NOx对La1-xMxMnO3催化氧化碳烟活性影响的研究

采用铯、钾、铈(Cs、K、Ce)部分取代镧(La)制备了La1-xMxMnO3催化剂,并分析了催化剂的比表面积和晶格结构。在O2、NO O2、NO2 O2三种不同的气体氛围下开展了碳烟、碳烟 催化剂的程序升温氧化试验,考察NOx对碳烟催化氧化活性的影响。研究结果表明,NOx的存在显著促进了碳烟的催化氧化,各特征温度降幅均在100 K左右,NO2的影响强于NO,但与无催化剂时相比,两者的差距明显缩小,这主要是由于NOx在催化剂表面可发生氧化还原循环反应。NOx存在并未影响催化剂活性的排序,Cs取代催化剂的活性依然最高,NO存在时碳烟的起燃温度、峰值温度和燃尽温度降低到618 K、667 K和706 K,NO2存在时碳烟的起燃温度、峰值温度和燃尽温度降低到592 K、657 K和679 K。初步分析了NOx存在时碳烟催化氧化的机理。     

La1-xKxMnO3钙钛矿型催化剂同时去除碳烟颗粒物和NOx的性能研究

通过柠檬酸络合法制备了一系列钙钛矿型催化剂La_(1-x)K_xMnO_3(x=0.0～0.5)。通过程序升温氧化反应测试了催化剂同时去除碳烟颗粒物和NO_x的性能。采用X射线衍射(XRD)、扫描电镜(SEM)、氢气程序升温还原(H_2-TPR)以及X射线光电子能谱(XPS)等表征技术分析了经过A位掺杂的催化剂与基础催化剂产生活性差异的原因。结果表明:所制备的催化剂均具有钙钛矿结构;K的掺杂使得催化剂拥有更加均匀的纳米颗粒且颗粒粒度减小;同时掺杂还改变了B位金属的化学状态,使得被掺杂的催化剂中高价态的Mn~(4+)和氧空位的含量增加。其中La_(0.7)K_(0.3)MnO_3具有较好催化活性,碳烟颗粒物的特征温度T_(50)和最大燃烧速率温度分别为344.0℃和349.8℃,NO的转化率为39.1%。     

掺K纳米LaMnO3催化分解柴油机PM排放的研究

用K+取代纳米LaMnO3催化剂中20%的La3+,制备了纳米催化剂La0.8K0.2MnO3,利用SEM和BET方法对其结构进行表征。在试验台架上研究了排气温度对催化分解碳烟排放的影响,利用SEM和EDS对La0.8K0.2MnO3催化分解前后的颗粒物(particular matter,PM)样品进行对比分析。研究结果表明:2种催化剂均属于纳米级颗粒,La0.8K0.2MnO3催化分解碳烟效果较好;La0.8K0.2MnO3催化分解后,PM样品的粒径变小,排列更致密,C含量显著降低。     

LaCoO3钙钛矿型催化剂对柴油机NOx净化性能研究

采用柠檬酸络合法制备了LaCoO3钙钛矿型催化剂。对其理化特性及NH3-选择性催化还原催化性能的研究结果表明：纯LaCoO3颗粒具有一定的NOx催化还原能力,在250～450℃活性较高;但该催化剂对NH3具有较高的氧化活性,且催化活性随反应温度的升高而提高;在SCR反应中,在400℃以下时,该催化剂显示出一定的NOx净化能力,但当温度超过400℃以后,还原剂的加入反而恶化了NOx排放。不管反应气组成如何,LaCoO3钙钛矿型催化剂对HC和CO都具有良好的催化性能。     

同时催化去除柴油机微粒和NO_x的试验研究(2)

通过在γ Al2O3小球和柴油机微粒过滤器(DPF)上涂覆复合金属氧化物催化剂Cu0.95K0.05Fe2O4和La0.9K0.1CoO3,利用程序升温反应(TPR)技术,对同时催化去除柴油机微粒(PM)和NOx反应进行了试验研究。研究结果表明,La0.9K0.1CoO3催化剂比Cu0.95K0.05Fe2O4催化剂具有更高的同时去除PM—NOx的催化反应活性。在低负荷下,柴油机的PM由于SOF含量多而使NOx降低的幅度比高负荷下的大,其燃烧温度也比高负荷下的低。同时,NO和O2的共存促进了PM的氧化燃烧。另外,PM和催化剂之间"松接触"的催化活性要比"紧接触"低。     

