Mechanism of heterogeneous mercury oxidation by HCl on V2O5(001) surface

The selective catalytic reduction (SCR) system for NO_X removal in coal-fired power plants has a promoting effect on the oxidation and removal of elemental mercury. In this study, basic mechanism of mercury oxidation by V₂O₅-based SCR catalyst is investigated via density functional theory method and the periodic slab models. Calculations are conducted to determine the adsorption energies and geometries of Hg⁰, HgCl, HgCl₂ and HCl on V₂O₅(001) surface, and to reveal the energy profile of oxidation reaction and the structures of relative transition states and intermediates. The results indicate that HCl can significantly promote Hg⁰ oxidation on V₂O₅(001) surface, by forming an intermediate HgCl-surface which is important for Hg⁰ oxidation. The Hg⁰ oxidation goes through Hg⁰ → HgCl → HgCl₂, and the two stages of the reaction follow Eley–Rideal mechanism and Langmuir-Hinshelwood mechanism, respectively. The formation of HgCl₂ is the rate-determining step due to its high energy barrier. Three detailed reaction pathways are obtained, and the related energy profiles and structures are analyzed in detail. The Hg⁰ oxidation reaction can take place through all three pathways even if differences exist in each other, while pathways I and II have relatively low energy barriers.     

Simultaneous removal of NO and Hg0 from flue gas over MnSmCo/Ti catalyst at low temperature

The MnSmCo/Ti catalyst was designed for the simultaneous removal of NO and Hg⁰ at low temperature. The MnSmCo/Ti catalyst exhibited 80% NO conversion, almost 100% N₂ selectivity and 100% Hg⁰ removal in the absence of HCl within the temperature range of 150–250 °C with a gas hourly space velocity of 100,000 h^?1. The influence of flue gas components on Hg⁰ oxidation was investigated and the NO and O₂ are mainly responsible for Hg⁰ oxidation. Hg balance analysis revealed that the Hg⁰ removal was achieved through chemisorption and catalytic oxidation. Furthermore, the Hg⁰ oxidation mechanism was explored using transient reaction along with temperature-programmed desorption of mercury and X-ray photoelectron spectroscopy. Hg⁰ oxidation proceeds through Mars–Maessen mechanism in which adsorbed Hg⁰ is bound to MnO_x to form weakly bonded HgMnO_x+1 species and follows Langmuir?Hinshelwood mechanism, where adsorbed Hg⁰ reacts with active NO₂ to generate HgO.     

Production ofH(2s) andH(2p) by electron detachment fromH − in collisions with nitrogen and oxygen

¹⁹⁹Hg Fourier Transform NMR studies of various solutions of diverse mercury salts in H₂O and D₂O or in the appropriate protonated and deuterated acids are reported for both Hg ₂ ⁺⁺ and Hg⁺⁺. In the different solutions investigated the¹⁹⁹Hg line positions depend on the concentration of the solution, on the solvents and their isotopic composition and on the temperature of the sample. A ratio of the Larmor frequency of¹⁹⁹Hg and of²H in a Hg(NO₃)₂ solution in dilute DNO₃ is given. Using this ratio and the measured chemical shifts, a ratio of the Larmor frequencies of¹⁹⁹Hg for infinite dilution relative to²H in pure D₂O is given. From this a g_I-factor for¹⁹⁹Hg is derived and compared with the g_I-factor of an optical pumping experiment. The resulting shielding constant is σ^* (hydrated¹⁹⁹Hg⁺⁺ versus¹⁹⁹Hg atom)=?24.32(5) · 10^?4. This yields an atomic reference scale for all measured NMR line shifts of mercury.     

Structure,electronic and magnetic properties of hexagonal boron nitride sheets doped by 5d transition metal atoms: First-principles calculations and molecular orbital analysis

A first-principles calculation based on density functional theory is carried out to reveal the geometry, electronic structures and magnetic properties of hexagonal boron nitride sheets (h-BNSs) doped by 5d transitional mental atoms (Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg) at boron-site (B_5d) and nitrogen-site (N_5d). Results of pure h-BNS, h-BNS with B vacancy (V_B) and N vacancy (V_N) are also given for comparison. It is shown that all the h-BNSs doped with 5d atoms possess a C_3v local symmetry except for N_Lu and N_Hg which have a clear deviation. For the same 5d dopant, the binding energy of B_5d is larger than that of N_5d, which indicates the substitution of a 5d atom for B is preferred. The total densities of states are presented, where impurity energy levels exist. Besides, the total magnetic moments (TMMs) change regularly with the increment of the 5d atomic number. Theoretical analyses by molecular orbital under C_3v symmetry explain the impurity energy levels and TMMs.     

