The direct decomposition of NO over the La2CuO4 nanofiber catalyst

The NO catalytic direct decomposition was studied over La₂CuO₄ nanofibers, which were synthesized by using single walled carbon nanotubes (CNTs) as templates under hydrothermal condition. The composition and BET specific surface area of the La₂CuO₄ nanofiber were La₂Cu_0.88²⁺Cu_0.12⁺O_3.94 and 105.0 m²/g, respectively. 100% NO conversion (turnover frequency-(TOF): 0.17 g_NO/g_catalyst s) was obtained over such nanofiber catalyst at temperatures above 300 °C with the products being only N₂ and O₂. In 60 h on stream testing, either at 300 °C or at 800 °C, the nanofiber catalyst still showed high NO conversion efficiency (at 300 °C, 98%, TOF: 0.17 g_NO/g_catalyst s; at 800 °C, 96%, TOF: 0.16 g_NO/g_catalyst s). The O₂ and NO temperature programmed desorption (TPD) results indicated that the desorption of oxygen over the nanofibers occurred at 80-190 and 720-900 °C; while NO desorption happened at temperatures of 210-330 °C. NO and O₂ did not competitively adsorb on the nanofiber catalyst. For outstanding the advantage of the nanostate catalyst, the usual La₂CuO₄ bulk powder was also prepared and studied for comparison.     

Influence of copper precursors in the steam reforming of methanol over Cu/SnO2/SiO2 catalysts

Cu/SnO₂/SiO₂ catalysts, prepared with three different copper precursors (copper nitrate, sulfate and chloride), were characterized and investigated for the steam reforming of methanol. Cu/SnO₂/SiO₂ catalyst, prepared with copper nitrate, showed the highest activity among the tested catalysts. The highest activity of the catalyst prepared with copper nitrate was ascribed to the highly dispersed Cu particles from CO adsorption experiment. The selectivity of methanol to H₂ decreased with an increase in the amount of acid on the surface of Cu/SnO₂/SiO₂ catalysts from FT-IR experiments.This revised version was published online in December 2005 with corrections to the Cover Date.     

静电纺丝法制备La2CuO4纳米管阴极材料及其电化学性质研究

采用静电纺丝法制备了一维管状中温固体氧化物燃料电池(ITSOFC)阴极材料La₂CuO₄。利用XRD、TG-DTA、FT-IR和SEM对材料的结构和微观形貌进行分析。研究表明,700℃烧结2h得到平均直径150纳米、形貌均一的La₂CuO₄纳米管。900℃烧结0.5h得到纳米管间连接充分并与电解质紧密接触的纤维电极。利用交流阻抗技术对电极的性能进行研究发现,La₂CuO₄纳米管阴极材料具有比粉体材料更优越的电极性能。纳米管阴极在700℃的极化电阻为1.03Ω·cm²,而同一组成粉体电极的极化电阻为1.61Ω·cm²;氧分压测试结果显示纳米管电极反应的速率控制步骤为电荷转移过程。     

静电纺丝法制备La_2CuO_4纳米管阴极材料及其电化学性质研究

采用静电纺丝法制备了一维管状中温固体氧化物燃料电池(ITSOFC)阴极材料La2CuO4。利用XRD、TG-DTA、FT-IR和SEM对材料的结构和微观形貌进行分析。研究表明,700℃烧结2 h得到平均直径150纳米、形貌均一的La2CuO4纳米管。900℃烧结0.5 h得到纳米管间连接充分并与电解质紧密接触的纤维电极。利用交流阻抗技术对电极的性能进行研究发现,La2CuO4纳米管阴极材料具有比粉体材料更优越的电极性能。纳米管阴极在700℃的极化电阻为1.03Ω·cm2,而同一组成粉体电极的极化电阻为1.61Ω·cm2;氧分压测试结果显示纳米管电极反应的速率控制步骤为电荷转移过程。     

Growth of La2CuO4 nanofibers under a mild condition by using single walled carbon nanotubes as templates

