN di-vacancy is multi-jump of either vacancy (rotating the di-vacancy). The calculated migration energy of the FN di-vacancy is lower than that of a mono-vacancy, so the FN di-vacancy is easier to migrate. All of the calculated results are in good agreement with the experimental values.     

Evidence of formation of tetravacancies in uniformly oxygen irradiated n-type silicon

High purity n-type silicon single crystal with resistivity in the order of 4000 Ω cm has been irradiated with high-energy oxygen ions at room temperature up to a fluence of 5E15 ions/cm². The energy of the beam was varied from 3 to 140 MeV using a rotating degrader to achieve a depthwise near-uniform implantation profile. Radiation induced defects and their dynamics have been studied using positron annihilation spectroscopy along with isochronal annealing up to 700 °C in steps of 50 °C for 30 min. After annealing the sample at 200 °C for 30 min, formation of silicon tetravacancies has been noticed. The formation of the tetravacancies was found to be due to agglomeration of divacancies present in the irradiated sample. An experimentally obtained positron lifetime value of 338±10 ps has been reported for silicon tetravacancies, which has a very close agreement with the value obtained from recent theoretical calculations. The tetravacancies were found to dissociate into trivacancy clusters upon further annealing. The trivacancies thus obtained were observed to agglomerate beyond 400 °C to form larger defect clusters. Finally, all the defects were found to anneal out after annealing the sample at 650 °C.