Simulation of diffusion instability of a mercury atomic distribution in the cadmium-mercury-tellurium alloy

The formation of inhomogeneities in Cd_xHg_1-x Te alloys upon post-growth cooling or upon low-temperature annealing is simulated numerically. The mechanism of the formation of inhomogeneities is based on the diffusion instability in a system involving mercury atoms located at lattice sites, interstitial mercury atoms, and cation vacancies. It is revealed that, upon prolonged annealing of the Cd_xHg_1-x Te alloys with a cadmium content x = 0.2 at a temperature of ∼200°C, the concentrations of mercury atoms at lattice sites, interstitial mercury atoms, and vacancies are characterized by an inhomogeneous nearly periodical distribution arising from a small fluctuation when the initial equilibrium concentration of interstitial mercury atoms exceeds a threshold value (∼3 × 10¹⁷ cm⁻³). The spatial and time scales of the concentration distribution are determined primarily by the equilibrium concentration of vacancies and do not depend on the type of fluctuation involved. The spatial period of the concentration distribution increases linearly from 0.01 to 3.00 μm as the equilibrium concentration of vacancies changes from 10¹⁹ to 10¹⁴ cm⁻³. At lower concentrations of vacancies, the periodic structure is formed for a considerably longer time.     

A Refinement of the Hg2F2 Structure by the Use of NMR Data

Abstract

The crystal structure of Hg₂F₂ was studied in works.^1,2 The Hg₂F₂elementary cell of the tetragonal syngony with a=3.66 Å and c=10.89 Å contains two formula units, the space-group being 14/mmm. Hg₂F₂ belongs to those types of structures which possess one non-fixed coordinate (z_F and zHg); hence, the position of the fluorine nuclei may be determined from the value of the second moment of the NMR spectrum of ¹⁹F for powder sample.³ In this case it is ostensibly important, inasmuch as determining the positions of fluorine nuclei near the heavy mercury atoms presents a difficulty for X-ray analysis.     

Heterogeneous reaction mechanism of elemental mercury oxidation by oxygen species over MnO2 catalyst

MnO₂-based catalysts have attracted great attention in the field of elemental mercury (Hg⁰) catalytic oxidation because of their superior catalytic performance and wide temperature window. Quantum chemistry calculations based on density functional theory (DFT) combined with periodic slab models were carried out to investigate the heterogeneous mechanism of Hg⁰ oxidation by oxygen species (gas-phase O₂, chemisorbed oxygen, and lattice oxygen) on MnO₂ surface. The results indicate that Hg⁰ and HgO are chemically adsorbed on MnO₂ surface with the adsorption energies of ?69.50 and ?226.48?kJ/mol, respectively. The adsorption of O₂ on MnO₂ surface belongs to chemisorption. O₂ can decompose on MnO₂ surface with an energy barrier of 97.46?kJ/mol to produce two atomic adsorbed oxygen. The perpendicular adsorbed O₂ and dissociative adsorbed O₂ are more favorable for Hg⁰ catalytic oxidation than lattice oxygen, and perpendicular adsorbed O₂ is the most active oxygen for Hg⁰ oxidation. The reaction pathway of Hg⁰ oxidation by perpendicular adsorbed O₂ includes three reaction steps: Hg⁰?→?Hg(ads)?→?HgO(ads)?→?HgO. The third step (HgO(ads)?→?HgO) is endothermic by 168.17?kJ/mol with an energy barrier of 179.48?kJ/mol, and it is the rate-limiting step of the whole Hg⁰ oxidation reaction.     

Damage and lattice location studies in Hg implanted Hg1–xCdxTe

Abstract

Rutherford backscattering (RBS) and ion induced X-ray (PIXE) channeling experiments have been used to study the damage accompanying Hg and Al implantations into Hg_0.8Cd_0.2 Te and its annealing as well as to determine the location of Hg in the crystal.

The damage induced by the implantation of 300 keV Hg and 250 keV Al ions at room temperature was found from RBS channeling studies to reach a saturation level at doses of 1 × 10¹⁴ cm^?2 and 3 × 10¹⁴ cm^?2 respectively. The damage resembles that characteristic for extended defects and it anneals at ≈ 300°C.

