Absorption coefficients of O3 at CO2 laser wavelengths

The O₃ absorption coefficients for the rotational lines P(12)–P(28) of the 9.4 μm emission band of the CO₂ laser are presented. Measurements were made in O₃–air dilute mixtures (20–600 ppm) at 25°C and a total pressure of 1013.25 h Pa using a frequency stabilized cw CO₂ laser and values have been determined with greater precision than in previously reported studies.     

Solid-state electrochemical CO2 sensor by coupling lithium ion conductor (Li2CO3-Li3PO4-Asl2O3) with oxide ion-electron mixed conductor (La0.9Sr0.1MnO3)

A solid-state electrochemical cell of the type O₂(air), PtLa_0.9Sr_0.1MnO₃/Li₂CO₃(+5 mol% Li₃PO₄ + 6 mol% Al₂O₃)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, was used as an electrolyte, and the perovskite-type oxide (La_0.9Sr_0.1MnO₃)/O₂-electrode as a reference electrode. The electromotive force (EMF) of the cell was found to be proportional to the logarithm of CO/₂ partial pressure in CO₂/O₂/N₂ gas mixtures at temperatures between 300 and 400 °C. The EMF responded to changes of CO₂ partial pressure within 1 min at 400 °C. The sensitivity to CO₂ of this cell was not affected by coexistence of O₂, and the EMF remained constant after the first 15 days. The mechanism for sensing CO₂ is discussed.     

O2/CO2气氛下循环流化床煤燃烧SO2排放

在热输入功率50 kW的循环流化床O₂/CO₂燃烧试验装置上研究燃煤SO₂排放特性及石灰石脱硫机理。结果发现,未添加石灰石时,O₂/CO₂气氛下SO₂排放量比相同O₂浓度的空气气氛下低;随着O₂浓度的升高,排放量升高。相同钙硫摩尔比下,O₂/CO₂气氛下石灰石的脱硫机理以直接脱硫为主,脱硫效率比空气气氛下高;随着O₂浓度的增加,石灰石脱硫效率提高。     

CO2及其碳同位素比值高精度检测研究

改进了一种基于傅里叶变换红外光谱法测量CO₂气体的装置, 改进后的装置能够提高CO₂检测精度, 并能同时测量CO₂碳同位素比值. 研究了温度和压力对CO₂浓度值和CO₂碳同位素比值测量的影响规律. 利用该装置连续测量了标准CO₂气体和环境大气, 对标准CO₂气体测量得到的CO₂浓度值及其碳同位素比值进行温度和压力影响修正, 获得了较好的精度和准确度. 关键词： 光谱学 同位素比值 傅里叶变换红外光谱 二氧化碳     

正磷酸盐晶体Ba3(PO4)2和Sr3(PO4)2高温拉曼光谱研究

测量了碱土金属正磷酸盐Ba₃(PO₄)₂和Sr₃(PO₄)₂常温及高温拉曼光谱, 对拉曼振动模式进行指认, 并分析了晶体拉曼振动光谱及晶体结构在高温下的变化. 在温度升高的过程中, 拉曼振动频率向低频移动且振动峰宽度展宽, 晶体中的P-O平均键长随温度升高而变长, 但O-P-O的键角并未发生变化. 晶体在900 ℃以下无结构相变发生. 关键词： 3(PO₄)₂和Sr₃(PO₄)₂')" href="#">Ba₃(PO₄)₂和Sr₃(PO₄)₂ 高温拉曼光谱 振动模式 高温结构     

Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O

The reaction of CO₂ and H₂O to form bicarbonate (HCO⁻₃) was examined on the nearly perfect and vacuum annealed surfaces of TiO₂(110) with temperature programmed desorption (TPD), static secondary ion mass spectrometry (SSIMS) and high resolution electron energy loss spectrometry (HREELS). The vacuum annealed TiO₂(110) surface possesses oxygen vacancy sites that are manifested in electronic EELS by a loss feature at 0.75 V. These oxygen vacancy sites bind CO₂ only slightly more strongly (TPD peak at 166 K) than do the five-coordinated Ti⁴⁺ sites (TPD peak at 137 K) typical of the nearly perfect TiO₂(110) surface. Vibrational HREELS indicates that CO₂ is linearly bound at the latter sites with a ν_a(OCO) frequency similar to the gas phase value. In contrast, oxygen vacancies dissociate H₂O to bridging OH groups which recombine to liberate H₂O in TPD at 490 K. No evidence for a reaction between CO₂ and H₂O is detected on the nearly perfect surface. In sequentially dosed experiments on the vacuum annealed surface at 110 K, CO₂ adsorption is blocked by the presence of preadsorbed H₂O, adsorbed CO₂ is displaced by postdosed H₂O, and there is little or no evidence for bicarbonate formation in either case. However, when CO₂ and H₂O are simultaneously dosed, a new CO₂ TPD state is observed at 213 K, and the 166 K state associated with CO₂ at the vacancies is absent. SSIMS was used to tentatively assign the 213 K CO₂ TPD state to a bicarbonate species. The 213 K CO₂ TPD state is not formed if the vacancy sites are filled with OH groups prior to simultaneous CO₂+H₂O exposure. Sticking coefficient measurements suggest that CO₂ adsorption at 110 K is precursor-mediated, as is known to be the case for H₂O adsorption on TiO₂(110). A model explaining the circumstances under which the proposed bicarbonate species is formed involves the surface catalyzed conversion of a precursor-bound H₂O–CO₂ van der Waals complex to carbonic acid, which then reacts at unoccupied oxygen vacancies to generate bicarbonate, but falls apart to CO₂ and H₂O in the absence of these sites. This model is consistent with the conditions under which bicarbonate is formed on powdered TiO₂, and is similar to the mechanism by which water catalyzes carbonic acid formation in aqueous solution.     