La₂CuO₄ nanofibers (ca. 30 nm in diameter and 3 μm in length) have been grown in situ by using single walled carbon nanotubes (SWNTs; ca. 2 nm in inner diameter; made via cracking CH₄ over the catalyst of Mg_0.8Mo_0.05Ni_0.10Co_0.05O_x at 800 °C) as templates under mild hydrothermal conditions and a temperature around 60 °C. During synthesis, the surfactant poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) and H₂O₂ were added to disperse SWNTs and oxidize the reactants, respectively. The structure of La₂CuO₄ nanofibers was confirmed by powder X-ray diffraction (XRD) and their morphologies were observed with field emission scanning electron microscope (FESEM) at the hydrothermal synthesis lasting for 5, 20 and 40 h, respectively. The La₂CuO₄ crystals grew from needle-like (5 h) through stick-like (20 h) and finally to plate-like (40 h) fibers. Twenty hours is an optimum reaction time to obtain regular crystal fibers. The La₂CuO₄ nanofibers are probably cubic rather than round and may capsulate SWNTs.     

R&D activities in Japan on methanol synthesis from CO2 and H2

Methanol synthesis from CO₂ and H₂ can be a useful process for conversion and transportation of hydrogen energy derived from non-fossil energies. More than ten research groups in Japan have extensively investigated the methanol synthesis from both academic and practical points of view. Recent R&D activities in Japan for developing high performance catalysts, for elucidating the reaction mechanism and also for operating a bench scale plant have been reviewed in this paper.     

Effect of ceria loading on the carbon formation during low temperature methane steam reforming over a Ni/CeO2/ZrO2 catalyst

The characterization and catalytic activity of a Ni/CeO₂/ZrO₂ catalyst for methane steam reforming at 600°C were investigated. The addition of ceria increased the surface area and basicity of the catalysts. The redox reaction capability of the ceria increased the hydrogen yield and carbon monoxide selectivity, and inhibited carbon formation.     

甲醇水蒸气重整制氢CuAl2O4催化材料的研究

以γ-Al₂O₃为原料采用原位合成法制备CuAl₂O₄催化材料，通过XRF、XRD、BET和H₂-TPR等手段对催化材料进行表征，考察铜铝物质的量比对CuAl₂O₄催化材料结构、性质及其催化甲醇水蒸气重整制氢性能的影响。结果表明，不同铜铝物质的量比主要影响了铜物种的还原性能，从而影响了其催化甲醇水蒸气重整制氢的性能。当铜铝物质的量比为1：2时，CuAl₂O₄催化材料的催化性能较好，在反应温度为260℃，水醇物质的量比为1.2，甲醇气体空速为800 h^-1时，甲醇转化率为100%，产氢速率为895 mL/（kg·s）。     

La2(CO3)3纳米线的微乳液法制备与表征

La₂(CO₃)₃ nanowires were prepared in the nonionic surfactant microemulsion(Triton X-100/cyclohexane/water)system. Transmission electron microscopy (TEM) and selected area electronic diffraction (SAED) were used to characterize the shape and size of the products. The results showed that the pH value and concentration of mother solution, temperature and aging time all could affect the morphology and size of the La₂(CO₃)₃ nanowires. The lengths of the nanowires were more than 10 μm and the diameters were in the range of 30～200 nm.     

CO2 reforming of methane over zirconia-supported nickel catalysts, I. Catalytic specificity

CO₂ reforming of methane is performed over zirconia-supported nickel catalysts. The catalysts show high activity toward CH₄ and CO₂ conversions. Over the high Ni loading catalyst, long-term performances without significant deactivations have been achieved at 1023 K for 30 h and 1123 K for 20 h, respectively. The effects of reduction and calcination temperatures on the catalytic activities are also examined.     

