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.     

羟基碳纳米管吸附SF6放电分解组分的DFT计算

本文根据密度泛函理论(density functional theory , DFT), 采用MS分子动力学仿真软件对羟基修饰的单壁碳纳米管(SWNT-OH) 吸附SF₆局部放电分解的四种主要组分SOF₂, SO₂F₂, SO₂和CF₄进行了详细的理论计算, 通过分析气体分子和SWNT-OH的前线轨道, 吸附过程中吸附能、电荷转移量和电子态密度的情况, 以及吸附前后SWNT-OH能隙的变化, 评判了SWNT-OH对气体分子的敏感性和选择性, 给出了SWNT-OH是否可以制备气体传感器检测SF₆局部放电分解组分的理论依据.     

Adsorption behaviour of SF6 decomposed species onto Pd4-decorated single-walled CNT: a DFT study

Metal nanocluster decorated single-walled carbon nanotubes (SWCNT) with improved adsorption behaviour towards gaseous molecules compared with intrinsic ones, have been widely accepted as a workable media for gas interaction due to their strong catalysis. In this work, Pd₄ cluster is determined as a catalytic centre to theoretically study the adsorption property of Pd₄-decorated SWCNT upon SF₆ decomposed species. Results indicate that Pd₄-SWCNT possessing good responses and sensitivities towards three composed species of SF₆ could realise selective detection for them according to the different conductivity changes resulting from the varying adsorption ability. The response of Pd₄-SWCNT upon three molecules in order is SOF₂ > H₂S > SO₂, and the conductivity of the proposed material is about to increase in SOF₂ and H₂S systems, while declining in SO₂ system. Such conclusions would be helpful for experimentalists to explore novel SWCNT-based sensors in evaluating the operating state of SF₆ insulation devices.     

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.     

CuO掺杂C3N对C5F10O分解组分吸附性能的第一性原理研究

全氟五碳酮（C5F10O）作为可替代SF6的新型环保绝缘气体已被投入到实际应用中. 在绝缘设备内部不可避免的会发生局部放电等故障,造成C5F10O绝缘气体分解产生弱绝缘性能甚至剧毒的分解组分,为保证绝缘设备的安全运行,在不影响气敏传感器正常检测绝缘设备内部故障的情况下,需对这些分解组分进行有选择地吸附去除. 新型类石墨烯C3N材料在气体吸附领域具有良好的应用前景,文中基于第一性原理计算了CuO分子掺杂C3N对主要分解组分CF4、C2F6及剧毒产物CF2O、HF的吸附过程,计算并分析了各分解组分吸附时的吸附能、态密度、电荷转移量、差分电荷密度以及不同环境温度下的恢复时间. 结果表明,CuO-C3N对HF表现出良好的吸附性,CF2O次之,但其无法吸附CF4与C2F6,因此CuO-C3N可以作为一种高性能的气体吸附剂对C5F10O绝缘设备内的剧毒分解组分HF进行吸附去除.     

Theoretical study on the interaction of heptafluoro-iso-butyronitrile decomposition products with Al (1 1 1)

Seeking environmentally friendly gas-insulated medium has become a research hotspot in recent years. At present, C₃F₇CN (Heptafluoro-iso-butyronitrile) is considered to be a potential SF₆ environment-friendly alternative gas and some achievements have been made in the study of its insulation and decomposition characteristics, but there are few reports on the compatibility between its characteristic decomposition products and materials. The investigation of compatibility between gas-insulated medium and material is an important part of evaluating its comprehensive performance. In this paper, we investigated the interaction between C₂F₅CN, CF₃CN, COF₂ and CF₄ with the aluminium widely used in electrical equipment. It was found that the interaction between C₂F₅CN, CF₃CN and Al (1 1 1) surface is strong. There are obvious charge transfer and electron orbital overlap between the C atom, N atom in CN group and Al (1 1 1). The interaction between COF₂, CF₄ and Al (1 1 1) surface is weak and van der Waal’s forces play the major role. Relevant results reveal the characteristics of C₃F₇CN decomposition products and provide theoretical guidance for evaluating the material compatibility between C₃F₇CN decomposition products and aluminium.     

