Pt掺杂MoSe_(2)吸附CF_(3)I分解组分的第一性原理研究

CF_(3)I作为SF_(6)最具潜力的新型环保绝缘气体,在电气设备出现局部放电、过热等缺陷故障时,会产生C_(2)F_(6)和C_(2)F_(4)等强温室气体,为确保电力设备稳定运行,有必要对CF_(3)I典型分解组分吸附去除.本文基于密度泛函理论的第一性原理计算方法,通过吸附能、吸附距离、电荷转移和态密度等吸附指标,分别探究了不同数量Pt掺杂MoSe_(2)对C_(2)F_(6)和C_(2)F_(4)气体分子的吸附性能.研究结果表明:不同数量Pt掺杂在MoSe_(2)表面均存在稳定的掺杂结构,且相较本征MoSe_(2),Pt掺杂后的MoSe_(2)导电性均得到了有效增强;Pt掺杂MoSe_(2)对CF_(3)I分解组分的吸附效果:Pt_(2)-MoSe_(2)>Pt-MoSe_(2)>Pt_(3)-MoSe_(2)>Pt_(4)-MoSe_(2),且Pt_(2)-MoSe_(2)对C_(2)F_(4)表现出强烈的化学吸附作用,而对C_(2)F_(6)为弱物理吸附;Pt_(2)-MoSe_(2)对CF_(3)I分解组分具有选择吸附性,有望用作CF_(3)I典型分解组分C_(2)F_(4)的吸附去除材料.     

Pt掺杂MoSe2吸附CF3I分解组分的第一性原理研究

CF₃I作为SF₆最具潜力的新型环保绝缘气体,在电气设备出现局部放电、过热等缺陷故障时,会产生C₂F₆和C₂F₄等强温室气体,为确保电力设备稳定运行,有必要对CF₃I典型分解组分吸附去除.本文基于密度泛函理论的第一性原理计算方法,通过吸附能、吸附距离、电荷转移和态密度等吸附指标,分别探究了不同数量Pt掺杂MoSe₂对C₂F₆和C₂F₄气体分子的吸附性能.研究结果表明：不同数量Pt掺杂在MoSe₂表面均存在稳定的掺杂结构,且相较本征MoSe₂,Pt掺杂后的MoSe₂导电性均得到了有效增强;Pt掺杂MoSe₂对CF₃I分解组分的吸附效果：Pt₂-MoSe₂>Pt-MoSe<...     

SF_6气体及其衍生物的红外光谱分析

SF6气体大量应用于气体绝缘组合电器(GIS)中。通过化学方法检测SF6气体及其衍生物是检测GIS设备故障的一种重要方法。该文采用红外光谱技术分析了三种情况下的GIS设备内SF6气体组成情况,得出S2F10气体含量可以用来分析GIS故障原因是否为强火花或者电弧放电引起;CF4气体可以用来表征GIS设备内绝缘气体的绝缘状态。另外,研究表明,GIS设备在线运行时,绝缘气体气室密封失效、造成气体泄漏,引入新的气体杂质的问题比较严重。所以在进行GIS设备维护工作时,绝缘气室的密封维护工作十分重要。文章在研究GIS设备绝缘气体SF6红外谱图的基础之上提出了建立基于红外光谱技术的GIS设备故障诊断专家系统的意见。     

Si改性MoS2对g3环保气体典型分解组分的吸附特性研究

g3(green gas for gird)环保气体(C₄F₇N/CO₂混合)作为SF₆最具潜力的新型环保绝缘替代气体,近几年来受到了广泛关注.通过分析g3气体绝缘组合开关设备中的分解组分来检测局部放电、过热等缺陷故障,对于电力设备运行状态的评估和诊断具有重要作用.本文提出利用Si原子掺杂改性来提高MoS₂的气敏和吸附性能,并基于密度泛函理论(DFT)的计算方法,通过吸附能、电荷转移、态密度和局部态密度等参数指标,探究了本征MoS₂、Si改性MoS₂(Si-MoS₂)对g3气体典型分解组分—COF₂、CF₄、CF₃CN的吸附气敏机理.分析表明Si原子在MoS₂表面具有稳定的掺杂结构,相比本征MoS₂,Si原子改性之后的MoS₂的导电性得到了有效增强;Si-MoS₂     