IR-spectra of (CO2)2 dimers and collision-induced absorption of carbon dioxide in the region of the fermi doublet (ν1, 2ν2)

The positions and intensities of all vibrational transitions in the (ν₁, 2ν₂) Fermi doublet region of (CO₂)₂ dimers are obtained by means of variational method. The collision-induced absorption in compressed carbon dioxide is shown to be mainly due to dimeric absorption. Assignment of ν₁ and 2ν₂ vibrational bands in isolated CO₂ molecule is performed by consideration of the symmetries and intensities of dimeric vibrations.     

Na2CO3的高压拉曼光谱研究

碳酸盐是碳在地球内部的重要载体之一,其在地幔高温高压条件下的晶体化学是理解地球深部碳的赋存状态和循环过程的关键,而结构稳定性和相变是晶体化学最基本的研究内容。碳酸钠（Na₂CO₃）是一种常见的碱性碳酸盐矿物,在产自地幔过渡带-下地幔的金刚石中已发现含钠的碳酸盐矿物包裹体,这成为碳酸钠能够俯冲进入地幔深部的直接矿物学证据。前人利用拉曼光谱技术研究了Na₂CO₃在常温常压下的晶格振动模式,但其在高压下的稳定性和结构变化却鲜有报道。利用金刚石压腔装置结合先进的共聚焦拉曼光谱技术,以硅油作为传压介质,在准静水压力条件下,在0.001～27.53 GPa压力区间对Na₂CO₃粉末在600~1 200 cm-1波段的振动特征进行了细致地分析。本次实验重点分析了[CO₃]2-基团振动模式在升压和卸压过程中的行为。结果表明,在0.001～11.88 GPa压力范围内,[CO₃]2-基团对称伸缩振动γ₁（1 088.06和1 070.76 cm-1）、反对称伸缩振动γ₃（865.10和797.50 cm-1）和面内弯曲振动γ₄（720.10和696.71 cm-1）都出现了振动峰的分裂。随着压力增加,所有振动峰都向高频率漂移,半高宽也逐渐增加。在13.40 GPa时,Na₂CO₃发生结构相变,具体表现为690.08 cm-1处出现1条新的拉曼峰,并且随着压力升高该峰的强度逐渐增大。同时反对称伸缩振动峰γ₃以及面内弯曲振动峰γ₄的强度持续减弱,半高宽也继续变大。这些现象表明Na₂CO₃结构相变源于[CO₃]2-内部晶格变化。当压力卸载到4.18 GPa时,[CO₃]2-的振动模式与常温常压下的完全吻合,相变出现的新峰也已经消失,表明该相变是由[CO₃]2-基团畸变引起的并且具有可逆性。继续升压至27.53 GPa,拉曼光谱继续蓝移,Na₂CO₃的拉曼谱线再没有变化,说明高压相在这一压强范围内保持稳定。在整个加压过程中,反对称伸缩振动γ₃和面内弯曲振动γ₄处的拉曼峰出现强度减弱现象。同时也计算了各个峰频率对压力的依赖系数dγ/dP,结果显示[CO₃]2-基团内各个振动模式对压力的响应是不同的,这很可能与Ｃ-Ｏ键的键长有关。最后,对比发现,对称伸缩振动γ₁峰的强度比反对称伸缩振动γ₃和面内弯曲振动γ₄峰的强度大,并且[CO₃]2-基团对称伸缩振动γ₁受压力影响相对较小,可以用来区别不同种类的碳酸盐矿物。     

