Simultaneous Removal of H<Subscript>2</Subscript>S and Dust in the Tail Gas by DC Corona Plasma

The removal of hydrogen sulfide and dust simultaneously by the DC corona discharge plasma with a wire-cylinder reactor was studied at atmospheric pressure and room temperature. The outlet gases were analyzed by Fourier Transform Infrared. Chemical compositions of the dust collected from ground electrode were analyzed by X-ray fluorescence. The results showed that the DC corona discharge is effective in removing H₂S and dust simultaneously. The best H₂S conversion was gained with the 2 cm discharge gap. The lower inlet H₂S concentration, the higher conversion efficiency was gained at any specific input energy (SIE), while the energy yield was on the contrary. The removal efficiency of H₂S decreased gradually as oxygen concentration increased, which means that the H₂S decomposition mainly depends on direct electron collisions or short-living species, such as^·O, ^·OH radicals in the non-thermal plasma. At the initial stage, the conversion efficiency of H₂S increased with the increasing of relative humidity, but later decreased while the relative humidity keep increasing with the same SIE. Existing of dust can not only reduce the energy consumption of H₂S conversion and improve the removal efficiency, but also inhibit the yield of SO₂ for it can further react with some compounds in the dust. With the discharge gap of 2 cm, inlet H₂S concentration of 2400 ppm, O₂ Of 0.5 %, relative humidity of 41 %, dust content of 4000 ± 5 % mg/m³ and SIE of 600 J/L, the H₂S conversion reached 98.8 %, and the dust removal efficiency was close to 100 %.     

Theoretical study on the H<Subscript>2</Subscript>S activation by PtCH<Subscript>2</Subscript><Superscript>+</Superscript> in the gas phase

The reaction mechanism of the gas-phase PtCH₂ ⁺ with H₂S has been systematically investigated on the doublet and quartet potential energy surfaces at BPW91/6-311++G(2d, p)∪ SDD level. The Pt in PtCH₂ ⁺ prefers to attack S–H bond in H₂S. For PtCH₂ ⁺ + H₂S reaction, the potential energy surfaces (PESs), including three reaction pathways of hydrogen (including one and two hydrogen elimination) and methane elimination, have been explored and characterized. By contrast with hydrogen elimination, methane elimination reaction channel is energetically favorable, which is in good agreement with the experimental observation. The optimal S–H bond activation is the first step, followed by cleavage of Pt–C and Pt–S bond. About the path a and b, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction \(\varDelta E_{\text{int}}^{ \ne }\), which is the actual interaction energy between the deformed reactants in the transition state.     

Diagnostics of Plasma Behavior and TiO<Subscript>2</Subscript> Properties Based on DBD/TiO<Subscript>2</Subscript> Hybrid System

Plasma catalysis is gaining increasing interest in environmental and energy applications, such as the destruction of gas pollutants and hydrocarbon conversion. In order to further improve the application of plasma catalysis, it is crucial to understand the fundamental mechanisms, especially the mutual interaction between plasma and catalyst. In this paper, a parallel-plate dielectric barrier discharge (DBD) reactor is developed to investigate the plasma behavior and TiO₂ properties in the plasma/catalytic hybrid system. The introduction of TiO₂ thin film coated on the dielectric improves the discharge intensity, which significantly contributes to the enhancement of reactive species and charges. The energy efficiency of generating ozone in DBD/TiO₂ system has been approximately raised by 38% compared to pure DBD when the applied voltage reaches 13 kV. It is fortunately found that the discharge does not change the crystal structure of the TiO₂, but the band gap increases from 3.13 to 3.39 eV, which has been proved to enhance the oxidizability of TiO₂ in the degradation of methyl orange experiment under UV light. The FTIR and XPS spectra also demonstrate that N element is doped into the structure of TiO₂. These results successfully illustrate the plasma behavior and catalyst properties in plasma/catalysis hybrid system and provide reference for the optimization of the plasma catalysis process.     

Perovskite LaMnO<Subscript>3</Subscript>/ZSM-5 composites for H<Subscript>2</Subscript>S reactive adsorption at high temperature

Perovskite LaMnO₃/ZSM-5 was used for reactive adsorption of hydrogen sulfide at 500–700 °C. The sorbents showed good desulphurization performance, the highest sulfur capacity of 1020 µmol S/g over 5La5Mn/ZSM-5 was obtained at 600 °C. The reducing gases (H₂ and CO) can obviously shorten the breakthrough time and reduce the sulfur capacity. Incorporating Mn ions into La₂O₃ lattice improved the sulfidation activity due to the formation of perovskite LaMnO₃ with good reducibility and structure stability.     