基于密度泛函理论的SF6分解特征组分激光拉曼特征频谱研究

六氟化硫(SF6)分解特征组分检测是判断气体绝缘设备早期潜伏性故障较有效的方法之一,通过监测分解特征组分的类型和浓度能够有效评估电气设备的运行状态,从而避免绝缘突发性事故。拉曼频谱分析技术可实现单一波长激光对气体样品进行无损检测,对SF6分解特征组分检测具有优异的适用性和高效性。针对4种SF6分解典型特征组分,以密度泛函理论(DFT)中的B3LYP方法建立了气体分子模型,采用6-311G(2df,p)基组对分子模型进行优化和拉曼频移特征仿真。同时,基于搭建的拉曼光谱实验平台,对相同含量的4种特征组分实现拉曼特征频谱检测。仿真结果表明密度泛函计算值和实测值与NIST标准值间具有良好的相关性,计算值中CF_(4)、CO、H_(2)S、SO_(2)的特征峰分别为908.97、2 221.11、2 688.82、1 175.24 cm^(-1),为用拉曼光谱实现SF6分解特征组分的定性和定量分析奠定了基础。     

ClF3O和环氧丙烷反应的理论研究

应用密度泛函理论对 ClF3 O 和环氧丙烷的反应机理进行了研究。在 B3PW91/6-31++G(d ,p )水平上优化了各驻点(反应物、中间体、过渡态和产物)的几何构型,并计算了它们的振动频率和零点振动能。采用 CCSD(T)/6-31++G(d ,p )//B3PW91/6-3l++G(d ,p )单点能计算方法求得各物质的能量,并做零点能校正。计算结果表明,ClF3 O 与 C3 H 6 O 可经过不同的反应路径,引发 C3 H 5 O 自由基和 ClOF2自由基生成环氧丙醇和三氟化氯,其中,位于 ClF3 O 周向位置的 F 原子与 C3 H 6 O 的 C(7)上与 CH 3异侧的 H(9)原子结合的活化能最低,仅15.63 kJ/mo1;ClF3 O 与 C3 H 6 O 反应生成的 C3 H 5 O 自由基和 ClOF2自由基继续反应,经过不同反应路径生成 C3 H 4 O、ClOF 和 HF,其中,ClOF2中的 F 原子和 C3 H 5 O 中的 H(2)或 H(4)原子结合是无能垒的过程。整个反应的主要路径为 C3 H 6 O+ClF3→O→TS12 P4(C3 H 5 O+HF+ClOF2→) P12(CH 2 CHCHO+2 HF+ClOF)。     

氟丙烯在高温下的热稳定性

用单脉冲激波管研究了全氟丙烯C3F6的分解。使用H2作为清扫剂。产物包括CH4、C2F4、CF3H和C2F3H,作为对断键反应过程的指示。C3F6的断键反应为 C3F6CF3+C2F3 （1） 得到其速率常数表达式为 k（C3F6CF3+C2F3)=10(17.4±0.2)exp-(355300±8360)/(RT)s-1 温度范围为1090K相似文献   

ClF_3O和环氧丙烷反应的理论研究（英文）

应用密度泛函理论对ClF3O和环氧丙烷的反应机理进行了研究。在B3PW91/6-31++G(d,p)水平上优化了各驻点(反应物、中间体、过渡态和产物)的几何构型,并计算了它们的振动频率和零点振动能。采用CCSD(T)/6-31++G(d,p)//B3PW91/6-3l++G(d,p)单点能计算方法求得各物质的能量,并做零点能校正。计算结果表明,ClF3O与C3H6O可经过不同的反应路径,引发C3H5O自由基和ClOF2自由基生成环氧丙醇和三氟化氯,其中,位于ClF3O周向位置的F原子与C3H6O的C(7)上与CH3异侧的H(9)原子结合的活化能最低,仅15.63kJ/mo1;ClF3O与C3H6O反应生成的C3H5O自由基和ClOF2自由基继续反应,经过不同反应路径生成C3H4O、ClOF和HF,其中,ClOF2中的F原子和C3H5O中的H(2)或H(4)原子结合是无能垒的过程。整个反应的主要路径为C3H6O+ClF3O→TS12→P4(C3H5O+HF+ClOF2)→P12(CH2CHCHO+2HF+ClOF)。     

应用扩展的2CJL模型确定微观势能参数

本文应用扩展的2CLJ势能模型优化了若干线型分子的微观势能参数.该模型包含了二分子间长程静电和诱导作用,同时也考虑了极性分子偶极矩与分子轴不平行的情况.通过第二维里系数的实验数据回归获得简单线型分子N2、O2、Cl2、F2、CO、NO、C2H6和C2F6的硬球直径σ和阱深ε.强极性分子CH3Cl、CH3F、CH3CF3、CF3CH2F和CH3CHF2的第二维里系数运用改进的混合规则计算得到,计算结果与实验数据符合很好.     