La2-xBixCuO4阴极材料的合成与电化学性质

采用甘氨酸-硝酸盐法合成了固体氧化物燃料电池阴极材料La_2-xBi_xCuO₄（x=0、0.05、0.10）,并利用X射线衍射（XRD）对材料的物相进行分析。结果表明,La_2-xBi_xCuO₄形成单一的类钙钛矿结构氧化物,且晶胞体积随着铋掺杂量的增加而增大。在950℃烧结24 h过程中,La_2-xBi_xCuO₄不与电解质Sm_0.2Ce_0.8O_1.9（SDC）发生反应,表明这种电解质材料具有良好的高温化学相容性。电导率测试结果表明Bi的掺入显著提高了材料电导率。程序升温脱附测试结果表明,铋的掺杂显著增强了材料的表面氧吸附能力。不同氧分压下的交流阻抗谱测试结果表明,La_1.9Bi_0.1CuO₄阴极在700℃空气中的极化电阻为0.26 Ω·cm²,以电解质SDC支撑的单电池NiO-SDC/SDC/La_1.90Bi_0.10O₄在700℃的最大输出功率密度为308 mW·cm^-2,电极反应的速控步骤为氧分子的扩散与表面吸附过程。     

Pressure-induced structural changes of the tetragonal Bi2CuO4

The tetragonal compound Bi₂CuO₄ was investigated at high pressures by using in situ Raman scattering and X-ray diffraction (XRD) methods. A pressure-induced structural transition started at 20 GPa and completed at ∼37 GPa was found. The high pressure phase is in orthorhombic symmetry. Raman and XRD measurements revealed that the above phase transition is reversible.     

A Structural Investigation of La2(GeO4)O and Alkaline-Earth-Doped La9.33(GeO4)6O2

The structures of the oxyorthogermanate La₂(GeO₄)O and the apatite-structured La_9.33(GeO₄)₆O₂ have been refined from powder neutron diffraction data. La₂(GeO₄)O crystallizes in a monoclinic unit cell (P2₁/c) and is cation stoichiometric in contrast to previous reports. La_9.33(GeO₄)₆O₂ crystallizes in a hexagonal unit cell (P6₃/m) and the powder diffraction data show anisotropic peak broadening that is observed in electron diffraction patterns as incommensurate diffuse spots at hkq reciprocal planes (with q=1.6-1.7) and can be attributed to a correlated disorder in the “apatite channels”. This compound was doped up to a nominal composition close to M₂La₈(GeO₄)₆O₂ with M=Ca, Sr, Ba. The dopant ions preferentially occupy the 4f sites as the number of La vacancies decreases. The measured ionic conductivity of La_9.33(GeO₄)₆O₂ is about 3 orders of magnitude larger than for La₂(GeO₄)O at high temperatures and decreases with increasing dopant content from the highest value of about 0.16 S cm⁻¹ at 1160 K.     

Synthesis and properties of the double perovskites La2NiVO6, La2CoVO6, and La2CoTiO6

The double perovskites La₂CoVO₆, La₂CoTiO₆, and La₂NiVO₆, are described. Rietveld fitting of neutron and powder X-ray diffraction data show La₂NiVO₆ and La₂CoVO₆ to have a disordered arrangement of B-cations whereas La₂CoTiO₆ shows ordering of the B-cations (with ∼5% Co/Ti inversion). Curie-Weiss fits to the linear region of the 1/χ plots reveal Weiss temperatures of −107, −34.8, and 16.3 K for La₂CoVO₆, La₂CoTiO₆, and La₂NiVO₆, respectively, and magnetic transitions are observed. La₂CoTiO₆ prepared by our method differs from material prepared by lower-temperature routes. A simple antiferromagnetic spin model is consistent with the data for La₂CoTiO₆. These compounds are semiconductors with bandgaps of 0.41 (La₂CoVO₆), 1.02 (La₂CoTiO₆) and 0.45 eV (La₂NiVO₆).     

CO2 reforming of methane over zirconia-supported nickel catalysts, II. Thermogravimetric analysis

Thermogravimetric analysis has been used to study carbon deposition during the CO₂ reforming of methane over Ni/ZrO₂ catalysts. The carbon deposits form on the reduced catalyst at a very fast rate during temperature-programmed surface reaction of reforming, and reach a steady state below 973 K. So, the amount of deposited carbon remains constant on the catalyst during the reaction at 973 K. A relationship between the amount of deposited carbon and the activity reveals that the initially formed carbon acts as a reaction intermediate and reacts with CO₂ to produce CO.     