Catalytic Properties of TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles in Plasma Chemical Treatment

We proposed here a new process coupling dielectric barrier discharge (DBD) plasma with magnetic photocatalytic material nanoparticles for improving yield in DBD degradation of methyl orange (MO). TiO₂ doped Fe₃O₄ (TiO₂/Fe₃O₄) was prepared by the sol-gel method and used as a new type of magnetic photocatalyst in DBD system. It was found that the introduction of TiO₂/Fe₃O₄ in DBD system could effectively make use of the energy generated in DBD process and improve hydroxyl radical contributed by the main surface Fenton reaction, photocatalytic reaction and catalytic decomposition of dissolved ozone. Most part of MO (88%) was degraded during 30 min at peak voltage of 13 kV and TiO₂/Fe₃O₄ load of 100 mg/L, with a rate constant of 0.0731 min^?1 and a degradation yield of 7.23 g/(kW h). The coupled system showed higher degradation efficiency for MO removal.     

Thermal analysis on C<Subscript>6</Subscript>H<Subscript>10</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>-doped MgB<Subscript>2</Subscript>

Additives to MgB₂ can improve the superconducting functional characteristics, such as critical current density (J _c) and irreversibility field (H _irr). Recently, we have shown that repagermanium (C₆H₁₀Ge₂O₇) is an effective additive, enhancing both J _c and H _irr. To look into details of the processes taking place during the reactive sintering, a thermal analysis study (0.167 K s^?1, in Ar) is reported. We used differential scanning calorimetry between 298 and 863 K and simultaneous thermogravimetric—differential thermal analysis between 298 and 1233 K. Samples were mixtures of powders with composition 97 mol% MgB₂ and 3 mol% C₆H₁₀Ge₂O₇. Up to 863 K, repagermanium decomposes by multiple steps and forms amorphous phases. A reaction with MgB₂ is not observed. Above this temperature, partial decomposition of MgB₂ occurs. Crystalline Ge and MgO are detected before formation of Mg₂Ge and MgB₄, when temperature approaches the melting point of Ge (1211 K). Carbon substitution for boron in the crystal lattice of MgB₂ is observed for samples heated above 863 K. The amount of substitutional C does not significantly change with temperature.     

CO<Subscript>2</Subscript> Biofixation and Growth Kinetics of <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> and <Emphasis Type="Italic">Nannochloropsis gaditana</Emphasis>

CO₂ biofixation was investigated using tubular bioreactors (15 and 1.5 l) either in the presence of green algae Chlorella vulgaris or Nannochloropsis gaditana. The cultivation was carried out in the following conditions: temperature of 25 °C, inlet-CO₂ of 4 and 8 vol%, and artificial light enhancing photosynthesis. Higher biofixation were observed in 8 vol% CO₂ concentration for both microalgae cultures than in 4 vol%. Characteristic process parameters such as productivity, CO₂ fixation, and kinetic rate coefficient were determined and discussed. Simplified and advanced methods for determination of CO₂ fixation were compared. In a simplified method, it is assumed that 1 kg of produced biomass equals 1.88 kg recycled CO₂. Advance method is based on empirical results of the present study (formula with carbon content in biomass). It was observed that application of the simplified method can generate large errors, especially if the biomass contains a relatively low amount of carbon. N. gaditana is the recommended species for CO₂ removal due to a high biofixation rate—more than 1.7 g/l/day. On day 10 of cultivation, the cell concentration was more than 1.7?×?10⁷ cells/ml. In the case of C. vulgaris, the maximal biofixation rate and cell concentration did not exceed 1.4 g/l/day and 1.3?×?10⁷ cells/ml, respectively.     

Structures and mutual transformations of isomers of germylium ions (CH<Subscript>3</Subscript>)H<Subscript>2</Subscript>Ge<Superscript>+</Superscript> and (CH<Subscript>3</Subscript>)<Subscript>2</Subscript>HGe<Superscript>+</Superscript> and their silicon analogs

The potential energy surfaces of the (CH₃)_nH_3?n M⁺ ions, where n = 1, 2; M = Si, Ge, were scanned using the B3LYP method with 6–31G* and aug-cc-pVDZ basis sets. The major attention was given to isomeric species having the form of complexes of the HM⁺ and CH₃M⁺ ions with hydrogen, methane, and ethane molecules. These species were characterized previously neither by experimental nor by theoretical methods. It was found that these species become more stable in going from Si to Ge; the complex [CH₃Ge⁺CH₄] is the second isomer in the energy after (CH₃)₂HGe⁺. However, the heights of the activation barriers to formation of these complexes from the most stable isomer, though decreasing in going from Si to Ge, remain relatively high and, what is particularly important, somewhat exceed the activation barrier to formation of the complex [H₃Ge⁺·C₂H₄].     

