Influence of SO2 on the durability of Ag/Al2O3 catalyst in lean NOx reduction by ethyl alcohol

The influence of SO₂ (200 ppm) on the durability of a Ag/Al₂O₃ catalyst for the reduction of NOx with ethyl alcohol was examined. The results strongly suggest that H₂O in diesel engine exhaust is essential for the high durability of Ag/Al₂O₃ catalyst in the presence of SO₂.     

Reducibility of Mo species in Pt/MoO3 and PtMo/Al2O3 catalysis

Recucibility of Mo species in Pt/MoO₃ and PtMo/Al₂O₃ has been investigated by temperature-programmed reduction (TPR), temperature-programmed desorption of hydrogen (H₂-TPD) and temperature programmed electronic conductivity (TPEC) techniques. In Pt/MoO₃ at H₂ atmosphere, it was found by TPEC and TPR that, a slight amount of Pt could activate the transfer of the species and H atoms between H₂ and MoO₃, and thus accelerate the reduction of MoO₃. In PtMo/Al₂O₃, TPR and H₂-TPD revealed that the reduction of surface Mo species could also be facilitated by Pt. Two kinds of hydrogen molybdenum species were proposed on the surface of the catalyst after prereduction.     

Review of Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Reductant System in the Selective Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Ag/Al₂O₃ is a promising catalyst for the selective catalytic reduction (SCR) by hydrocarbons (HC) of NO _x in both laboratory and diesel engine bench tests. New developments of the HC-SCR of NO _x over a Ag/Al₂O₃ catalyst are reviewed, including the efficiencies and sulfur tolerances of different Ag/Al₂O₃-reductant systems for the SCR of NO _x ; the low-temperature activity improvement of H₂-assisted HC-SCR of NO _x over Ag/Al₂O₃; and the application of a Ag/Al₂O₃-ethanol SCR system with a heavy-duty diesel engine. The discussions are focused on the reaction mechanisms of different Ag/Al₂O₃-reductant systems and H₂-assisted HC-SCR of NO _x over Ag/Al₂O₃. A SO₂-resistant surface structure in situ synthesized on Ag/Al₂O₃ by using ethanol as a reductant is proposed based on the study of the sulfate formation. These results provide new insight into the design of a high-efficiency NO _x reduction system. The diesel engine bench test results showed that a Ag/Al₂O₃-ethanol system is promising for catalytic cleaning of NO _x in diesel exhaust.     

Effect of H2S-uptake on the conversion of cyclohexene on Ru- and Pd-promoted molybdena-alumina catalysts

The effect of H₂S on the activity and selectivity of catalysts (Ru/Al₂O₃, Pd/Al₂O₃ and Ru and Pd promoted molydena-alumina) was different (on differnt catalysts and different conversions of cyclohexene). Ru-containing catalysts showed higher sulfur sensitivities than the Pd-containing ones. The sequence of catalysts by their H₂S uptake related to mass of catalyst was PdMo/Al₂O₃RuMo/Al₂O₃Mo/Al₂O₃>Pd/Al₂O₃Ru/Al₂O₃.     

Ni0.8Co0.15Al0.05C2O4@Graphene的合成及电化学性能研究

过渡金属氧化物/石墨烯复合材料具有优异的电化学性能被广泛应用在锂离子电池中。本文以硫酸镍、硫酸钴、硫酸铝、草酸为原料按一定的物质的量比配制成溶液,在120°C的条件下水热反应12小时,得到多元过渡金属氧化物前驱体Ni_0.8Co_0.15Al_0.05C₂O₄(NCA-C₂O₄);该前驱体经聚烯丙基胺盐酸盐修饰后,与氧化石墨烯进行复合并还原得到石墨烯包覆的多元过渡金属氧化物/石墨烯负极材料Ni_0.8Co_0.15Al_0.05C₂O₄@Graphene(NCA-C₂O₄@G)。对材料的结构、形貌和电化学性质进行了表征。扫描电镜测试结果显示样品粒度均一,具有两端不规则长方体形貌。电化学性能测试结果表明：石墨烯包覆后的NCA-C₂O₄@G充放电容量高于前驱体NCA-C₂O₄,NCA-C₂O₄@G复合材料在0.1C电流密度 (1C=1000 mAh/g)下首次放电比容量为1956 mA h/g;经过0.1C、0.2C、0.5C、1C、2C高倍率循环后,当测试电流密度恢复至100 mA/g时,复合材料比容量可迅速回升至720 mA h/g,并在随后50次循环中比容量保持稳定,显示出良好的循环稳定性和倍率性能。     