Electrical conductivity and defect structure of Mg-doped Cr2O3

The electrical conductivity of Cr₂O₃ nominally doped with 2 mol% MgO has been studied by the four point a.c. technique as a function of the oxygen activity (O₂ + Ar, CO + CO₂ and H₂ + H₂O) in the temperature range 400–1200 °C. It is concluded that Cr₂O₃ doped with MgO is an extrinsic conductor and that the dissolved Mg-dopant is compensated by the formation of electron holes at near atmospheric oxygen pressures and by oxygen vacancies (or possibly interstitial chromium ions) at highly reduced oxygen activities (in CO + CO₂ and H₂ + H₂O gas mixtures). In H₂ + H₂O mixtures Mg-doped chromia also dissolves hydrogen as protons and significantly affects the defect structure and electrical conductivity. The defect structure of the oxide under various conditions is discussed.     

O2/CO2气氛下CO对煤焦异相还原NO影响的研究

为揭示O₂/CO₂燃烧过程中高浓度的CO对煤焦异相还原NO的影响,在1073 K温度下使用山西褐煤在卧式炉上进行了实验。分别对O₂/CO₂浓度比及CO浓度下NO的还原特性进行详细实验研究。研究结果表明:在O₂/CO₂气氛下,O₂浓度为30%时具有较高的还原率;相同O₂浓度下O₂/CO₂气氛较空气气氛NO还原率高,表明在CO存在的条件下,高浓度的CO₂会促进NO的还原;当CO浓度从1.5%逐渐升高时,NO的还原率逐渐降低,到CO浓度为5%时,NO还原率比没有加入CO时还要低,而在空气气氛下CO浓度的变化对NO的还原率影响较小。     

稀释剂对H2/CH4预混火焰熄灭特性影响

掺氢天然气在稀释气体作用下的熄灭特性研究对实际燃烧设备的设计和优化具有重要的指导意义。本文利用对冲火焰法测量了掺氢天然气层流火焰在N₂和CO₂作用下的熄灭拉伸率,并采用数值模拟耦合详细化学反应机理对N₂,CO₂和He的稀释剂效应展开研究。结果表明,Li、GRI Mech 3.0和FFCM-1机理均能定性反映燃料熄灭拉伸率随当量比的变化规律,且FFCM-1机理综合预测精度最高。实验和模拟发现,不同稀释剂气体对掺氢天然气熄灭拉伸率降低幅度满足:He22。进一步研究发现,CO₂由于热容大,在反应体系中会降低火焰温度,同时增强了链终止反应强度,通过热效应和化学效应两方面对火焰熄灭特性起作用。He则能显著改变燃料混合物的平均摩尔质量,从而改变体系中重要反应物和自由基的扩散特性,从扩散效应方面影响火焰的熄灭特性。     

Emission spectroscopy of ν10 band of vinyl bromide

By pumping with a pulsed CO₂ laser we have observed many FIR emissions in vinyl bromide that we have assigned to the ν₁₀ band at 942 cm⁻¹. We have been able also to assign many other FIR lines observed in previous works, so that we have derived new spectroscopic constants for the vibrational excited level.     

Interaction of CO2 with Cs-promoted Fe(110) as compared to Fe(110)/K+CO2

The interaction of CO₂ with Cs-promoted Fe(110) at 85 K as well as temperature-dependent reactions between 100 and 700 K have been studied by means of ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). Several surface species could be detected at 85 K, i.e. carbon monoxide (CO), carbonate (COⁿ⁻₃), physisorbed linear carbon dioxide (CO^lin₂) and very small amounts of oxidic oxygen (O_ox). An oxalate species (C₂O^m−₄) could not be identified definitively, but from comparison with the literature there is evidence that C₂O^m−₄ is present. Increasing the temperature after saturation with CO₂ leads to a complicated reaction behaviour. CO₂ either desorbs or dissociates into CO and COⁿ⁻₃ or forms C₂O^m−₄ at temperatures between 85 and 160 K. Above 160 K C₂O^m−₄, decomposes in parallel reactions into CO₂, COⁿ⁻₃ and CO. Above 320 K, adsorbed CO either desorbs into the gas phase or dissociates into C and O. In the temperature region between 500 and 700 K a recombination of C and O to CO and the desorption of Cs take place. As in the case of Fe(110)/K+CO₂, at high alkali coverages two carbonate species could be detected which dissociate upon heating at different temperatures. The system Fe(110)/Cs+CO₂ is proved to be very similar to the system Fe(110)/K+CO₂.     