Effects of carbon coating from sucrose and PVDF on electrochemical performance of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C composites in different potential ranges

The carbon coated nanoflower-like Li₄Ti₅O₁₂/C composites were prepared via hydrothermal method followed by surface modification using sucrose or polyvinylidene fluoride (PVDF) as carbon sources. X-ray diffraction, SEM, TEM, Raman spectroscopy, TGA, and the electrochemical measurements were used for the materials characterization. Such modification leads to the formation of a high-conductive carbon coating. In the case of polyvinylidene fluoride use, fluorination of Li₄Ti₅O₁₂ surface takes place also. As a result, electrochemical performance of the obtained composites is improved. In the potential range of 1–3 V, Li₄Ti₅O₁₂, Li₄Ti₅O₁₂/C_PVDF, and Li₄Ti₅O₁₂/C_sucrose exhibit, respectively, the discharge capacities of 142.5, 154.3, and 170.4 mAh/g at a current of 20 mA/g and 57.2, 82.1, and 89.3mAh/g at a current of 3200 mA/g. When cycled in a potential range of 0.01–3 V, the discharge capacity of Li₄Ti₅O₁₂/C_PVDF increases up to 252 mAh/g at 20 mA/g.     

Preparation and methane adsorption of two-dimensional carbide Ti<Subscript>2</Subscript>C

Here a novel material for methane adsorption was synthesized and studied, which is a graphene-like two-dimensional (2D) carbide (Ti₂C, a member of MXenes), formed by exfoliating Ti₂AlC powders in a solution of lithium fluoride (LiF) and hydrochloric acid (HCl) at 40 °C for 48 h. Based on first-principles calculation, theoretically perfect Ti₂C with O termination has a specific surface area (SSA) of 671 m² g^?1 and methane storage capacity is 22.9 wt%. Experimentally, 2.85 % exfoliated Ti₂C with mesopores shown methane capacity of 11.58 cm³ (STP: 0 °C, 1 bar) g^?1 (0.82 wt%) under 5 MPa and the SSA was 19.1 m² g^?1. For Ti₂C sample intercalated with NH₃·H₂O, the adsorbed amount was increased to 16.81 cm³ (STP) g^?1 at same temperature. At the temperature of 323 K, the adsorbed amount of as-prepared Ti₂C was increased to 52.76 cm³ (STP) g^?1. For fully exfoliated Ti₂C, the methane capacity was supposed to be 28.8 wt% or 1148 V (STP)v^?1. Ti₂C theoretically has much larger volume methane capacity than current methane storage materials, though its SSA is not very high.     

Natural graphite enhanced the electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> cathode material for lithium ion batteries

Natural graphite treated by mechanical activation can be directly applied to the preparation of Li₃V₂(PO₄)₃. The carbon-coated Li₃V₂(PO₄)₃ with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li₃V₂(PO₄)₃ (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g^?1 at 0.1 C and 162.9 mAh g^?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.     

Synthesis and characterization of a new monophosphate (C<Subscript>6</Subscript>H<Subscript>16</Subscript>N<Subscript>2</Subscript>)(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Chemical preparation, crystal structure, and NMR spectroscopy of a new trans-2,5-dimethylpiperazinium monophosphate are given. This new compound crystallizes in the triclinic system, with the space group P-1 and the following parameters: a = 6.5033(3), b = 7.6942(4), c = 8.1473(5) Å, α = 114.997(3), β = 92.341(3), γ = 113.136(3), V = 329.14(3) ų, Z = 1, and D_x = 1.565 g cm^?3. The crystal structure has been determined and refined to R = 0.030 and R _w(F ²) = 0.032 using 1558 independent reflections. The structure can be described as infinite [H₂PO₄] _n ^n? chains with (C₆H₁₆N₂)²⁺ organic cations anchored between adjacent polyanions to form columns of anions and cations running along the b axis. This compound has also been investigated by IR, thermal, and solid-state, ¹³C and ³¹P MAS NMR spectroscopies and Ab initio calculations.     