Li修饰的C_6分子对H_2O的吸附研究

采用密度泛函理论中的广义梯度近似研究C6Li吸附H2O分子并将之进行分解的催化过程.几何优化发现:Li原子最稳定的吸附位置是位于C原子顶位上方.研究表明,第一个H2O分子吸附在C6Li上需要克服1.77 eV的能量势垒,然后分解为H和OH且与Li原子成键.当吸附第二个H2O分子时,第二个H2O分子需要克服1.2 eV的能量势垒分解为H和OH,其中H与Li原子上的H原子结合成H2,OH则替代Li原子上的H结合在Li原子上.因此C6Li可以作为催化剂将H2O分子进行分解得到H2.分析可知:C6Li主要是通过Li原子与H2O之间形成的偶极矩作用来吸附H2O分子,与C60Li12的储氢机制类似.研究结果可为储氢材料的制备提供一个新的思路.     

Adsorption behaviour of SO2 and SOF2 gas on Rh-doped BNNT: a DFT study

Abstract

As the insulating medium, SF₆ is widely used in gas insulation equipment. Partial discharge and local overheating can cause the decomposition of SF₆, resulting in a decrease in insulation strength of the equipment. The detection of SF₆ decomposition gas can be used for on-line insulation detection of gas insulation equipment in electric power industry. In order to develop a new sensor gas sensing material for gas detecting. In this work, based on the first-principles density functional calculation (DFT) method of DMol³, the adsorption of SF₆ decomposition gas on (5,0) Z-type Rh-BNNT in different ways was explored. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. The results show that the adsorption strength between SO₂ molecule with Rh-BNNT is larger than with SOF₂ molecule, combined with desorption time, theoretically predicts Rh -BNNT have the potential to be a material for SO₂ gas sensors.     

电荷调控下Ti3C2O2和V2CO2吸附CH4的第一性原理计算

本文采用第一性原理计算首先研究了Ti3C2O2和V2CO2与CH4气体分子之间的相互作用,发现Ti3C2O2和V2CO2对CH4的吸附较弱属于物理吸附,不适宜用作探测CH4。在此基础上研究了电荷调控下CH4气体分子与Ti3C2O2和V2CO2之间的相互作用。结果表明：随着体系电荷态的增加,Ti3C2O2和V2CO2对CH4气体分子的吸附作用逐渐增加变为化学吸附。当体系电荷态大于或等于-2时,CH4气体分子在Ti3C2O2和V2CO2表面可以被有效捕获。撤去电荷后,Ti3C2O2、V2CO2与CH4气体分子之间的吸附恢复至物理吸附,CH4气体分子易脱附。因此,通过调控Ti3C2O2和V2CO2的电荷态,可以简单地实现CH4的捕获与释放。Ti3C2O2和V2CO2有望成为CH4探测或捕获材料。     

Cantilever enhanced photoacoustic spectrometry: Quantitative analysis of the trace H2S produced by SF6 decomposition

As one of the key characteristic components that result from sulfur hexafluoride (SF₆) decomposition in SF₆ gas-insulated equipment, hydrogen sulfide (H₂S) can reflect the severity of the internal insulation faults and indicate whether or not such faults involve solid insulation material effectively. The decomposition of SF₆ and its reaction with other impurities to form H₂S are simulated in this study via Materials Studio. The simulation verifies that H₂S is generated only when serious faults occur in the equipment; thus, the online monitoring of the trace H₂S is highly necessary. To achieve a high detection accuracy and avoid cross interference, the spectral line R (8) of the H₂S ν₁ + ν₂ + ν₃ co-frequency absorption band is taken as the absorption line for the gas detection by online simulation based on the HITRAN on the Web. In addition, this study develops a cantilever-enhanced photoacoustic spectrometry trace gas detection platform and conducts experimental research on the quantitative detection of trace H₂S/SF₆ and H₂S/N₂. Experimental results show that the detection sensitivity of the detection platform to trace H₂S under the background gas N₂ and SF₆ is 0.84 and 1.75 μL/L, respectively, and a strong linear relationship exists between the trace H₂S concentration and its corresponding PA signal. Moreover, based on both the theoretical simulation and experiment, the influence of temperature and pressure on the detection platform is discussed and analyzed. The results indicate that the change in the PA signal amplitude decreases with an increase in the pressure or temperature of the PA cell, and the detection platform is more sensitive to pressure.     