The location of the constituents of Hg implanted Hg_0.8 Cd_0.2 Te was studied by PIXE channeling observing the characteristic X-rays for each element. Angular scans indicate that the channels are mostly blocked by Hg atoms for both unannealed and, to a lesser extent, annealed crystals. This observation supports the suggestion that interstitial Hg atoms may be responsible for the conductivity of Hg implanted Hg_1–x Cd_g Te.     

Sputter cleaning and dry oxidation of CdTe,HgTe, and Hg0.8Cd0.2Te surfaces

The analyses of CdTe, HgTe, and Hg_0.8Cd_0.2Te surfaces by XPS and LEED after Ar⁺ sputtering and after the subsequent onset of a dry oxidation are described, and a quantitative evaluation of the XPS spectra is attempted. The results are: Ar⁺ sputtering yields a perfect unreconstructed CdTe surface of stoichiometric composition, whereas the composition of sputtered HgTe and Hg_0.8Cd_0.2Te surfaces generally deviates from the stoichiometry of the respective compound. This deviation is a function of the energy of the Ar ions (1 to 15 keV) and is characterized by an increasing deficit in Hg as the ion energy is raised. The Hg deficit of sputtered Hg_0.8Cd_0.2Te surfaces is substitutionally compensated by an equivalent increase in Cd, and due to this substitution the resulting surfaces are sufficiently ordered to display a distinct LEED pattern. The oxidation of sputtered CdTe, HgTe, and Hg_0.8Cd_0.2Te surfaces in an O₂ atmosphere is an extremely slow process. Therefore, the surfaces to be oxidized were additionally exposed to UV radiation (low pressure mercury lamp), and due to UV generated ozone as an oxidizing agent ultrathin native oxide layers of up to 15 Å thickness were readily obtained. The predominant constituents of these native oxide layers on Hg_0.8Cd_0.2Te are concluded to be CdTeO₃ and TeO₂.     

Electronic Emission from Hg-Atoms and HgCl-Radicals Due to Collisions of Nitrogen Ions and HgCl2/Hg2Cl2 Molecules

Emission spectra of the (B-X), (C-X) and (D-X) band systems of HgCl-radical and mercury atomic lines from highly excited levels to various lower levels have been observed during collisions of N⁺ and N⁺ ₂ ions and HgCl₂/Hg₂Cl₂ molecules at different laboratory kinetic energies of the projectile ions. Emission cross-sections of the most intense mercury atomic lines and the (C-X) band system of the HgCl-radicals, have been measured in the laboratory kinetic energy range of 100–900 eV.     

Sonication-Assisted Synthesis of Bimetallic Hg/Pd Alloy Nanoparticles for Catalytic Reduction of Nitrophenol and its Derivatives

In this article, we report a facile approach for the synthesis of an inexpensive catalyst of bimetallic Hg/Pd alloys comprising nanoparticles with various structures using a unique ultrasonic reaction that is conducted without the use of any reducing agent. The nanoparticles of Hg/Pd alloys (HgPd and Hg₂Pd₅) were achieved for the first time by sonicating an aqueous solution of Palladium (II) nitrate with metallic liquid mercury, as evidenced by XRD. EDS further confirmed the presence of Pd and Hg elements in the alloy. The surface morphology and structure of the nanoparticles have been systematically investigated by HRSEM, HRTEM and SAED pattern. In order to explore the catalytic activity of the as-synthesized nanoalloys, the catalytic reduction of 4-nitrophenol and a few other nitrophenol derivatives were investigated. Excellent catalytic activity was obtained for Hg/Pd (1:1) alloy, and the rate constant for the reduction of 4-NP with Hg/Pd at room temperature was found to be 58.4 × 10⁻³ s⁻¹, which is possibly the highest ever reported. The catalyst exhibited superior stability and reusability when compared with those reported in the literature for other catalysts based on noble metals.     