Molecular mechanism of propane oxidative dehydrogenation on surface oxygen radical sites of VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/TiO<Subscript>2</Subscript> catalysts

Minimum energy pathways of propane oxidative dehydrogenation to propene and propanol on supported vanadium oxide catalyst VO _x /TiO₂ were studied by periodic discrete Fourier transform (DFT) using a surface oxygen radical as the active site. The propene formation pathway was shown to consist of two consecutive hydrogen abstraction steps. The first step includes C_β–H bond activation of propane followed by the formation of a surface hydroxyl group V–O _t H and a propyl radical n-C₃H₇. This step with the activation energy E* = 0.56 eV (54.1 kJ/mol) appears to be rate-determining. The second step involves the reaction of the bridging O _b oxygen atom with the methylene C–H bond of propyl radical n-C₃H₇ followed by the formation of a hydroxylated surface site HO _t –V⁴⁺–O _b H and propene. The initial steps of the C–H bond activation during propane conversion to propanol and propene by ODH on V⁵⁺–(O _t O _b )^? active sites are identical. The obtained results demonstrate that participation of surface oxygen radicals as the active sites of propane ODH makes it possible to explain relatively low activation energies observed for this reaction on the most active catalysts. The presence of very active radical species in low concentration seems to be the key factor for obtaining high selectivity.     

Effects of Pressure and Electrode Length on the Abatement of N<Subscript>2</Subscript>O and CF<Subscript>4</Subscript> in a Low-Pressure Plasma Reactor

The emission of greenhouse gases, such as N₂O and fluorinated gases, has been increasingly regulated in the semiconductor industry. Pressure effects on the abatement of N₂O and CF₄ were investigated in a low-pressure plasma reactor by using Fourier transform infrared (FTIR) spectroscopy. The destruction and removal efficiency (DRE) of N₂O and CF₄ was significantly lowered below 0.2 Torr. When the pressure was increased, the DRE of CF₄ with H₂O as the reactant gas increased continuously, but that with O₂ or without any reactant gas first increased and then decreased. A larger electrode length yielded a higher DRE of N₂O and CF₄, especially at lower pressures. To understand this phenomenon, the electrical waveforms for the discharge in N₂O were analyzed in conjunction with its optical emission profiles, and the rotational temperatures for different electrode lengths were compared using the N₂ ⁺ ion band (λ = 391.4 nm). They provided insights into the mechanism involved in terms of plasma property and gas residence time.     

LiMO<Subscript>2</Subscript>@Li<Subscript>2</Subscript>MnO<Subscript>3</Subscript> positive-electrode material for high energy density lithium ion batteries

Li[Ni_1/3Co_1/3Mn_1/3]O₂ (NCM 111) is a promising alternative to LiCoO₂, as it is less expensive, more structurally stable, and has better safety characteristics. However, its capacity of 155 mAh g^?1 is quite low, and cycling at potentials above 4.5 V leads to rapid capacity deterioration. Here, we report a successful synthesis of lithium-rich layered oxides (LLOs) with a core of LiMO₂ (R-3m, M?=?Ni, Co) and a shell of Li₂MnO₃ (C2/m) (the molar ratio of Ni, Co to Mn is the same as that in NCM 111). The core–shell structure of these LLOs was confirmed by XRD, TEM, and XPS. The Rietveld refinement data showed that these LLOs possess less Li⁺/Ni²⁺ cation disorder and stronger M*–O (M*?=?Mn, Co, Ni) bonds than NCM 111. The core–shell material Li_1.15Na_0.5(Ni_1/3Co_1/3)_core(Mn_1/3)_shellO₂ can be cycled to a high upper cutoff potential of 4.7 V, delivers a high discharge capacity of 218 mAh g^?1 at 20 mA g^?1, and retains 90 % of its discharge capacity at 100 mA g^?1 after 90 cycles; thus, the use of this material in lithium ion batteries could substantially increase their energy density.