Characterization and evaluation of Fe2O3/Al2O3 oxygen carrier prepared by sol–gel combustion synthesis

The sol-gel combustion synthesis (SGCS) for oxygen carrier (OC) to be used in chemical looping combustion (CLC) was first designed and experimented in this work, which is a new method of OC synthesis by combining sol-gel technique and solution combustion synthesis. Cheap hydrated metal nitrates and urea were adopted as precursors to prepare Fe₂O₃/Al₂O₃ OC at the molar ratio to unity (Fe1Al1), which was characterized through various means, including Fourier transforms infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffractor (XRD), and N₂ isothermal adsorption/desorption method. FTIR analysis on the chemical structure of the dried gel of Fe1Al1 indicated that urea was partly hydrolyzed and the hydrated basic carbonate was formed by the combination of groups such as (Fe(_1−yAl_y)_1−xO_1−3x, CO₃²⁻ and -OH-. By analyzing the staged products during SGCS, calcination was found as a necessary step to produce Fe₂O₃/Al₂O₃ OC with separate phases of α-Fe₂O₃ and α-Al₂O₃. Through TGA-DTA, the decomposition of the dried gel was found to undergo five stages. The analysis of the evolved gases from the gel decomposition using FTIR partially confirmed the staged decomposition and assisted a better understanding of the mechanism of SGCS. XRD identification further substantiated the necessity of calcination to synthesize Fe₂O₃/Al₂O₃ OC with separate phases of α-Fe₂O₃ and α-Al₂O₃, though it was not necessary for the synthesis of single phase α-Fe₂O₃ and α-Al₂O₃. Structural characterization performed on N₂ adsorption analyzer displayed that the pore shape of Fe1Al1 particles was heterogeneous. Finally, H₂ temperature-programmed reduction (TPR) of Fe1Al1 products in TGA indicated that the reduction reaction of Fe1Al1 OC after calcination was a single step reaction from α-Fe₂O₃ to Fe, and calcination benefited to improve the transfer rate of the lattice oxygen from the OC to fuel H₂. Furthermore, four times of reduction and oxidization (redox) reaction by alternating with H₂ and air demonstrated the synthesized OC had good reactivity and sintering-resistance, much suitable to be used in the realistic CLC. Overall, the SGCS method was found superior to other existent methods to prepare Fe₂O₃/Al₂O₃ OC for CLC application.     

Fe-Ag/Al_2O_3催化丙烯还原NO的实验研究

以蜂窝状陶瓷为载体,采用溶胶凝胶法和浸渍法制备了不同Fe/Ag负载量的Fe-Ag/Al_2O_3催化剂。以C_3H_6为还原剂,在模拟烟气条件下和200-700℃范围内,程序控温的陶瓷管流动反应器上进行了催化还原NO的性能评估。结果表明,7.2Fe/1.9Ag/20Al_2O_3/CM在500和550℃时催化C_3H_6还原NO的脱硝效率分别超过90%和达到100%。铁离子能有效地提高Ag/20Al_2O_3/CM催化剂抵抗烟气中的SO_2和H_2O的能力。结果表明,当烟气中含有体积分数为0.02%的SO2和8%的H_2O时,在500℃时7.2Fe/1.9Ag/20Al_2O_3/CM催化C_3H_6还原NO的脱硝效率不受影响,在6 h的连续实验中保持90%的脱硝效率而没有下降。而未经铁离子修饰的2Ag/20Al_2O_3/CM的催化活性则受烟气中的SO2和H_2O影响很大,0.02%的SO2和8%的H_2O分别使2Ag/20Al_2O_3/CM在500℃时催化C_3H_6还原NO的脱硝效率迅速从70%分别下降至46%和25%。XRD和SEM表征结果表明,经铁离子修饰后的7.2Fe/1.9Ag/20Al_2O_3/CM催化剂中,形成了AgFeO_2以及Fe~(3+),催化剂表面变得疏松多孔,形成以Fe_3O_4为主的针状和片状晶体。H_2-TPR结果表明,7.2Fe/1.9Ag/20Al_2O_3/CM比Ag/20Al_2O_3/CM在更宽的温度范围内具有更好的还原特性。吡啶吸附红外光谱(Py-FTIR)实验结果显示,Fe增加了催化剂表面的Lewis酸性位。     

