Cr改性钒基催化剂对NH3低温选择性催化还原NOx的影响

火电厂和机动车辆等的NOx排放量与日俱增, NOx的治理已成为环境保护的重要组成部分.以NH3作为还原剂的选择性催化还原(SCR)技术是目前消除NOx最为高效的方法之一.该反应最为典型的催化剂是V2O5–WO3(MoO3)/TiO2,催化活性窗口为250–400 oC.国外通常将SCR系统置于省煤器之后,此时烟气温度在300 oC以上,催化剂能保持较高的活性,但易受到烟气中高浓度烟尘、SO2和碱金属等的影响,寿命相对较短.此外,高温工艺中副产物硫酸铵的堵塞也是一个不可忽视的问题.因此,将SCR脱硝装置设在脱硫除尘之后成为一种优选技术之一,但烟气温度会降至250 oC以下,而常规的钒基催化剂不能满足低温活性要求.通过添加助剂或改变载体可改善钒基催化剂的低温活性,同时保持其高效的抗硫能力.
　　本文以Cr和V为活性组分, TiO2为载体,采用浸渍法制备了铬钒钛(Cr–VOx/TiO2)系列催化剂,考察了它们的低温脱硝活性和抗水抗硫性,并通过N2吸附-脱附、X射线衍射、NH3程序升温脱附(NH3-TPD)、H2程序升温还原(H2-TPR)和X射线光电子能谱等手段对催化剂进行了表征,分析了Cr–V催化剂的作用机制.
　　结果显示,当n(Cr)：n(V)为0.2：0.8,活性组分负载量为10 wt%时, Cr–VOx/TiO2催化剂表现出最佳的低温催化活性;当反应温度为160°C时, NOx转化率达到90%以上,明显优于其他催化剂,同时活性窗口(160–300°C)得到拓宽. NH3-TPD结果表明, VOx/TiO2催化剂表面呈中弱酸性,随着Cr的添加,钒基催化剂的NH3脱附峰向高温拓宽,说明其表面强酸量有所增加, Cr0.2–V0.8/TiO2在160–300°C范围内均出现了NH3的脱附峰,此时催化剂表面弱酸量最大.当n(Cr)：n(V)大于0.2：0.8时,催化剂表面出现强酸位,这种强酸位不利于NH3脱附,从而不利于SCR反应的进行.因此适量Cr的添加有助于提高钒基催化剂表面弱酸及中性酸量. H2-TPR结果发现,助剂Cr的添加使得催化剂表面氧量增加,这可能是由于Cr的添加形成了较多的氧空穴和未饱和的化学键.催化剂表面化学吸附氧是氧化还原反应最活跃的氧物种,在SCR反应中,表面氧可作为NO的吸附介质参与到催化剂表面反应中,可有效提高SCR反应速率.通过考察活性组分负载量对催化剂活性的影响,发现不同负载量催化剂的催化活性依次为10 wt%>20 wt%>50 wt%>5 wt%. XPS分析发现,当负载量为10 wt%时,催化剂表面非计量的钒离子和化学性质活跃的自由电子最多,因此表现出最佳的SCR活性;当负载量过高时,大量氧化物堆积烧结形成V2O5和Cr2V4O13,覆盖了钒离子活性位点,降低了催化剂脱硝效率.
　　催化剂在220°C表现出良好的抗硫性,在通入100 ppm SO212 h后NOx的转化率仍可达99%以上,并未出现硫中毒现象.同时该催化剂也表现出较好的抗水性,在通入10 vol%水蒸气12 h后, NOx转化率仍能达85%以上.     

Direct determination of acrylamide in food by gas chromatography with nitrogen chemiluminescence detection

A method of gas chromatography with nitrogen chemiluminescence detection and using standard addition is described for the determination of acrylamide in heat‐processed foods. Using a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation method removes the acrylamide precursors completely, and the risk of overestimating acrylamide concentration due to additional analyte formation in the hot gas chromatograph inlet is also avoided. Sample preparation is rapid and inexpensive. A Deans switch device is utilized to heart‐cut acrylamide and to prevent interferences from the solvent and matrix from reaching the detector. The pre‐column is backflushed at high temperature to maintain a clean baseline and shorten the cycle time compared to baking out the column. Quantitation using standard addition is employed for compensation of potential variability in the acrylamide extraction efficiency in acetonitrile. The limit of detection and the limit of the quantification obtained for this method are 27 and 81 μg/kg, respectively, in food samples (equivalent to 3.5 and 10.6 μg/L in acetonitrile, respectively), and the linear range is 76–9697 μg/kg in food samples (equivalent to 10–1280 μg/L in acetonitrile) with an R² value of 0.9999.     