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Graphical Abstract Average voltage vs. number of cycles for the core–shell and pristine materials at 20 mA g^?1 for 10 cycles followed by 90 cycles at 100 mA g^?1

     

Preparation of Boron Carbide from BF<Subscript>3</Subscript> and BCl<Subscript>3</Subscript> in Hydrogen Plasma of Arc RF Discharge

A comparative study was carried out of the process of plasma chemical deposition of boron carbide from hydrogen plasma containing the mixtures of BF₃ + CH₄ and BCl₃ + CH₄ sustained by RF arc (13.56 MHz) discharge. It was shown that in the case of synthesis of B₄C from a mixture of BF₃ + CH₄, carbon and complex coordination compound [X₃B]^?H⁺ (R₃B·FH) are formed as the by-products of condensed products. In the case of synthesis of B₄C from the BCl₃ + CH₄ mixture, the only condensed product is carbon. Mechanisms for the formation of boron carbide on the surface of heated electrodes are proposed. The main feature of these mechanisms is the preliminary deposition of a graphite layer from CH₄ and then the precipitation of boron with the participation of the radicals BF₂, BF and BCl. B₄C samples were obtained and the impurity composition, morphology and structure of bulk boron carbide samples obtained using both of its halides were studied. It was found that in both cases a carbon phase is present in boron carbide samples. The main impurities entering the B₄C, in the case of using a mixture of BF₃ + CH₄, is silicon, and in the case of a mixture of BCl₃ + CH₄, is tungsten.     

Effects of Air/H<Subscript>2</Subscript>O Discharge Plasma on Propane Combustion Enhancement Using Dielectric Barrier Discharges

Combustion provides about 80% energy for our daily life and industrial production. But thermal efficiency of traditional combustion technologies is low, which causes energy waste and serious environmental pollution. In order to improve the combustion efficiency, a combined method based on non-equilibrium plasma generated by dielectric barrier discharge and OH radicals coming from water-steam additive was proposed in this work, and plasma assisted propane combustion was examined and evaluated. The results indicated that when relative humidity (RH) was 20% and applied peak voltage was fixed at 8.75 kV, the relative intensity of OH radical and the flame temperature reached the maximum value at the flame root. At the same time, propane combustion was the most complete. In addition, we found that the erosion of the inner electrode was weakened by H₂O addition, and the symmetry of discharge current was changed from symmetry to asymmetry with the increase of RH. Compared with the pure air undischarged combustion, when the relative humidity was 20% and under the discharge conditions of 8.75 kV, the lean-burn extinction limit was extended to 0.4,which is far lower than the traditional lean-burn limit (0.51).     

Effect of C<Subscript>2</Subscript>H<Subscript>4</Subscript>/N<Subscript>2</Subscript> Ratio in an Atmospheric Pressure Dielectric Barrier Discharge on the Plasma Deposition of Hydrogenated Amorphous Carbon-Nitride Films (a-C:N:H)

The goal of this study was to investigate the properties and growth mechanisms of nitrogen-containing carbon-based coatings obtained with an atmospheric pressure dielectric barrier discharge in an N₂-C₂H₄ atmosphere. Radically different chemical compositions were observed depending on C₂H₄/N₂ ratio. With a low C₂H₄ concentration (<400 ppm) as a function of the residence time in the discharge, two different growth mechanisms were observed consisting of a highly nitrogenated coating (N/C > 0.8) and low hydrogen content. At the short residence time, growth was due to mobile small radicals that procured a smooth yet soluble coating, while at the longer residence time, diffusion-limited aggregation of high sticking N-containing radicals produced a cauliflower-like structure. With a high C₂H₄ concentration (≥2,000 ppm), a polymer-like coating with relatively lower nitrogen content (N/C ~ 0.2) was observed with a cauliflower morphology for the entire coating. Nanoindentation measurements revealed very different physical properties in the two types of coatings.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Time-Resolved CO<Subscript>2</Subscript> Dissociation in a Nanosecond Pulsed Discharge

Electrical discharges are increasingly used to dissociate CO₂ in CO and O₂. This reaction is the first step in the way for the synthesis of value-added compounds from CO₂ by using renewable electricity. If efficient, this technology might allow at the same time recycling CO₂ and storing renewable energy in chemical form. At present, while the dissociation degree is measured in the reactor exhaust, little is experimentally known about the dissociation kinetics in the discharge and post-discharge. This knowledge is however critical to increasing the overall efficiency of the plasma process. To estimate the time dependence of the CO₂ dissociation following a discharge event, we have coupled a LIF diagnostics to a nanosecond repetitively pulsed discharge in a mixture of CO₂ and H₂O. This paper discusses a procedure to obtain data on the time evolution of the CO₂ dissociation, its limits and future perspectives. In addition, the local gas temperature is measured as well. We find that a few microseconds after the discharge pulse, CO₂ is highly dissociated with a temperature around 2500 K. In about 100 µs, the temperature decreases at about 1500 K while the dissociation is reduced by about a factor of three.