ZIF-67/CeO2催化CO2和甲醇直接合成碳酸二甲酯

采用沉淀法将ZIF-67负载到CeO₂上,制备了具有多重活性位点的非均相催化剂ZIF-67/CeO₂,并研究其催化CO₂和甲醇直接反应生成碳酸二甲酯(DMC)的性能。采用 X 射线衍射、N2吸附-脱附、傅里叶变换红外光谱和 X 射线光电子能谱研究了ZIF-67/CeO₂的各种理化性质。结果表明,ZIF-67的引入使ZIF-67/CeO₂催化剂产生更多的氧空位。在考察的ZIF-67/CeO₂系列催化剂中,0.3-ZIF-67/CeO₂(0.3为Co、Ce物质的量之比)在具有高的比表面积的同时还能保持介孔结构,具有丰富的酸碱位点,并且具有较高的CO₂吸附容量,表现出最好的催化性能。在反应温度为140℃、压力为4.5 MPa的条件下反应4 h,DMC收率可达到3.79 mmol_DMC·gcat^-1。     

ZIF-67/CeO2催化CO2和甲醇直接合成碳酸二甲酯

采用沉淀法将ZIF-67负载到CeO₂上,制备了具有多重活性位点的非均相催化剂ZIF-67/CeO₂,并研究其催化CO₂和甲醇直接反应生成碳酸二甲酯(DMC)的性能。采用X射线衍射、N₂吸附-脱附、傅里叶变换红外光谱和X射线光电子能谱研究了ZIF-67/CeO₂的各种理化性质。结果表明,ZIF-67的引入使ZIF-67/CeO₂催化剂产生更多的氧空位。在考察的ZIF-67/CeO₂系列催化剂中,0.3-ZIF-67/CeO₂(0.3为Co、Ce物质的量之比)在具有高的比表面积的同时还能保持介孔结构,具有丰富的酸碱位点,并且具有较高的CO₂吸附容量,表现出最好的催化性能。在反应温度为140℃、压力为4.5 MPa的条件下反应4 h,DMC收率可达到3.79 mmol_DMC·g_cat^-1。     

High pressure induced coordination evolution in chain compound Li2CuO2

Using diamond anvil cell technique with angle dispersive X-ray diffraction (ADXD) of synchrotron radiation and electrical conductivity measurements, we have observed that CuO₂ chain compound Li₂CuO₂ transforms from ambient orthorhombic symmetry into a new phase at above 5.4 GPa and room temperature. The new phase was found to be of monoclinic structure with an increased oxygen coordination number of Cu²⁺ from four at ambient to six at high pressure that provides a structural basis of the evolution of principle physical properties. The high pressure phase of Li₂CuO₂ is discussed in line with the first principle calculations.     

Methane steam reforming over rhodium promoted Ni/Al2O3 catalysts

The effect of Rh addition upon catalyst characteristics and performance in methane steam reforming was investigated using Rh-promoted Ni/Al₂O₃ catalysts. The number of reduced metal atoms exposed on the surface increased for the Rh-promoted catalysts. Rh-promoted catalysts showed an increase in CH₄ reforming activity; however, constant turnover frequencies for promoted and unpromoted catalysts suggest that the increase in the number of metal surface atoms caused the activity enhancement. Rh also facilitated reduction of Ni/Al₂O₃.     

Catalytic properties of Mg-modified Ni-based hexaaluminate catalysts for CO2 reforming of methane to synthesis gas

CO₂ reforming of CH₄ over hexaaluminates LaNi _x Mg_1−x Al₁₁O_19+δ and LaNi _x Mg_0.8Al_11.2−x O_19+δ were studied. XRD analysis confirmed that modifier Ni as well as Mg was inlaid into the hexaaluminate lattice. Hexaaluminate LaNi _x Mg_1−x Al₁₁O_19+δ (1.0 ≥ x ≥ 0.4) showed better catalytic activities and higher resistance to carbon deposition, which was attributed to their pure magnetoplumbite-type structure. For this reaction, x-value between 0.6 and 0.4 was the most suitable.