Optical properties of the ternary compound Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se:Co

We present the results of experimental studies of the optical properties of cobalt-doped Cd _x H_1−x Se (x = 0.18) single crystals with cobalt ion concentrations of NCo = 5·10¹⁸, 5·10¹⁹, and 1·10²⁰ cm⁻³ at T = 90 K and 300 K. The composition (x = 0.18) of the Cd _x Hg_1−x Se solid solution was selected so that the hypothetical resonance level is found on the bottom of the conduction band. We show that the cobalt ions in the mercury selenide can form a resonance donor level only for cobalt concentrations N_Co < 5·10¹⁸ cm⁻³. For N_Co ∼ 5·10¹⁸ cm⁻³, the cobalt ions substitute for mercury atoms, forming a solid solution and leading to an increase in the bandgap width and a change in the physical properties. The solubility of cobalt in the HgSe lattice can be greater than 5%–10%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 73–77, January–February, 2007.     

N2微空心阴极放电特性及其阴极溅射的PIC/MC模拟

采用两维PIC/MCC模型模拟了氮气微空心阴极放电以及轰击离子 (N₂⁺,N⁺) 的钛阴极溅射. 主要计算了氮气微空心阴极放电离子 (N₂⁺,N⁺) 及溅射原子Ti的行为分布, 并研究了溅射Ti 原子的热化过程. 结果表明: 在模拟条件下, 空心阴极效应是负辉区叠加的电子震荡; 在对应条件下, 微空心较传统空心放电两种离子 (N₂⁺,N⁺) 密度均大两个量级, 两种离子的平均能量的分布及大小几乎相同; 在放电空间N⁺的密度约为N₂⁺的1/6, 最大能量约大2倍; 在不同参数 (P, T, V)下, 轰击阴极内表面的氮离子(N₂⁺,N⁺)的密度近似均匀, 其平均能量几乎相等; 从阴极溅射出的Ti原子的初始平均能量约6.8 eV, 离开阴极约0.15 mm处几乎完全被热化. 模拟结果为N₂微空心阴极放电等离子体特性的认识提供了参考依据. 关键词： 微空心阴极放电 PIC/MC模拟 2等离子体')" href="#">N₂等离子体     

Single crystal of the 1223/1234 intergrowth phase Hg1.44Re0.5Ba4Ca5Cu7O20: structure and properties

A single crystal of Hg_1.44Re_0.5Ba₄Ca₅Cu₇O₂₀ (HgRe-2457) has been grown with a gas-phase high pressure technique at 10 kbar. X-ray single-crystal structure analysis showed that the crystal is composed of alternating blocks of 1223 and 1234 units. Until now, intergrowth structures in the Hg based series have only been observed in a small submicron scale or as a defect. Rhenium substitutes 25% of mercury and forms short bonds of 1.98 Å to oxygen atoms. They coordinate Re octahedrally and are shifted off their ideal positions to (0.36, 0.36, z). The bond lengths are in the range of pure 1223 or 1234 compounds. The stacking sequence is disturbed by double or triple layers of 1223 or 1234, like …3-4-3-4-4-3-4-3…. This feature is visible in Fourier maps and included in the refinement. The transition temperature of this 2457 crystal is 83 K.     

Influence of thermal processing of Mn x Hg1−x Se crystals in mercury and selenium vapor on their magnetic susceptibility

We report a study of the influence of thermal processing of Mn _x Hg_1–x Se crystals in mercury and selenium vapor on the temperature dependence of their magnetic susceptibility. It is shown that thermal processing of Mn _x Hg_1–x Se in mercury vapor leads to diffusion of Hg atoms into the crystal, with a resulting increase in the number of interstitial mercury atoms, which act as donors and increase the electron concentration in the samples. As a consequence, the diamagnetic contribution of the interstitial mercury increases, along with the dia- or paramagnetic contribution of the increasing electron concentration, and there is a change in the contribution of the Mn atoms, which migrate during the anneal, leading to a change in the magnetic susceptibility of the Mn _x Hg_1–x Se crystals. We also show that thermal processing of Mn _x Hg_1–x Se in Se vapor leads to the formation of new clusters in the crystal, or a change in size for ones which preexist (either by increasing or decreasing the size) due to the thermodynamic equilibrium conditions in the Mn _x Hg_1–x Se system, i.e. the relationship between the cluster size and the concentration.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 54–59, August, 1993.     

