Microscopic insight into catalytic HCN removal over the CuO surface in chemical looping combustion

Hydrogen cyanide (HCN) is well-accepted as a main nitrogen-containing precursor from fuel nitrogen to nitrogen oxides. When using coal as fuel with a CuO-based oxygen carrier in chemical looping combustion (CLC), complex heterogeneous reactions exist among the system of HCN, O₂, NO, H₂O, and CuO particles. This work performs density functional theory (DFT) calculations to systematically probe the microscopic HCN heterogeneous reactions over the CuO particle surface. The results indicate that HCN is chemisorbed on the CuO surface, and the third dissociation step within the consecutive three-step HCN dissociations (HCN*→CN*→NCO*→N*) is the rate-determining step. Namely, the CN*/NCO* radicals can be deemed as an indicator of the performance of HCN removal due to their quite higher dissociation energies. With the existence of O₂, H₂O, and NO, the reaction mechanism of HCN conversion becomes extremely complex. Both DFT calculations and kinetic analyses determine that O₂, NO, and H₂O all significantly accelerate the consumption of CN*/NCO* radicals to produce various N-containing species (NOx or NH₃) to different extents. Finally, a skeletal reaction network in a system of O₂/NO/H₂O/HCN is concluded, which clearly elucidates that CuO exhibits excellent catalytic activity toward HCN removal.     

Population inversion between the H4 and the F4 excited states of Tm investigated by means of numerical solutions of the rate equations system in Tm-doped and Tm, Ho-codoped fluoride glasses

Population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ ions responsible for the 1.5 μm emission in Tm³⁺ singly doped (0.5%) and Tm³⁺, Ho³⁺-codoped fluoride (ZBLAN) glasses and its dependence on the Ho³⁺ concentration (x=0.2-1%) was investigated by means of numerical solution of the rate equations system for continuous pumping at 797 nm. Mean lifetimes of donor and acceptor states were evaluated by using the integration method applied to the best fitting of fluorescence curves previously reported. Lifetime values were used to obtain the rate constants of all non-radiative energy-transfer processes involved and a complete set of rate equations better describing the observations was given. The rate equations were solved by numerical method and the population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ was calculated to examine the beneficial effects on the gain associated with Ho³⁺ codoping. The results have shown that Tm³⁺ population inversion is reached only for high Ho³⁺-codoping (?0.3 mol%). Highest population inversion (∼1.6×10¹⁸ Tm³⁺ ions cm⁻³) was obtained in Tm(0.5%), Ho(1%)-codoped (ZBLAN) pumped by 2.8 kW cm⁻². This population inversion density is ∼6.4 times higher than that one observed in Tm:Tb:GLKZ, Tm:Tb:Ge-Ga-As-S-CsBr and Tm:Ho:Ge-Ga-As-S-CsBr for a similar pumping condition (∼2.5×10¹⁷ cm⁻³). In addition, Tm(0.5%):Ho(1%):ZBLAN presents the highest population inversion that linearly increases with the pumping intensity; this behavior does not show saturation effect at least for the maximum intensity of 12 kW cm⁻² employed. The use of 1 mol% of Ho³⁺-codoping maximizes the potential gain of Tm³⁺-doped (0.5%) ZBLAN to produce stimulated emission near 1.5 μm, making this material suitable for using it as fiber optical amplifier and/or fiber laser operating in 1.4-1.5 μm region of the spectrum.     

Electronic transition CN laser

An electric discharge pumped CN laser oscillating on the A²Π-X²Σ system is reported. Peak power of 20 kW in a 150 nsec fwhm pulse is obtained using a simple longitudinal electric discharge in several mmHg of HCN. Oscillation occurs on the (0,1) and (0,2) bands at ? 1.42 and 2.0μm respectively.     

Weakly forbidden vibration-rotation transitions ΔR ≠ 0 in CF4 laser

Known spectroscopic data on the 16 μm CF₄ laser are completely explained by considering weakly forbidden ΔR ≠ 0 vibration-rotation transitions. A rich fine structure of the v₂ + v₄ pumping band with specific spectral interval 0.01 + 0.03 cm^-1 has been experimentally observed. The components of this structure have been used for optical pumping of a CF₄ laser by a quasi-single mode continuously tunable high-pressure CO₂ laser.     