Crystal-chemistry of mullite-type aluminoborates Al18B4O33 and Al5BO9: A stoichiometry puzzle

Orthorhombic Al₂O₃-rich aluminoborate is an important ceramic material for which two slightly different compositions have been assumed: Al₅BO₉ (5Al₂O₃:B₂O₃) and Al₁₈B₄O₃₃ (9Al₂O₃:2B₂O₃). The formula Al₁₈B₄O₃₃ (=Al_4.91B_1.09O₉) was derived from results of chemical analyses when crystal structure data were not yet available. Subsequent structural investigations indicated Al₅BO₉ composition. Nevertheless, Al₁₈B₄O₃₃ was still accepted as the correct stoichiometry assuming that additional B replaces 9% Al.Powder samples of both compositions and ones with excess boron were prepared by solid state reactions between α-Al₂O₃ and B₂O₃/H₃BO₃ at temperatures above 1100 °C and single-crystals were grown from flux at 1100 and 1550 °C. Products were investigated by single-crystal and powder XRD, ¹¹B and ²⁷Al solid-state MAS-NMR, Raman and FTIR spectroscopy as well as Laser-ablation ICP-MS. No indication of the predicted 9% B→Al substitution was found. LA ICP-MS indicated 12.36(27) wt% B₂O₃ corresponding to Al_4.97B_1.03O₉. Hence, the suggested Al₁₈B₄O₃₃ stoichiometry can be excluded for all synthesized samples. A very low amount of Al vacancies at a five-fold coordinated site are likely, charge balanced by an additional nearby three-fold coordinated B site. All evidences indicate that the title compound should be reported as Al_5−xB_1+xO₉ with x<0.038(6), which is close to Al₅BO₉.     

Vapor phase hydrofluorination of acetylene to vinyl fluoride over La2O3-Al2O3 catalysts

A series of La-doped Al₂O₃ catalysts were prepared and tested for the vapor phase hydrofluorination of C₂H₂ to vinyl fluoride (CH₂CHF, VF). It was found that the La-doped catalyst gave a stable catalytic performance and a higher selectivity to the desired VF and a lower selectivity to coke deposition compared with the pure Al₂O₃ catalyst. The enhancement in VF selectivity on the La-doped catalyst was due to the elimination of acidic sites on the Al₂O₃ surface by the addition of La₂O₃, evidenced by NH₃-TPD results, which could also explain the declined selectivity to coke deposition on the catalyst. Raman result indicated there were two different vibration forms of CH distortion and CC expansion for the coke deposition.     

过渡金属修饰Fe2O3/Al2O3氧载体的Redox性能研究

采用冷冻干燥法分别制备了经Cu、Co、Mn、Ni修饰的Fe₂O₃/Al₂O₃氧载体。利用化学吸附仪,通过程序升温还原(H₂-TPR)和程序升温氧化(TPO)来研究经不同过渡金属修饰的Fe₂O₃/Al₂O₃与H₂和O₂的反应性能。实验发现,在Fe₂O₃/Al₂O₃中加入Cu、Co、Ni以后,氧载体与H₂的反应性都有提高,但是当在Fe₂O₃/Al₂O₃中加入Mn以后,氧载体的反应性和载氧能力反而下降。经Cu修饰的Fe₂O₃/Al₂O₃与H₂的反应性最高,且具有很好的反应稳定性,适合用于化学链燃烧。     

Nox reduction with CO over supported Pd catalysts under simulated post Euro-IV diesel exhaust conditions

The catalytic reduction of NO_x with CO over Pd/Al₂O₃ and Pd/TiO₂/Al₂O₃ under simulated post Euro-IV diesel exhaust conditions was studied. The catalytic activities obtained by using various Pd and TiO₂ loadings and total amounts of reductant and the influence of H₂ and H₂O was investigated.     

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.     