NPAC技术降低柴油机NOx和碳烟排放的试验研究

利用等体积溶液浸渍法制备一种CeO2-CuO/γ-Al2O3负载型催化剂,应用X衍射分析仪(XRD)、电镜扫描仪(SEM)等表面分析技术对催化剂进行了表征,考察了该催化剂的性能.设计了一种低温等离子体(NTP)发生器,并建立了低温等离子体辅助催化(NPAC)试验系统.通过台架试验研究了NPAC技术对柴油机有害排放的作用规律,探索了排放物浓度、流量、滞留时间等因素对有害排放转化效果的影响.研究结果表明:NPAC技术可以有效降低柴油机碳烟排放,NOx排放明显降低;在NPAC作用下,碳烟转化效率最高接近60%.标定转速工况下,Ce02-CuO/γ-A1203催化剂活性较好,NOx排放转化率最高,在中高负荷工况下,转速越高对应的NOx转化效率越低.     

NTP协同LKFMCO催化剂对柴油机NO_x和碳烟排放的影响

采用柠檬酸溶胶法制备了La_(0.8)K_(0.2)Fe_(0.5)Mn_(0.45)Co_(0.05)O_3纳米催化剂,利用X射线衍射分析、扫描电镜和能量色散谱仪对LKFMCO催化剂进行了表征,并协同低温等离子体技术,通过发动机台架试验,研究了NTP协同LKFMCO催化剂脱除氮氧化物(NO_x)和碳烟的作用规律。研究结果表明:所制备的催化剂为介孔结构,催化剂粉体具有较高的纯度,粒径较小且尺寸均匀。与空载体作用相比,在NTP+LKFMCO作用下,NO_x转化率高达65%,碳烟排放总体上大幅降低,副产物N_2O浓度变化幅度较小,表明该技术不会引起二次污染。     

CuO/γ-Al2O3催化剂选择性催化还原NO

利用溶胶凝胶法制备CuO/γ-Al2O3,催化剂颗粒,在固定床上测试催化脱硝活性.CuO/γ-Al2O3在250～400℃范围内脱硝效率达到90%以上.硫化作用后催化剂的最佳温度窗口向高温方向移动.利用程序升温方法研究了.CuO/γ-Al2O3对NH3的氧化性能,经硫化后催化剂NH3的氧化性能下降,降低了催化剂在低温区脱硝活性.NH3和NO的脱附实验显示NH3和NO在催化剂表面存在明显的吸附现象.经硫化经后催化剂增加了对NH3的吸附量,降低了对NO的吸附量.暂态实验证明NH3以吸附态参与反应,而NO以气态或者弱吸附态参与反应.NO的吸附在实际SCR反应过程中影响有限.动力学计算显示溶胶凝胶法制备CuO/γ-Al2O3拥有较低的选择性催化还原反应活化能.     

WO_3对于V_2O_5/TiO_2脱硝催化剂的抗中毒作用

实验室制备了V2O5/TiO2以及添加了不同含量WO3的催化剂,并在催化剂上负载碱金属氧化物K2O模拟中毒.在SCR活性试验台上研究不同含量K2O对催化剂脱硝活性,N2O生成率和SO2的氧化率的影响.结果发现,K2O对于催化剂的毒性较强,随着添加量的增大,NO脱除率急剧下降,SO2的氧化率大大提高.K2O通过与V2O5的活性酸性位结合,使催化剂中有效活性位数量大为降低,导致脱硝活性下降.添加WO3后,K2O对催化剂的中毒作用明显减弱,源于WO3较强的Bronsted酸性对催化剂性能的促进作用.综合考虑认为在V2O5/TiO2催化剂上添加10%左右的WO3抗中毒性能较好.     