The Influence of Admixtures of Molecular Gases on the Efficiency of Radiation Production by Ar?Hg Mixture Plasmas used in Fluorescent Lamps

Starting from former investigations of pure Ar? Hg mixture plasmas in parameter ranges typical of fluorescent lamps we studied the influence of additional admixtures of molecular gases (N₂, H₂) on the energy transfer from the electrons heated by an electric field to the lowest excited states of Hg atoms which are the energy source for the resonance radiation production. By calculation of the different power loss rates via solving the appropriate Boltzmann equation for three component mixture plasmas it was found that already a threshold level of molecular impurities of about 10^?4 Torr leads to a marked energy dissipation by the impurities and thus to a pronounced reduction of the efficiency of the resonance radiation production. This is caused by the great effectivity of vibrational excitation of molecules in electron collisions due to the great cross sections for such collisions and their low thresholds.     

Magneto-optical trapping of neutral mercury

We report on the cooling of neutral mercury in a magneto-optical trap utilizing the spin forbidden ¹S₀ → ³P₁ transition at 253.7 nm. We trapped two Hg isotopes, i.e. the bosonic ²⁰²Hg and the fermionic ¹⁹⁹Hg isotope, respectively. The temperature of the cold atom cloud was determined to be approximately 300 μK using a modified TOF-method. It is currently limited by the quality of the laser lock. Trapped neutral Hg has many interesting avenues such as a time standard and high precision measurements. Here, we discuss the possibilities of photo-association spectroscopy and the generation of ultra-cold Hg₂ dimers.     

Environmental perturbations on foreign atoms and molecules in solid argon,krypton and xenon

Perturbations which are responsible for the shifts of electronic and vibrational spectra of species trapped in a solid are considered in terms of the intermolecular potential which describes interactions between these species and neighbouring atoms. It is shown that in certain instances London's theory can give an adequate approximation to the dispersion energy between an electronically excited species and a rare gas atom. The experimental shifts in the electronic absorption spectra of Hg, NH and C₂ at lattice sites in rare gas crystals at 4·2°k are explained quantitatively on the basis of a Lennard-Jones (6-12) or (6-8-12) potential between the trapped species and the rare gas atoms. The theory does not adequately explain the shifts in those cases where strong angular dependent forces differing appreciably in the two electronic states are present, data on trapped NH₂ free radicals being presented as a case in point. The interaction of sodium atoms with argon at 4·2°k is very complex, the data being consistent with multiple trapping sites for the atoms, a large repulsive interaction between the excited state of sodium and the rare gas, and apparent removal of the three-fold orbital degeneracy in the excited state by the environmental perturbation. The three-fold orbital degeneracy in the ³P₁ state of mercury was found also to be removed. The blue shift of 1281 cm^-1 for the ³P₁ ← ¹S₀ transition of mercury in solid argon at 4·2°k corresponds almost exactly with the position of one of the two prominent features in the spectrum of mercury in argon gas at comparable densities and illustrates the similarity of structure in the two physical states. The interesting perturbations on the vibrational states of NH and C₂ suggest a close similarity to the effect which causes environmental variations of coupling constants for hyperfine interactions in trapped hydrogen atoms.     

Photoassociation spectroscopy of collisional pairs of mercury atoms: Determination of parameters of molecular terms

The photoassociation spectrum of an equilibrium vapor of mercury atoms in the range of 34960–37250 cm^?1 is recorded with the help of a tunable laser in observations of laser-induced fluorescence. The Franck-Condon fstructure, i.e., periodic variations in absorption intensity against a continuous background, is observed. The structure makes it possible to determine spectroscopic parameters of the upper attractive potential and the lower repulsive potential including that with a van der Waals well. The absorption spectrum of collisional pairs of mercury atoms is calculated using the Numerov-Cooley procedure for integrating the Schrödinger equation. Potential curves of the upper and lower states Hg₂(D1_u) and Hg₂(X0 _g ⁺ ) are determined by comparing the calculated spectra with the experimental one.     

A new optical method of measuring electron impact excitation cross section of atoms: Cross section of the metastable 6s6p P0 level of Hg

We report a new method that is potentially applicable to the measurement of electron impact excitation cross section of any atoms. Measurement of the cross section of the metastable 6s6p ³P₀ level of mercury is conducted to demonstrate the method, which involves using cavity ringdown spectroscopy to determine the absolute number density of mercury atoms in the 6s6p ³P₀ energy level. The measured cross section is 1.7×¹⁰−17 cm² and in agreement with the literature values. Compared with the optical methods that have been used during the last three decades, this new approach not only serves as an alternative optical method, but also is applicable to the atoms under both high and low pressure conditions.