First-principle study on the structural and electronic properties of H2S and SO2 adsorption on Pd-doped MoS2 monolayer

The partial discharge in SF₆-insulated equipment produces characteristic decomposition products: SO₂ and H₂S. The characteristic decomposition products vastly speed up the process of discharge faults. Based on density functional theory (DFT) calculation, single layer Pd-doped MoS₂ (Pd-MoS₂) is adopted as the adsorbent to adsorb SO₂ and H₂S to ensure the operational stability of SF₆-insulated equipment. The adsorption energy, charge transfer and structure parameters of SF₆, H₂S, and SO₂ adsorption on the Pd-MoS₂ monolayer are analysed to find the most stable adsorption structure. The molecular orbital theory, total density of states and partial density of states are studied to analyse the adsorption mechanism. The results show that Pd-MoS₂ adsorbent possesses high catalytic activity and excellent adsorption performance to H₂S and SO₂ by strong chemical adsorption. This study is of great significance to ensure the operational stability of SF6-insulated equipment by removing these characteristic decomposition products.     

Adsorption Regularity and Characteristics of sp~3-Hybridized Gas Molecules on Anatase TiO_2(101) Surface

We report the anatase titanium dioxide(101) surface adsorption of sp~3-hybridized gas molecules,including NH_3,H_2O and CH_4,using first-principles plane-wave ultrasoft pseudopotential based on the density functional theory.The results show that it is much easier for a surface with oxygen vacancies to adsorb gas molecules than it is for a surface without oxygen vacancies.The main factor affecting adsorption stability and energy is the polarizability of molecules,and adsorption is induced by surface oxygen vacancies of the negatively charged center.The analyses of state densities and charge population show that charge transfer occurs at the molecule surface upon adsorption and that the number of transferred charge reduces in the order of N,O and C.Moreover,the adsorption method is chemical adsorption,and adsorption stability decreases in the order of NH_3,H_2O and CH_4.Analyses of absorption and reflectance spectra reveal that after absorbed CH_4 and H_2O,compared with the surface with oxygen vacancy,the optical properties of materials surface,including its absorption coefficients and reflectivity index,have slight changes,however,absorption coefficient and reflectivity would greatly increase after NH_3 adsorption.These findings illustrate that anatase titanium dioxide(101) surface is extremely sensitive to NH_3.     

Impurities Effect on e-beam-excited KrF Laser

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O2在Si掺杂石墨烯上吸附与活化

采用包含色散力校正的密度泛函理论方法(DFT-D)研究了O2在Si掺杂石墨烯(Si-Gra)上吸附与活化. 研究结果表明: 1) 与纯净石墨烯相比, Si掺杂极大的增强了石墨烯对O2的吸附能力. O2的最稳定吸附构型是以Side-on 模式吸附在掺杂的Si的顶位, 形成O-Si-O三元环. 次稳定吸附构型是与Si及近邻的一个C形成O-Si-C-O四元环结构. 两个吸附构型对应的吸附能分别为-2.40和-1.93 eV; 2) O2有两种分解路径: 直接分解路径(势垒为0.53 eV)和整体扩散后的分解路径(势垒为0.81 eV); 3) 分解之后的两个O原子分别吸附在Si的顶位和相邻碳环的两个碳原子的桥位; 4) 电子结构分析表明吸附的O2从Si-Gra获得较多电荷, 从而被活化. 总之, Si-Gra具有较强的催化氧气还原能力, 是一种潜在的良好的非金属氧还原催化剂.     

O_2在Si掺杂石墨烯上吸附与活化

采用包含色散力校正的密度泛函理论方法(DFT-D)研究了O2在Si掺杂石墨烯(Si-Gra)上吸附与活化.研究结果表明:1)与纯净石墨烯相比,Si掺杂极大的增强了石墨烯对O2的吸附能力.O2的最稳定吸附构型是以Side-on模式吸附在掺杂的Si的顶位,形成O-Si-O三元环.次稳定吸附构型是与Si及近邻的一个C形成O-Si-C-O四元环结构.两个吸附构型对应的吸附能分别为-2.40和-1.93eV;2)O2有两种分解路径:直接分解路径(势垒为0.53eV)和整体扩散后的分解路径(势垒为0.81eV);3)分解之后的两个O原子分别吸附在Si的顶位和相邻碳环的两个碳原子的桥位;4)电子结构分析表明吸附的O2从Si-Gra获得较多电荷,从而被活化.总之,Si-Gra具有较强的催化氧气还原能力,是一种潜在的良好的非金属氧还原催化剂.