MoO3界面修饰提升刮涂钙钛矿太阳电池性能

在空穴传输层Spiro-OMeTAD和Ag电极之间引入三氧化钼(MoO₃)空穴修饰层,并研究其对空气中刮涂的钙钛矿太阳电池光伏性能的影响,结合导电性测试、稳态光致发光光谱和水接触角测试等探究其影响机制。实验和测试结果表明MoO₃可提升空穴传输能力和减小界面电阻,同时对下方的Spiro-OMeTAD及钙钛矿起到保护作用,可减缓空气中水氧侵蚀。基于MoO₃界面修饰层的在空气中刮涂制备的钙钛矿太阳电池光电转换效率由15.14%提升至18.30%,尤其是填充因子的平均值由60%提升至76%,电池稳定性得到改善,未封装电池在400 h后仍保持初始效率的90%。     

Burning velocities and kinetics of H2/NF3/N2, CH4/NF3/N2, and C3H8/NF3/N2 flames

The combustion characteristics and reaction mechanism of mixtures containing nitrogen trifluoride (NF₃) were investigated. Burning velocities for H₂/NF₃/N₂, CH₄/NF₃/N₂, and C₃H₈/NF₃/N₂ flames were determined for the first time at various equivalence ratios and N₂ mole fractions. The burning velocities of the latter two flames were similar and showed peaks at equivalence ratios of ∼1.0, while those of the H₂/NF₃/N₂ flames had the pronounced peak at low equivalence ratios where the formation of the wrinkled flames was observed. A detailed kinetic model was constructed to simulate the laminar burning velocities of H₂/NF₃/N₂ and CH₄/NF₃/N₂ flames. The model accurately reproduced the experimental results. Analyses of the reaction mechanism revealed the major reaction pathways that involve the decomposition of NF₃, the oxidation and chain-fluoridation of H₂ and CH₄, and the formation of N₂.     

Preparation and dehydrogenation properties of two cobalt-based ammine borohydrides: CoCl3·3NH3/3LiBH4 and CoCl2·3NH3/2LiBH4

Two new cobalt-based ammine borohydrides were prepared via ball milling of LiBH₄ and CoCl_n·3NH₃ (n = 3, 2) with molar ratios of 3:1 and 2:1, respectively. X-ray diffraction (XRD) results revealed the as-prepared composites having amorphous state. Thermogravimetric analysis-mass spectrometry (TG-MS) measurements showed that the two composites mainly release H₂, concurrent with the evolution of a small amount of NH₃. Further results showed that the excessive addition of LiBH₄ can suppress the liberation of NH₃, resulting in the release of H₂ with a high purity (>99 mol.%). By combination with the temperature-programmed-desorption (TPD) results, the CoCl₃·3NH₃/4LiBH₄ and CoCl₂·3NH₃/3LiBH₄composites can release 7.3 wt.% (4.2 wt.% including LiCl) and 4.2 wt.% (2.0 wt.% including LiCl) pure hydrogen, respectively, in the temperature range of 25–300 °C. Isothermal dehydrogenation results reveal that CoCl₃·3NH₃/3LiBH₄ shows favorable dehydrogenation rate at low temperatures, releasing about 5.2 wt.% (2.9 wt.% including LiCl) of hydrogen within 45 min at 80 °C.     

Synthesis and dehydrogenation of LiCa(NH2)3(BH3)2

We report the synthesis of a new hydrogen storage material with a composition of LiCa(NH₂)₃(BH₃)₂. The theoretical hydrogen capacity of LiCa(NH₂)₃(BH₃)₂ is 9.85 wt.%. It can be prepared by ball milling the mixture of calcium amidoborane (Ca(NH₂BH₃)₂) and lithium amide (LiNH₂) in a molar ratio of 1:1. The experimental results show that this material starts to release hydrogen at a temperature as low as ca. 50 °C, which is ca. 70 °C lower than that of pure Ca(NH₂BH₃)₂ possibly resulting from the active interaction of NH₂⁻ in LiNH₂ with BH₃ in Ca(NH₂BH₃)₂. ca. 4.1 equiv. or 6.8 wt.% hydrogen can be released at 300 °C. The dehydrogenation is a mildly exothermic process forming stable nitride products.     