Quantification of nitrogen compounds in diesel fuel samples by comprehensive two‐dimensional gas chromatography coupled with quadrupole mass spectrometry

Although several methods for the analysis of nitrogen compounds in diesel fuel have been described in the literature, the demand for rapid, sensitive, and robust analyses has increased in recent years. In this study, a comprehensive two‐dimensional gas chromatographic method was developed for the identification and quantification of nitrogen compounds in diesel fuel samples. The quantification was performed using the standard addition method and the analysis was conducted using comprehensive two‐dimensional gas chromatography coupled with fast quadrupole mass spectrometry. This study is the first to report quantification of nitrogen compounds in diesel fuel samples using the standard addition method without fractionation. This type of analysis was previously performed using many laborious separation steps, which can lead to errors and losses. The proposed method shows good linearity for target nitrogen compounds evaluated (m‐toluidine, 4‐ethylaniline, indole, 7‐methylindole, 7‐ethylindole, carbazole, isoquinoline, 4‐methylquinoline, benzo[h]quinolone, and acridine) over a range from 0.05 to 2.0 mg/L, and limits of detection and quantification of <0.06 and 0.16 mg/L, respectively, for all nitrogen compounds studied.     

First-principles study on Fe2B2 as efficient catalyst for nitrogen reduction reaction

Ammonia (NH₃) is considered an attractive candidate as a clean, highly efficient energy carrier. The electrocatalytic nitrogen reduction reaction (NRR) can reduce energy input and carbon footprint; therefore, rational design of effective electrocatalysts is essential for achieving high-efficiency electrocatalytic NH₃ synthesis. Herein, we report that the enzymatic mechanism is the more favourable pathway for NRR, due to lower limiting potential (−0.44 V), lower free energy (only 0.02 eV) of the first hydrogenation step (*N–N to *NH–N), and more electron transfer from Fe₂B₂ to the reaction species. In addition, both vacancies and dopants can be helpful in reducing the reaction energy barrier of the potential-determining step. Therefore, we have demonstrated that Fe₂B₂ is a potential new candidate for effective NRR and highlighted its potential for applications in electrocatalytic NH₃ synthesis.     

光电光谱仪测定合金结构钢中的氮

本文叙述了用光谱仪快速定量分析合金钢中的氮,并对测定氮光谱线的选择、氮的分析条件、校准曲线的拟合及样品分析等问题进行了讨论。本方法的分析范围在0.0010%-0.021%之间,检出限为0.0007%。为冶炼品种钢提供了快速准确的分析方法。     

Surface relaxation and near-surface atomic displacements in the N/Cu(1 0 0) self-ordered system

The atomic displacements of Cu atoms induced by nitrogen adsorption on Cu(1 0 0) have been studied by channelling–blocking of swift ⁴He ions. This study has been performed at two adsorption stages. The first one corresponds to the formation of a dense, two-dimensional, self-ordered array of square-shaped islands covered by nitrogen. The second one corresponds to uniform coverage at saturation. We have determined by nuclear reaction analysis the absolute quantity of nitrogen adsorbed at these two stages. The values obtained, when confronted to previous observations of these stages by low energy electron diffraction and by scanning tunnelling microscopy, demonstrate that nitrogen remains mostly at the sample surface and that the N concentration in bulk Cu could not exceed 1%. However, channelling measurements show that this surface adsorption generates atomic displacements of Cu atoms down to depths of a few ten (1 0 0) interplanar distances. In the mean time, blocking measurements reveal that nitrogen adsorption induces a strong surface expansion: the interplanar distance between the first two (1 0 0) planes increases of about 0.2 Å, in contrast with the weak contraction observed on bare Cu(1 0 0) surfaces. This observation supports the hypothesis that, when nitrogen is adsorbed, the surface is submitted to stress variations, from tensile to compressive stress for, respectively, bare and nitrogen-covered surface regions. The surface forces corresponding to such variations have been introduced in molecular dynamics simulations. For coverage leading to self-ordering, these simulations do indeed predict displacements of subsurface Cu atoms. The adjustment of these displacements to those measured by channelling gives the amplitude of the stress variation.     