Mass spectrometry of arcs in SF6 circuit breakers

Today, SF₆ is used to a great extent as insulating and arc-quenching medium in high-voltage gas-blast circuit breakers. The arcing in SF₆ during current interruption forms decomposition products. These can influence the arc-quenching properties of the circuit breaker. Furthermore, they can cause corrosion of the circuit breaker housing. In this comprehensive study we present results obtained for the first time from a direct mass spectrometric investigation of the exhaust gases of a high pressure SF₆ arc in a model circuit breaker. Our mass spectrometric system consists of a time-of-flight mass spectrometer (TOFMS) equipped with a molecular beam sampling systems. This device allows us to measure mass spectra of high pressure sources with a time resolution of up to 10,000 spectra per second. We have determined the formation rate of the most abundant decomposition products in a SF₆ arc at 1 bar. These products are SF₄, CF₄, WF₆, SOF₂, SO₂, CS₂ S₂F₂ and HF. The fast detection time inherent to our system permits also the determination of the formation of SF₄, which is 0.45–0.50 Vol. %/(kJ/1SF₆). In addition, we have studied the influence of water and oxygen impurities which are responsible for the production of highly corrosive HF. Finally, we have considered the influence of the thermal degradation of teflon (P.T.F.E.), which is used as nozzle and insulating material in circuit breakers. On this occasion we have demonstrated that CF₄, which exhibits dielectric properties similar to SF₆, is the main decomposition product formed from teflon. However, we have found that besides CF₄ also excess carbon is formed, which is deposited on insulators of the model circuit breaker.Our time-resolved mass spectra reveal that the CF₄ production from teflon is delayed by a few milliseconds with respect to the SF₆ dissociation in the arc. This delay can influence the interrupting process of the circuit breaker by changing the plasma composition during the arcing period. Although our experiments have been performed on a model circuit breaker we claim that the results presented in this study can be applied to real circuit breakers, since the arc current density and the energy dissipated per liter SF₆ are of the same order of magnitude in both devices.     

Total cross sections of electron scattering by several sulfur-containing molecules OCS, SO2, SF4, SF6, SF5CF3, SO2Cl2 and SO2ClF at 30–5000?eV

Total cross sections of electron scattering by several sulfur-containing molecules OCS, SO₂, SF₄, SF₆, SF₅CF₃, SO₂Cl₂ and SO₂ClF are calculated at the Hartree-Fork level employing the modified additivity rule approach. The modified additivity rule approach, which was proposed by Shi et al. [Eur. Phys. J. D 45, 253 (2007); Nucl. Instrum. Meth. B 254, 205 (2007)], takes into consideration that the contributions of the geometric shielding effect vary as the energy of incident electrons, the target’s molecular dimension and the atomic and electronic numbers in the molecule. The present investigations cover the impact energies ranging from 30 to 5000 eV. The quantitative total cross sections are compared with those obtained by experiments and other theories. Good agreement is observed even at energies of several tens of eV. It shows that the modified additivity rule approach is applicable to carry out the total cross section calculations of electron scattering by these sulfur-containing molecules at intermediate and high energies, especially over the energy range above 100 eV or so. In the present calculations, the atoms are still represented by the spherical complex optical potential, which is composed of static, exchange, polarization and absorption terms.     

The fluorescence and IR energy deposition from from CO2 laser irradiation of SF6−H2 mixtures

The multiple photon excitation and dissociation of SF₆ and hydrogen mixtures is measured by using simultaneously pulsed optoacoustic detection to monitor the energy deposition and time resolved HF fluorescence to monitor the production of vibrationally hot HF. From these studies we deduce that at least three mechanisms lead to production of vibrationally excited HF. One mechanism produces free F from the unimolecular laser-induced decomposition of SF₆. The second mechanism involves the reaction between two vibrationally hot SF₆ molecules to produce free F. In both of these cases the F atom subsequently react with H₂ to produce vibrationally hot HF. The third involves the reaction between a vibrationally hot SF₆ molecule and a hydrogen molecule producing vibrationally hot HF directly.     

Effective ionization coefficients and electron drift velocities in gasmixtures of CF3I with N2 and CO2 obtained from Boltzmannequation analysis

The electron swarm parameters including the density-normalized effective ionization coefficients (α-η)/N and the electron drift velocities V_e are calculated for the gas mixture of CF₃I with N₂ and CO₂ by solving the Boltzmann equation in the condition of steady-state Townsend (SST) experiment. The overall density-reduced electric field strength is from 100 Td to 1000 Td (1 Td=10^-17 V·cm²), while the CF₃I content k in the gas mixture can be varied over the range from 0% to 100%. From the variation of (α-η)/N with the CF₃I mixture ratio k, the limiting field strength (E/N)_lim for each CF₃I concentration is derived. It is found that for the mixtures with 70% CF₃I, the values of (E/N)_lim are essentially the same as that for pure SF₆. Additionally, the global warming potential (GWP) and the liquefaction temperature of the gas mixtures are also taken into account to evaluate the possibility of applying in the gas insulation of power equipment.     