MoO3 nanorods/Fe2(MoO4)3 nanoparticles composite anode for solid oxide fuel cells

MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite has been prepared by a hydrothermal method combined with an in situ diffusion growth process. Single cells based on 300 μm LSGM electrolyte have been fabricated with the MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite anode and a composite cathode consisting of Sr_0.9Ce_0.1CoO_3−δ and Sm-doped ceria (SDC). The peak power densities reach 225, 50, 75 mW cm⁻² at 900 °C in H₂, CH₄ and C₃H₈, respectively. The cell shows excellent long-term stability at 850 °C. The preliminary results demonstrate that the MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite is a promising alternative anode for solid oxide fuel cells.     

Improved dehydrogenation of MgH2-Li3AlH6 mixture with TiF3 addition

MgH₂-Li₃AlH₆ mixture shows a mutual activation effect between the components. But the dehydrogenation kinetics is still slow, especially at temperature as low as 250 °C. Hereby, an additive (TiF₃) was introduced into the mixture in the present study. The reaction mechanisms were studied by the combined analyses of X-ray diffraction (XRD), thermogravimetric analysis (TGA), as well as thermodynamic calculations. A two-step ball milling method could reduce the mechanical decomposition of Li₃AlH₆ effectively and was adopted. During milling, Li₃AlH₆ reacts with TiF₃ and produces Al₃Ti while MgH₂ remains stable. All the species are well mixed after milling and the grain size is as small as 100 nm. During TGA test, all the reactions occur at lower temperatures compared with undoped mixture, especially the dehydrogenation of MgH₂, which shows a decrease of 60 °C. Its activation energy is reduced by 32.0 kJ mol⁻¹. The first three isothermal (250 °C) cycles indicate that the kinetics of dehydrogenation has been greatly enhanced, showing a reversible capacity of 4.5 wt.% H₂. The time needed for the 1st dehydrogenation has been shortened to 3600 s from 8000 s for the undoped mixture. These improvements are mainly attributed to the catalytic effect of the in-situ formed Al₃Ti. But there is no influence on the rehydrogenation kinetics and the enthalpy of the dehydrogenation of MgH₂ is unchanged.     

Improved hydrogen storage reversibility of LiBH4 destabilized by Y(BH4)3 and YH3

In the present study, the synthesis of two different LiBH₄–Y(BH₄)₃ and LiBH₄–YH₃ composites was performed by mechanochemical processing of the 4LiBH₄–YCl₃ mixture and as-milled 4LiBH₄–YCl₃ plus 3LiH. It was found that Y(BH₄)₃ and YH₃ formed in situ during milling are effective to promote LiBH₄ destabilization but differ substantially from each other in terms of the dehydrogenation pathway. During LiBH₄–Y(BH₄)₃ dehydriding, Y(BH₄)₃ decomposes first generating in situ freshly YH₃ and subsequently, it destabilizes LiBH₄ with the formation of minor amounts of YB₄. About 20% of the theoretical hydrogen storage was obtained via the rehydriding of YB₄–4LiH–3LiCl at 400 °C and 6.5 MPa. As a novel result, a compound containing (B₁₂H₁₂)²⁻ group was identified during dehydriding of Y(BH₄)₃. In the case of 4LiBH₄–YH₃ dehydrogenation, the increase of the hydrogen back pressure favors the formation of crystalline YB_4, whereas a reduction to ≤0.1 MPa induces the formation of minor amounts of Li₂B₁₂H₁₂. Although for hydrogen pressures ≤0.1 MPa direct LiBH₄ decomposition can occur, the main dehydriding pathway of 4LiBH₄–YH₃ composite yields YB₄ and LiH. The nanostructured composite obtained by mechanochemical processing gives good hydrogen storage reversibility (about 80%) regardless of the hydrogen back pressure.     

AlF3-coated LiCoO2 and Li[Ni1/3Co1/3Mn1/3]O2 blend composite cathode for lithium ion batteries

Surface modifications of electrode materials can improve the electrochemical and thermal properties of cathodes for use in lithium batteries. In this study, AlF₃-coated LiCoO₂ and AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode materials are blended, as both have the same crystal structure and exhibit similar electrochemical properties. The composite electrodes exhibit high discharge capacities of 180-188 mAh g⁻¹ in a voltage range of 3.0-4.5 V at room temperature. The capacity retention of the composite electrode is greater than 95% of the initial capacity after 50 cycles. The thermal stability of these composite electrodes is greatly improved because of the superior thermal stability of AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂. The blended AlF₃-coated LiCoO₂ and AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode shows two exothermic peaks, one at 227 °C from AlF₃-coated LiCoO₂ and another at 277 °C from AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂, accompanied by significantly reduced exothermic heat generation.     