致密的5%Al3+掺杂的SnP2O7-SnO2复合陶瓷在中温燃料电池中的应用

首先制备了未掺杂和5%(摩尔分数)Al³⁺掺杂SnO₂的多孔性基片, 然后将基片与85%的H₃PO₄在600℃下反应, 分别得到了致密的未掺杂和5%Al³⁺掺杂的SnP₂O₇-SnO₂复合陶瓷样品. 采用X射线衍射(XRD), 扫描电子显微镜(SEM)和X射线能量色散谱(EDS)测试方法对样品进行了表征, 采用电化学阻抗谱法(EIS)测试了样品在中温(100-250℃)下, 湿润空气和湿润氢气气氛中的电导率. 结果表明, 在湿润空气和湿润氢气中, 5%Al³⁺掺杂的SnP₂O₇-SnO₂复合陶瓷样品的电导率均高于未掺杂的SnP₂O₇-SnO₂复合陶瓷样品的电导率, 且该复合陶瓷样品在湿润空气和湿润氢气中250℃下, 电导率分别达到最大值: 4.30×10^-2和6.25×10^-2 S·cm^-1, 高于至今报道的SnP₂O₇-SnO₂基复合陶瓷及SnP₂O₇基陶瓷在类似条件下的电导率. 以5%Al³⁺掺杂的SnP₂O₇-SnO₂复合陶瓷样品(厚度: 1.45 mm)为电解质, 多孔性铂为电极组装成的氢气/空气燃料电池具有良好的中温电池性能, 175、200、250℃的最大输出功率密度分别为52.0、61.9、82.3 mW·cm^-2. 良好的中温电池性能与该复合陶瓷电解质较高的电导率和致密度及该燃料电池较低的界面极化电阻有关.     

TiO2微粒功能化多孔Al2O3膜的光电化学研究

用恒电位法制备了多孔Al₂O₃薄膜, 通过在Al₂O₃薄膜孔内水蒸汽水解钛酸异丙酯生成了锐钛矿型TiO₂微粒, 制备出了Al₂O₃与TiO₂微粒的复合薄膜. 用XRD, SEM, 光电化学方法进行了研究. 实验表明: 该复合薄膜具有光电转换特性, 在光催化、光电化学太阳能转换中具有应用价值.     

可回收Fe3O4@SiO2-Ag磁性纳米微球对染料污染物的快速脱色处理

介绍了一种采用无毒廉价的前驱物制备Fe₃O₄@SiO₂-Ag磁性纳米微球的快捷方法,制备的Fe₃O₄@SiO₂-Ag纳米微球在NaBH₄存在下可以催化还原染料污染物.实验结果表明,Fe₃O₄@SiO₂-Ag磁性纳米粒子保持了Ag纳米粒子和Fe₃O₄纳米粒子的双重优点,不仅对染料罗丹明B和曙红Y具有良好的催化还原效率,而且可以在外加磁场作用下从溶液中快速有效的分离.催化还原反应速率与反应温度及Fe₃O₄@SiO₂-Ag催化剂用量有关,反应体系中表面活性剂和无机盐(Na₂SO₄)的存在也会影响催化剂的催化活性.该Fe₃O₄@SiO₂-Ag磁性纳米粒子在工业染料污染物处理方面具有应用前景.     

铜物种对Cu/Fe2O3水煤气变换反应催化剂性能的影响

采用共沉淀法制备了系列铜负载量不同的Cu/Fe₂O₃水煤气变换(WGS)催化剂,并考察了铜负载量对催化剂结构和水煤气变换反应性能的影响. 结果表明,Cu/Fe₂O₃催化剂呈现出良好的水煤气反应性能,当CuO质量分数为20%时,催化剂的WGS性能最优,250 ℃时CO转化率高达97.2%,同时热稳定性也最好. 运用X射线粉末衍射(XRD)、N₂物理吸脱附和H₂程序升温还原(H₂-TPR)等手段对Cu/Fe₂O₃催化剂的物相、织构特征及还原性能进行了表征,结果表明,CuFe₂O₄物种的存在极大地改善了催化剂的还原性能和WGS反应活性. 这是由于CuFe₂O₄特殊的尖晶石结构有利于Cu微晶的稳定;同时,CuFe₂O₄在低温下即被还原为单质铜,有利于促进催化剂体系中电子的转移. 此外,通过(NH₄)₂CO₃溶液处理,研究了独立相CuO对Cu/Fe₂O₃催化剂WGS反应性能的影响,结果发现,独立相CuO的存在,有利于H原子在各组分传递,从而促进催化剂的CuFe₂O₄的还原,改善Cu/Fe₂O₃催化剂的WGS反应性能.     