Ba2(Cu0.7Cd0.3)O3: a new double-center perovskite structure

A new phase of Ba₂(Cu_0.7Cd_0.3)O₃ has been discovered. The composition of the phase was examined by energy dispersive X-ray spectrometry. The phase exhibits a tetragonal structure with lattice constants a=4.077 Å and c=7.970 Å, and its space group is P4/mmm. We propose a double-center-perovskite structure model, which is similar to that of (Ba, Sr)₂CuO₂(CO₃) [1, 2]. The simulated XRD is close to the observed one. The analysis results of elemental analyzer and Fourier transform infrared spectrometer reveal that the phase does not contain CO . The cuprate is an insulator, but its new cell structure and the large size of the CuO₂ planes seem to suggest a good reason for researching new superconductors. The roles of CdO in the solid state reaction and the formation of the new phase are discussed.     

Cold-cathode, glow-discharge, electron-beam gun pumped short pulse CO2 lasers

A pulsed cold-cathode glow-discharge electron beam gun emitting an electron-beam of 150 keV energy and 45 cm² cross-sectional area has been used to pump a short pulse CO₂ laser. A fast discharge capacitor bank was used to help make the design simpler than that employed in liquid coaxial lines. The system developed is capable of producing a CO₂ laser pulse of 1 J for about 200 ns duration.     

Infrared fluorescence from exciting the v1 and v8 modes of CF2Cl2 with a TEA CO2 laser

Infrared fluorescence from CF₂Cl₂ molecules excited with a TEA CO₂ laser below dissociation threshold, is time resolved with a HgCdTe detector without spectral resolution in the range 1100-700 cm^-1. The signal fits well to a sum of three exponentials, which are interpreted as a bulk vibration-vibration (V-V) energy transfer between the fraction of highly excited and non-excited molecules in the irradiated volume, vibro-translation (V-T) deactivation and diffusional heat and mass transport to the surrounding. The measured V-V and V-T rates increase with vibrational excitation and the V-T deactivation is independent on the observed modes (v₁/v₆ or v₈) if v₈ or v₁ are excited respectively.     

CO2在金属有机骨架材料有机链上的吸附机理研究

金属有机骨架是一种新型的温室气体CO₂吸附材料。本文采用密度泛函理论（DFT）方法研究CO₂在MOF-5有机链上的6种不同吸附位置及其3种不同构型下的吸附行为。考虑GGA水平下三种不同泛函对计算结果的影响,对比发现GGA/PW91泛函能够较好地计算CO₂分子与有机链原子之间的弱范德华力;发现CO₂分子与苯环边相交以及与苯环上的碳原子平行是两种吸附能最大的构型;利用Br原子替代苯环上的H原子可以显著增强对CO₂分子的吸附能力,为设计具有较高CO₂吸附能力的MOFs材料提供理论依据。     

Surface interaction between H2 and CO2 over silicalite-supported platinum

Infrared spectroscopic evidence is presented for the formation of linearly bonded CO species, as a result of surface interaction between H₂ and CO₂ at room temperature over silicalite-supported Pt. Comparison with direct CO adsorption results suggests that the active sites for this CO₂ reaction are the corner or step sites on platinum particles. The CO formed on these active sites then migrates to other sites on the surface of Pt particles. Co-adsorbed hydrogen and water make the linearly bonded CO species more strongly adsorbed on Pt particles. However, exposure to oxygen or air at room temperature effectively removes these CO species.     

载体结构对固态胺吸收CO2性能的影响

利用六种孔结构不同的商业无定形硅胶制备了不同四乙烯五胺（TEPA）担载量的固态胺吸收剂。吸收剂的微观结构通过BET和SEM测试;并在TGA反应器中,考察固态胺在30～80℃,CO2体积分数为1%～100%范围内的吸收性能。实验表明,固态胺吸收CO₂性能与温度、CO₂浓度以及载体结构有密切的联系。固态胺适合在低温（30～60℃）低CO₂浓度下（约10%）进行CO₂分离。载体结构通过影响最优担载量,从而影响固态胺吸收性能,孔容和孔径分别在1.211 cm³/g和13 nm附近的载体在担载量为45%时拥有最好的吸收能力（2.87 mmol/g）。     

新型燃煤发电-CO2捕获-供热一体化系统

本文在深入分析燃煤电站CO₂捕获和汽水系统热平衡的基础上,提出一种新型燃煤发电-CO₂捕获-供热一体化系统。该系统通过汽水流程、碳捕获流程及地暖供热流程的有效集成,实现了系统中、低温余热的高效利用,降低了碳捕获对电厂效率的影响。分析结果显示,本文提出的一体化系统,在CO₂回收率90%时,供电效率可达31.32%,供电效率降低8.96%,而传统化学吸收法碳捕获电站效率惩罚普遍在10～12个百分点或更高。同时,该系统可供热350 MW,全厂（火用）效率达34.49%,全厂热效率高达55.88%;该系统以较少的能耗代价实现高效供电、供热与CO₂减排,为燃煤发电机组碳减排提供了独特的学术思路与技术方案。