Mixed-metal Li3N-based systems for hydrogen storage: Li3AlN2 and Li3FeN2

The hydrogen storage systems Li₃AlN₂ and Li₃FeN₂ were synthesized mechanochemically by two different routes. In each case an intermediate material formed after milling, which transformed into Li₃MN₂ (M = Al or Fe) upon annealing. The synthesis route had a measurable effect on the hydrogen storage properties of the material: Li₃AlN₂ prepared from hydrogenous starting materials (LiNH₂ and LiAlH₄) performed better than that synthesized from non-hydrogenous materials (Li₃N and AlN). For both Li₃AlN₂ materials, the hydrogen storage capacity and the absorption kinetics improved significantly upon cycling. Ti-doped Li₃AlN₂ synthesized from LiNH₂ and LiAlH₄ showed the best hydrogen storage characteristics of all, with the best kinetics for hydrogen uptake and release, and the highest hydrogen storage capacity of 3.2 wt.%, of which about half was reversible. Meanwhile, Li₃FeN₂ synthesized from Li₃N and Fe displayed similar kinetics to that synthesized from Li₃N and Fe_xN (2 ≤ x ≤ 4), but demonstrated lower gravimetric hydrogen storage capacities. Li₃FeN₂ displayed a hydrogen uptake capacity of 2.7 wt.%, of which about 1.5 wt.% was reversible. For both Li₃AlN₂ and Li₃FeN₂, doping with TiCl₃ resulted in enhancement of hydrogen absorption kinetics. This represents the first study of a ternary lithium-transition metal nitride system for hydrogen storage.     

NH3BH3/LiBH4·NH3 modified by metal hydrides for advanced dehydrogenation

The significantly enhanced dehydrogenation performance of binary complex system, NH₃BH₃/LiBH₄·NH₃, were achieved through a chemical modification of LiH to form ternary composites of x (LiH–NH₃BH₃)/LiBH₄·NH₃. Among the studied composites, 3LiH–3NH₃BH₃/LiBH₄·NH₃ released ca. 10 wt. % high-pure hydrogen (>99.9 mol%) below 100 °C with fast kinetics, while less than 8 wt. % hydrogen, accompanied with a fair number of volatile byproducts, were released from 3NH₃BH₃/LiBH₄·NH₃ at the same conditions. Further investigations revealed that the hydrogen emission from x (LiH–NH₃BH₃)/LiBH₄·NH₃ composites is based on the combination mechanism of H^δ+ and H^δ− through the interaction between LiH–NH₃BH₃ and NH₃ group in LiBH₄·NH₃, in which the controllable protic hydrogen source from the stabilized NH₃ group played a crucial role in providing optimal stoichiometric ratio of H^δ+ and H^δ−, and thus leading to the significant improvement of dehydrogenation capacity and purity.     

Reversible hydrogen storage in a 3NaBH4/YF3 composite

A 3NaBH₄/YF₃ hydrogen storage composite was prepared through ball milling and its hydrogen sorption properties were investigated. It is shown that NaBH₄ does not react with YF₃ during ball milling. The dehydrogenation of the composite starts at 423 °C, which is about 100 °C lower than the dehydrogenation temperature of pure NaBH₄, with a mass loss of 4.12 wt%. Pressure–Composition–Temperature tests reveal that the composite has reversible hydrogen sorption performance in the temperature range from 350 °C to 413 °C and under quite low hydrogenation plateau pressures (<1 MPa). Its maximum hydrogen storage capacity can reach up to 3.52 wt%. The dehydrogenated composite can absorb 3.2 wt% of hydrogen within 5 min at 400 °C. Based on the Pressure–Composition–Temperature analyses, the hydrogenation enthalpy of the composite is determined to be −46.05 kJ/mol H₂, while the dehydrogenation enthalpy is 176.76 kJ/mol H₂. The mechanism of reversible hydrogen sorption in the composite involves the decomposition and regeneration of NaBH₄ through the reaction with YF₃. Therefore, the addition of the YF₃ to NaBH₄ as a reagent forms a reversible hydrogen storage composite.