Nitrogen atom detection in low-pressure flames by two-photon laser-excited fluorescence

Nitrogen atoms have been detected in stoichiometric flat premixed H₂/O₂/N₂ flames at 33 and 96 mbar doped with small amounts of NH₃, HCN, and (CN)₂ using two-photon laser excitation at 211 nm and fluorescence detection around 870 nm. The shape of the fluorescence intensity profiles versus height above the burner surface is markedly different for the different additives. Using measured quenching rate coefficients and calibrating with the aid of known N-atom concentrations in a discharge flow reactor, peak N-atom concentrations in these flames are estimated to be on the order of 10¹²–5×10¹³ cm^–3; the detection limit is about 1×10¹¹ cm^–3.     

Tm and Tm-Tb-doped germanate glasses for S-band amplifiers

The mechanism involved in the Tm³⁺(³F₄)→Tb³⁺(⁷F_0,1,2) energy transfer as a function of the Tb concentration was investigated in Tm:Tb-doped germanate (GLKZ) glass. The experimental transfer rate was determined from the best fit of the ³F₄ luminescence decay due to the Tm→Tb energy transfer using the Burshtein model. The result showed that the 1700 nm emission from ³F₄ can be completely quenched by 0.8 mol% of Tb³⁺. As a consequence, the ⁷F₃ state of Tb³⁺ interacts with the ³H₄ upper excited state of Tm³⁺ slighting decreasing its population. The effective amplification coefficient β(cm⁻¹) that depends on the population density difference Δn=n(³H₄)-n(³F₄) involved in the optical transition of Tm³⁺ (S-band) was calculated by solving the rate equations of the system for continuous pumping with laser at 792 nm, using the Runge-Kutta numerical method including terms of fourth order. The population density inversion Δn as a function of Tb³⁺ concentration was calculated by computational simulation for three pumping intensities, 0.2, 2.2 and 4.4 kWcm⁻². These calculations were performed using the experimental Tm→Tb transfer rates and the optical constants of the Tm (0.1 mol%) system. It was demonstrated that 0.2 mol% of Tb³⁺ propitiates best population density inversion of Tm³⁺ maximizing the amplification coefficient of Tm-doped (0.1 mol%) GLKZ glass when operating as laser intensity amplification at 1.47 μm.     

Ni2+ doped LaMgAl11O19: A potential vibronic laser system near 1.1 μm

We report here the optical absorption and fluorescence characteristics of the Ni²⁺ ions in lanthanum hexa-aluminate LaMgAl₁₁O₁₉. It shows the existence of a broad-band emission extending from 0.95 up to 1.4 μm associated with the lower energy downward vibronic transition ³T₂(³F) → ³A₂(³F) of Ni²⁺ ions in quasi-octahedral symmetry sites. The lifetime of t his infrared emission has been measured at different temperatures from 14 up to 600 K and as a function of Ni²⁺ ion concentration. The results indicate that LaMgAl₁₁O₁₉:Ni²⁺ could be a solid-state laser material of great interest, since it would work at room temperature in a large spectral domain, provided that one uses pumping wavelengths which correspond to regions of minimal absorption by tetrahedrally coordinated Ni²⁺ ions, and also if one favours the relative occupancy of the Ni²⁺ ions in the octahedral sites by appropriate chemical treatments.     

Suppression of laser noise in CW 337μm HCN lasers

In a d.c.-discharge-excited 337 μm HCN laser, amplitude laser noise has been observed at the frequency range of 30 kHz to 1 MHz. The laser noise is classified into three types; oscillation noise having sharp peaks, broadly distributed noise having a center frequency and 1/f-noise. Characteristics of the laser noise have been studied experimentally. The laser noise is caused by small oscillation which appears on d.c.-discharge current and by random fluctuations of current and plasma density. The laser noise has been suppressed more than 30 dB by adjusting the laser parameters such as discharge current, pressure and flow rates of mixed gas (CH4₄ + N₂ + He) and added He.     