Adsorption of SO2 on Li atoms deposited on MgO (1 0 0) surface: DFT calculations

The adsorption of sulfur dioxide molecule (SO₂) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic and defect (F_s-center) sites located on various geometrical defects (terrace, edge and corner) has been studied using density functional theory (DFT) in combination with embedded cluster model. The adsorption energy (E_ads) of SO₂ molecule (S-atom down as well as O-atom down) in different positions on both of O⁻² and F_s sites is considered. The spin density (SD) distribution due to the presence of Li atom is discussed. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces (terrace, edge and corner). The oxygen vacancy formation energies have been evaluated for MgO substrate surfaces. The ionization potential (IP) for defect free and defect containing of the MgO surfaces has been calculated. The adsorption properties of SO₂ are analyzed in terms of the E_ads, the electron donation (basicity), the elongation of S-O bond length and the atomic charges on adsorbed materials. The presence of the Li atom increases the catalytic effect of the anionic O⁻² site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the catalytic effect of the F_s-site of MgO substrate surfaces. Generally, the SO₂ molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F_s-center.     

同步辐射光激励的二氧化硅薄膜刻蚀研究

利用热氧化法在硅晶片上生长SiO₂薄膜，结合光刻和磁控溅射技术在SiO₂薄膜表面制备接触型钴掩模，通过掩模方法在硅表面开展了同步辐射光激励的表面刻蚀研究，在室温下制备了SiO₂薄膜的刻蚀图样.实验结果表明：在同步辐射光照射下，通入SF₆气体可以有效地对SiO₂薄膜进行各向异性刻蚀，并在一定的气压范围内，刻蚀率随SF₆气体浓度的增加而增加，随样品温度的下降而升高；如果在同步辐射光照射下，用SF₆和O₂的混合气体作为反应气体，刻蚀过程将停止在SiO₂/Si界面，即不对硅刻蚀，实现了同步辐射对硅和二氧化硅两种材料的选择性刻蚀；另外，钴表现出强的抗刻蚀能力，是一种理想的同步辐射光掩模材料. 关键词： 同步辐射刻蚀 接触型钴掩模 二氧化硅薄膜     

The analytical potential energy function of flue gas SO2（X1A1）

The equilibrium structure of flue gas SO2 is optimized using the density functional theory （DFT）/B3P86 method and CC-PV5Z basis. The result shows that it has a bent （C2v, X1A1） ground state structure with an angle of 119.1184°. The vibronic frequencies and the force constants are also calculated. Based on the principles of atomic and molecular reaction statics （AMIIS）, the possible electronic states and reasonable dissociation limits for the ground state of SO2 molecule are determined. The potential functions of SO and 02 are fitted by the modified Murrell-Sorbie＋c6 （M-S＋c6） potential function and the fitted parameters, the force constants and the spectroscopic constants are obtained, which are all close to the experimental values. The analytic potential energy function of the SO2 （X1A1） molecule is derived using the many-body expansion theory. The contour liues are constructed, which show the static properties of SO2 （XIA1）, such as the equilibrium structure, the lowest energies, the most possible reaction channel, etc.     

±100 kV气体轨道开关击穿特性

 研制了一种用于快Marx发生器的三电极场畸变结构的气体轨道开关,针对3种不同的绝缘介质N₂、干燥空气和SF₆/Ar混合气体开展了轨道开关的自击穿特性和触发特性研究。结果表明:轨道开关的自击穿电压与气压基本呈现线性关系,并且在相同实验条件下,相对于N₂和干燥空气,当绝缘介质为SF₆/Ar混合气体时,轨道开关具有工作电压范围宽、工作系数低、触发击穿延时短、抖动小的优点。采用数码相机拍摄了开关导通过程中形成的放电通道积分图像,初步研究了绝缘介质、电流大小等因素对开关形成多通道的影响。结果表明:提高触发电压、充电电压和放电电流及采用SF₆/Ar混合气体均能够有效增加放电通道数目。     