ZrO4/SiO2-Al2O3催化肉桂醛MPV转移加氢性能

以九水合硝酸铝（Al（NO₃）₃·9H₂O）与正硅酸乙酯（TEOS）为前驱盐,采用溶胶-凝胶法制备一系列不同Al₂O₃含量的SiO₂-Al₂O₃复合氧化物,并通过浸渍硝酸氧锆引入ZrO₂,制备ZrO₂/SiO₂-Al₂O₃复合氧化物催化剂,考察催化剂在肉桂醛（CAL）MPV转移加氢中的催化性能,并结合N₂物理吸附、X射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）、NH₃-程度升温脱附（NH₃-TPD）、Py-原位红外（Py-IR）等技术,研究催化剂结构、织构以及表面性质与其催化性能间的构效关系.研究表明,所制备的催化剂均以L酸为主,并含有少量B酸中心,这使得加氢产物以肉桂醇（COL）为主,并含有少量1-苯丙烯-2-丙基醚（CPE）.Al₂O₃含量不仅影响催化剂表面的酸中心数量,而且对催化剂的织构参数有较大影响.随Al₂O₃含量的增加,催化剂表面L酸与B酸中心均有所增加,而孔径则持续变小,这使得催化反应呈现CAL转化率先增加后减少、目标产物COL选择性先稍有减小后有所增加的趋势.在Si/Al比为2时,催化剂具有最优的催化性能,优化反应条件下,CAL转化率达96%,目标产物COL选择性达90%.     

Oxidative conversion of methane and methanol on M/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite structured metal oxide catalysts (m = Ni,Cu, Zn)

A study was carried out on the properties of Ni/Al₂O₃ and Cu-ZnO/Al₂O₃ composites supported on ceramic honeycomb monoliths made from synthetic cordierite in the carbon dioxide conversion of methane and the partial oxidation of methanol. The structured nickel-alumina catalysts are significantly more efficient than the conventional granulated catalysts. The improved working stability of these catalysts was achieved by adjusting the acid-base properties of the surface by introducing sodium and potassium oxides, which leads to inhibition of surface carbonization. The hydrogen yield was close to 90% in the partial oxidation of methanol with a stoichiometric reagent ratio in the presence of the Cu-ZnO/Al₂O₃/cordierite catalyst. A synergistic effect was found, reducing the selectivity of CO formation in the presence of the Cu-ZnO catalyst relative to samples derived from the individual components Cu and ZnO. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 299–306, September–October, 2007.     

A simple and effective strategy to synthesize Al2O3-coated LiNi0.8Co0.2O2 cathode materials for lithium ion battery

A facile method has been developed to synthesize Al₂O₃-coated LiNi_0.8Co_0.2O₂ cathode materials. The sample was characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and energy dispersive analysis of X-rays (EDAX). Electrochemical tests show that the cycling stability of LiNi_0.8Co_0.2O₂ at room temperature is effectively improved by Al₂O₃ coating. The differential scanning calorimetry (DSC) and high temperature (60 °C) cycling tests indicate that Al₂O₃ coating can also improve the thermal stability of LiNi_0.8Co_0.2O₂, which is attributed to that the coating layer can protect the LiNi_0.8Co_0.2O₂ particles from reacting with the electrolyte.     

Ag/PANI/Fe_2O_3复合纳米粒子的合成与催化性能

借助于PANI的还原性质,PANI/Fe2O3复合载体与AgNO3发生表面氧化还原反应,合成了Ag/PANI/Fe2O3复合纳米粒子。TEM和XRD结果表明,立方晶系纳米银的平均粒径10nm。FTIR结果表明,Ag与PANI及Fe2O3复合载体之间不存在化学键合作用,但由于PANI与Ag之间的电子相互作用,Ag/PANI/Fe2O3复合纳米粒子的FTIR吸收峰发生蓝移。Ag/PANI/Fe2O3复合纳米粒子对于间硝基苯磺酸钠的硼氢化钠还原反应表现出良好的催化活性,30min内间硝基苯磺酸钠的转化率达到86.77%。