Excitation,inversion, and relaxation mechanisms of the HCN FIR discharge laser

Millimeter/submillimeter rotational absorption spectroscopy has been used as a diagnostic probe of a cw HCN discharge laser. This sensitive technique allowed in situ absolute population measurements of a number of vibrational states of HCN (including the upper lasing state) and other pertinent molecules. This unique set of data, which was obtained under a variety of discharge and laser conditions, is directly related to excitation, inversion, and relaxation processes. Along with elucidating several fundamental aspects of inversion and relaxation these results also strongly indicate that the primary laser excitation mechanism is near-resonant energy transfer from vibrationally excited nitrogen, N₂ (v=1), to the fundamental symmetric stretching mode of hydrogen cyanide, HCN(100), and subsequent thermal population exchange between HCN (100) and the upper laser state, HCN (110).Work supported by ARO Contract DAAG-29-83-K-0078     

New FIR laser lines from an optically pumped far-infrared laser with isotopic 13C16O2 pumping

A ¹³C¹⁶O₂ laser optically pumping a FIR laser has resulted in 17 new FIR cw emissions from 78.5 μm to 917 μm. The FIR media were: CD₃OD, CH₃OD, CD₃OH, NH₃ and ¹⁵NH₃. Interesting effects have been observed with a combination of NH₃ and CD₃OD resulting in a new FIR emission. Two new FIR emissions at 181.5 μm and 355.5 μm have been observed with a ¹²C¹⁶O₂ laser optically pumping CD₃OD.     

New FIR laser lines from optically pumped C2H3F, C2H3Cl, C2H3Br, C2H3CN, C2H5F, CH2CF2, HCOOH and CH3Br

Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C₂H₃F, C₂H₃Cl, C₂H₃Br, C₂H₅F, C₂H₃CN, CH₂CF₂, HCOOH and CH₃Br with a CO₂ laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.     

Self-activated Nd:Ba2NaNb5O12 optical super-lattices: Micro characterization and non-collinear laser light generation

Czochralsky grown Nd³⁺-ion doped barium sodium niobate (Ba₂NaNb₅O₁₂, “banana”) optical super-lattices have been characterized by a combination of chemical etching, optical microscopy, micro-Raman and micro-photoluminescence experiments. The presence of ferroelectric domains, induced during growth process, is accompanied by a periodic modulation of Nd³⁺-ion concentration as well as by a small lattice distortion. When Nd³⁺-ion laser action at ≈1.06 μm is achieved under 0.808 μm laser diode pumping, the singularities of refractive index caused by opposed ferroelectric domains lead to non-collinear intra-cavity propagation.     

Growth and optical properties of a new self-Q-switched laser crystal: Cr:Yb3Al5O12

Cr⁴⁺:YbAG (Cr⁴⁺:Yb₃Al₅O₁₂) crystal with a size up to Φ24 mm×30 mm was grown by the Czochralski method. In the absorption spectrum, there are two absorption bands at 939 and 969 nm, respectively, which are suitable for InGaAs diode laser pumping, and there is an absorption band at 1030 nm, which is suitable for passive Q-switched laser output at 1.03 μm. A broad emission spectrum from 970 to 1100 nm was exhibited from 940 nm wavelength pumping. This crystal is promising as a self-Q-switched laser crystal used for compact, efficient, highly stable, passive self-Q-switched thin chip solid-state lasers.     

Laser plasma plume kinetic spectroscopy of the nitrogen and carbon species

The formation and decay of carbon and nitrogen atoms, CN radicals and C₂ molecules were monitored using spatial‐ and time‐resolved emission spectroscopy in a plasma plume formed during laser ablation of a graphite target in nitrogen atmosphere. A simple exponential model was used to explain the effect of the individual chemical reactions and plasma dynamics on the measured kinetic characteristics. The succession of emissions C → N → CN was observed in the time‐resolved spectra, supporting the suggestion that the CN radical is formed mainly by the direct reaction C + N → CN or C₂ + N₂ → 2CN. The formation of CN radical was enhanced by the additional generation of atomic nitrogen through the RF discharge. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Infrared and far-infrared laser emissions from a TE CO2 laser pumped NH3 gas

In this paper, infrared (IR) and far-infrared (FIR) laser emissions from a TE CO₂ laser pumped NH₃ gas are reported. 8 IR laser emissions near the wavelength of 12 μm were observed by using 4 different CO₂ laser lines for the pumping. 3 IR laser emissions in P-branch of vibrational-rotational band (ν₂ → G) oscillated simultaneously in two pumping cases, i.e. pumping with the R(30) or R(16) line of 9.4 μm band from the CO₂ laser. 26 FIR laser emissions (26.45 μm ～ 281.0 μm) were observed by using 12 different CO₂ laser lines, and the 10 FIR emissions of them may be new laser emissions as far as we know.     