An investigation of paddle wheel Cu2(μ2-O2CCH3)4 for gas molecule adsorptions

Metal organic frameworks (MOFs) have been well-known and extensively researched due to the high storage /good selectivity for gas molecules. Herein, the structures and electron paramagnetic resonance (EPR) spectra for dicopper paddle wheel MOF compound (Cu₂(µ₂-O₂CCH₃)₄ with various gas molecule are theoretically investigated by density functional theory (DFT) calculations. The adsorption energies and isotherms (including pure gas molecules and the mixed ones) are calculated for the gas molecules interacting with the unsaturated Cu₂(µ₂-O₂CCH₃)₄. Both quantities exhibit the roughly consistent orders (e.g. H₂S?>?NH₃?>?CO₂?>?CO?>?H₂O?>?N₂?>?NO?>?H₂ for isotherms and H₂S?>?NH₃?>?N₂?>?CO₂?>?NO?>?H₂O?>?H₂?>?CO for adsorption energies), possibly suggesting that this material may act as a potential adsorbent of these gas molecules. The catalytic property of Cu₂(µ₂-O₂CCH₃)₄ for oxidation of CO and NO into non-toxic molecules and splitting of H₂O into H₂ and O₂ in the solvent condition are uniformly discussed. Simulation of Grand Canonical Monte Carlo (GCMC) in MS 8.0 and calculations in Langmuir model reveal that Cu₂(µ₂-O₂CCH₃)₄ has good selectivity for CH₄ in natural gas (CH₄/CO₂/N₂) and SO₂ in fog (SO₂/NO/NO₂/H₂O/O₂), which would exhibit potential environmentally friendly applications.     

Sulfur dioxide adsorbed on graphene and heteroatom-doped graphene: a first-principles study

The adsorption of sulfur dioxide (SO₂) on intrinsic graphene and heteroatom-doped (B, N, Al, Si, Cr, Mn, Ag, Au, and Pt) graphene samples was theoretically studied using first-principles approach based on density functional theory to exploit their potential applications as SO₂ gas sensors. The structural and electronic properties of the graphene-molecule adsorption adducts are strongly dependent on the dopants. SO₂ molecule is adsorbed weakly on intrinsic graphene, and B-, N-doped graphene; in general, strong chemisorption is observed on Al-, Si-, Cr-, Mn-, Ag-, Au-, and Pt-doped graphene. The adsorption mechanisms are discussed from charge transfers and density of states. This work reveals that the sensitivity of graphene-based chemical gas sensors for SO₂ can be drastically improved by introducing appropriate dopant, and Cr, as well as Mn, may be the best choices among all the dopants.     

First-principles calculations of SO<Subscript>2</Subscript> sensing with Si nanowires

High chemical reactivity and large surface-to-volume ratio have recently led to growinginterest in the employment of silicon nanowires (SiNWs) in sensing applications forchemical species detection. The working principle of SiNWs sensors resides in thepossibility to induce modifications in their electronic properties via molecularinteraction. A detailed analysis of the interaction of Si with molecular compounds is thenrequired to design and optimize NW-based sensors. Here we study the mechanisms ofadsorption on SiNWs of SO₂, an air pollutant with pernicious effects on humans.First-principles density-functional calculations are performed to calculate the electronicstructure of a SO₂molecule adsorbed at a silicon surface in case of undoped substrate and in presence ofsubstitutional subsurface and deep boron impurities. Comparing the results with the caseof NO₂ adsorption –a similar molecule that, nonetheless has a very different interaction with a Si surface –,we show the specific traits of SO₂ interaction: formation of localized states in theband-gap and absence of reactivation of pre-existing and passivated sub-surfaceimpurities. A connection between the modifications in the system electronic structure andthe strength of the molecular interaction is discussed.     

Pressure-shock-controlled pulsed molecular beams

A method of controlling the duration of pulses of intense molecular beams is suggested. The idea of the method is the shortening of an initial molecular beam pulse by producing a pressure shock in front of a solid surface through which the beam passes. Experiments on shortening H₂, He, SF₆, SF₆/H₂(1/10), and SF₆/He(1/10) molecular beam pulses are reported. The parameters of the beams incident on, and transmitted through, the surface are studied. The gas density in the initial beam and in the pressure shock before the surface is estimated. The intensity and duration of shortened molecular pulses are found as a function of the initial intensity, angle of incidence, and the diameter of a hole on the surface through which the beam passes. It is established that the duration of the shortened beam decreases greatly with increasing incident intensity and decreasing hole diameter. It is shown that intense pulsed H₂, He, SF₆, SF₆/H₂(1/10), and SF₆/He(1/10) molecular beams with a pulse duration of ≤10–15 μs and an extent of ≤1–2 cm can be generated with the method suggested.     

The Application of SF6 in the Geochemical Research

For mass spectrometric measurements of δ³¹S, pure sulphur hexafluoride was prepared quantitatively from different mineral sulphides by the reaction with elemental fluorine under pressure. The results of δ³¹S measurements on SF₆ samples were confirmed by comparison of δ³¹S values with the classical method leading to SO₂. Numerous mass spectrometric measurements of SF₆ and SO₂ with regard to the experimental conditions of the synthesis, the influence of background, memory effect, and adsorption were made. The measurements of small isotopic variations of sulphur with SF₆ has advantages in comparison to the SO₂ technique. The method described can be successfully used for routine work.