介质阻挡放电等离子体脱除氮氧化物的发射光谱研究

在大气压下, NO/N2体系中, 利用发射光谱技术对50 Hz和5 kHz交流介质阻挡放电等离子体在200～900 nm范围内进行了诊断. 在632、674.5、715.5和742 nm等处测得了N原子的谱线. 利用化学发光法NOx分析仪, 模块式红外吸收气体分析检测仪, 大气压下直连质谱多种检测手段对放电前后的稳定物种进行了分析, 观察到O2的生成. 初步讨论了无氧条件下介质阻挡放电等离子体中NO脱除的反应机制.     

高钛钛铁中氮的滴定法测定

利用经典的滴定法,用0.005mol·L~(-1)H_2SO_4溶液吸收在强碱性条件下,用水蒸气蒸馏出的氨,并以0.01mol·L~(-1)NaOH标准溶液返滴定过量的H_2SO_4,测定样品中氮的含量,研究了测定的最佳条件,拟定了高钛钛铁中氮的测定方法,样品的加标回收率为94%～97%,方法用于测定高钛钛铁中的氮,测定下限可至0.04%,RSD<3.5%(n=5),且稳定性好,结果满意.     

Synthesis,Structures and Properties of Three New Compounds Based on Multidentate Ligand Containing Triazole and Pyrimidine

Three new compounds, namely, [Zn(mtpo)₂(H₂O)4](1), [Cd(mtpo)₂·CH₃CH₂OH]_n(2) and [Mn(mtpo)₂·CH₃CH₂OH]_n(3)(Hmtpo=4,7-dihydro-5-methyl-7-oxo-[1,2,4]triazolo[1,5-a]pyrimidine), have been synthesized via hydrothermal or solvothermal methods and characterized by means of elemental analyses, Fourier transform infrared(FTIR) spectroscopy, powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and single-crystal X-ray diffraction. The results obtained from the single-crystal X-ray diffraction indicate that compound 1 has a mononuclear structure, and crystallizes in a monoclinic crystal system with P2₁/c space group, which exhibits a 2D supramolecular network constructed by hydrogen bonds and π-π interactions. Compounds 2 and 3 are isomorphous and crystallize in a tetragonal system with space group of I4₁/a. The M²⁺(M=Cd, Mn) ions in compounds 2 and 3 have the octahedral coordination geometry. Hmtpo acts as a bridging ligand linking the metal ions to form an infinite 3D framework with 4-connected {4²·8⁴} topology. There are hydrogen bonds between the guest ethanol molecules and the mtpoligands, which make the ethanol molecules exist in a 3D framework. In addition, luminescent properties of compounds 1 and 2 as well as magnetic property of compound 3 were investigated and water vapor adsorption and nitrogen sorption for compounds 2 and 3 were researched at 298 and 77 K, respectively.     

马铃薯光谱及数字图像特征参数对氮素水平的响应及其应用

为准确、快速地掌握马铃薯氮素状况,提高马铃薯对氮素的利用率,采用便携式高光谱地物波谱仪、数码相机与SPAD-502叶绿素仪获取马铃薯冠层图像、叶片光谱、叶片SPAD值,分析不同施氮水平下马铃薯两个关键生育时期数字化指标、叶片光谱指标、SPAD、产量的变化状况,以SPAD为辅助验证指标,以产量为氮素施用效率评价,分析数字化指标、叶片光谱与SPAD、产量的关系,明确最佳施氮水平下数字化指标、叶片光谱指标的临界值,以期探讨快速、简便进行马铃薯氮素营养诊断的方法。结果表明：(1)随着施氮水平的增加红边位置出现了“红移”,红边参数REP,Lwidth,FD_Max增加,Lo减小。(2)随着施氮水平增加数字化指标G/B和(G-B)/(R+G+B)逐渐降低,B/(R+G+B)逐渐增加。(3)SPAD随施氮量增加而提高,施氮量增加低氮水平增产效果明显,高氮水平增产效果不明显。光谱、红边参数、数字化指标与SPAD、产量相关性较好,据此建立了各个指标评价马铃薯氮营养丰缺的量化标准。表明运用数字图像与光谱技术进行马铃薯氮素营养诊断具有可行性,为马铃薯精准氮素营养监测提供研究思路与技术支撑。