Diode-pumped colour-centre lasers tunable in the 1.5 µm range

Under pumping with a 990 nm, 1 W laser diode, continuous-wave (cw) tunable laser emission in the 1.5 µm wavelength range was obtained from two different colour centres: Tl⁰(1) in NaCl:Tl⁺ and (F ₂ ⁺ )_H in NaCl:OH^–. The results are compared to those recently obtained with a similar apparatus and Tl⁰(1) centres in KCl:Tl⁺. The highest output power (30 mW) and the broadest tuning range (1.48–1.68 µm) were achieved with (F ₂ ⁺ )_H centres.     

Theoretical performance of an HF chemical CW laser

A quantitative analysis of an HF cw chemical laser is presented that includes the influence of stimulated emission on the reacting medium. The numerically determined solutions encompass one-dimensional fluid mechanics, chemical kinetics, radiative de-excitation, and their mutual interaction. A comprehensive parametric study examines the effects due to changed plenum conditions, mixture ratios and cavity parameters. Best efficiency is obtained when the pumping is by the F + H₂ reaction. Pumping by the chain reaction sequence F + H₂ → HF(υ ≤ 3) + H and H + F₂ → HF(υ ≤ 6) + F results in substantially lower efficiencies due to increased HF-HF vibration-translation deactivation. Detailed discussions are presented of (1) vibration-vibration and vibration-translation energy exchange, (2) chemical efficiency, (3) mechanisms that cause lasing termination, and (4) cavity operation with a selective grating.     

Mössbauer studies of photochemical reaction products of Ru(bpy)3 2+ iron cyanide double complexes

The reductive and the oxidative electron-transfer photochemical reaction system of light-irradiated the mix solutions of Ru(bpy)₃ ²⁺ with [Fe(CN)₆]^4–, [Fe(CN)₆]^3–, [Fe(CN)₅NO]^2– and PB (Prussian Blue) have been studied. The double complexes which isolated from the precipitates of the photochemical reaction have been identified by means of Mössbauer spectroscopy. In order to clarify the chemical states of these isolated double complexes, we have (prepared and) studied Mössbauer spectra of the double complexes such as [Ru(bpy)₃]₃[Fe(CN)₆]₂.14H₂O, [Ru(bpy)₃]₂[Fe(CN)₆].10H₂O, [Ru(bpy)₃][Fe(CN)₅NO].4H₂O, and [Ru(bpy)₃][PB]₂.xH₂O.     

A CW DCN waveguide laser of high volumetric efficiency

This paper describes a CW submillimeter waveguide laser operating on 190 and 195 μm DCN lines with high volumetric efficiency. The laser cavity is a 3.2 cm inner diameter, 70 cm long, Pyrex tube with plane reflectors (one of them is a copper mesh) against its ends. After optimization of various parameters (such as the N₂:CD₄:He gas mixture, the pressure and the discharge current, the wall temperature and the output coupling), this laser, with only 57 cm long active discharge, delivers 8.4 and 7.6 mW on the 190 and 195 μm lines, respectively, for the EH₁₁ mode. This represents volumetric powers of 75 and 65 μW cm^-3. The free space propagation of the EH₁₁ fundamental mode was found to be as for a gaussian beam, and the absorption of the laser beam in the atmosphere was also measured.     

Dy3+掺杂Ge-Ga-S-CsI玻璃中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy³⁺:Ge-Ga-S-CsI硫卤玻璃样品,测试了样品拉曼光谱、折射率、吸收光谱、近红外及中红外荧光谱.应用Judd-Ofelt理论计算了Dy³⁺离子的强度参数 (Ω_i, i=2,4,6)、自发辐射跃迁概率(A)、荧光分支比(β)、以及辐射寿命(τ_rad)等光谱参数.研究了810 nm激光抽运下样品中红 关键词： 硫系玻璃 中红外发光 3+掺杂')" href="#">Dy³⁺掺杂 多声子弛豫