粉末冶金法制备TiB2与Al基复合材料与性能研究

使用粉末冶金法制备了Ti B₂/Al基复合材料，使用X射线衍射仪(XRD)对复合材料进行衍射图谱分析，确定复合材料的物相组织，复合材料晶界处为增强体Ti B₂的主要分布位置，随着Ti B₂质量分数的增加，团聚现象增多。探讨了Ti B₂/Al基体的显微结构和机械性质的变化，并分析了Ti B₂粒子的加入对Ti B₂/Al基体的影响。实验发现，Ti B₂/Al与Ti B₂/Al的界面结合较好。在1 h的保温、610℃烧结、20%质量分数硼化钛的硬度最高，维氏硬度值为68.2 HV。此时的复合材料在Ti B₂质量分数15%时的综合力学性能最好，抗拉强度为153.43 MPa，比纯铝提高了19.68%。     

B2O3负载量对MoO3/CeO2-Al2O3耐硫甲烷化性能的影响

考察B₂O₃负载量对于MoO₃/CeO₂-Al₂O₃催化剂对耐硫甲烷化活性的影响,利用BET、XRD、TEM、NH₃-TPD等手段对催化剂进行了表征。结果表明,催化剂的耐硫甲烷化活性随B₂O₃负载量增加呈现先升高后降低的变化规律;当B₂O₃负载量为0.5%时,催化剂的耐硫甲烷化活性最高,CO转化率达到55%。结合表征分析,发现添加B₂O₃会影响催化剂载体的结构和表面酸度,从而影响活性组分的分散程度,进而影响MoO₃/CeO₂-Al₂O₃催化剂的耐硫甲烷化性能。催化剂的晶化程度太高或单位面积上的强酸量太多均不利于甲烷化反应;较好的活性组分分散度有利于催化剂甲烷化活性的提高。     

Al2O3溶胶对铝基磷酸盐涂层组织及性能的影响

为提高铝基磷酸盐涂层的耐腐蚀性能和力学性能,通过在铝基磷酸盐涂料中添加 Al₂O₃溶胶,经空气喷涂与热固化得到 Al₂O₃颗粒增强铝基磷酸盐复合涂层,采用 X射线衍射仪（ XRD）、扫描电镜（ SEM）、胶粘拉脱法、维氏硬度、电化学腐蚀试验和模拟海水浸泡试验考察 Al₂O₃溶胶含量对复合涂层微观组织、力学性能和耐腐蚀性能的影响。结果表明： Al₂O₃溶胶在涂层 500 ℃热固化的物相演化为 Al₂O₃溶胶 -AlOOH-Al₂O₃,随 Al₂O₃溶胶含量从 0增加到（γ相）生成的 Al₂O₃颗粒在涂层呈弥散分布;4%,复合涂层的孔隙减少,致密性提高, Al₂O₃颗粒弥散强化作用得到发挥,涂层结合强度由 15 MPa提高为 25 MPa,硬度由 38 HV提高为 65 HV;添加 Al₂O₃溶胶制备得到的铝基磷酸盐复合涂层耐腐蚀性能明显提高,自腐蚀电流密度由 2. 38×10-7 A/cm2下降至 2. 79×10^-8 A/cm²,极化电阻由 1. 95×10⁴ Ω提升至 4. 73×10⁵ Ω。     

Bi2Sn2O7/CeO2 Z型异质结光催化剂在可见光下降解有机污染物性能研究

利用水热法将Bi₂Sn₂O₇纳米颗粒负载到CeO₂微球上制备Z型异质结光催化剂并用于光催化降解水污染物。结果表明,在光照下60 min时,优化的Bi₂Sn₂O₇/CeO₂(BSC-5)对盐酸四环素的降解效率达到88.4%(反应速率常数k=0.033 4 min^-1),是CeO₂的8.25倍和Bi₂Sn₂O₇的4.71倍。Z型异质结可以形成更多暴露的活性中心,具有更好的光电子-空穴对分离效率、优异的氧化还原能力以及有效产生超氧自由基(·O^-₂)和羟基自由基(·OH)。此外,Bi₂Sn₂O₇/CeO₂在光催化降解实验中表现出良好的稳定性,经过5次循环后降解效率保持在85%以上。同...     

La的掺杂方式对CeO2-MnOx催化氧化氯苯性能的影响

采用共沉淀法制备CeO₂-MnO_x和La₂O₃-CeO₂-MnO_x催化剂，再用沉积-沉淀法制备La₂O₃/CeO₂-MnO_x催化剂，并对催化剂的氯苯催化氧化反应活性进行检测。结果表明，La的加入可以显著提高催化剂催化氧化氯苯的活性。XRD和TPR表征结果表明，La的加入抑制CeO₂晶粒尺寸的长大，增强CeO₂的晶格应变，并促进Mn进入CeO₂的晶相，形成较好的MnCeO_x固溶体。催化剂的热稳定性评价结果表明，La的加入有效提高CeO₂-MnO_x催化剂的热稳定性。     

B2O3改性Na2CO3催化剂用于甲醇脱氢制无水甲醛

以B₂O₃为助催化剂,采用研磨混合法改性Na₂CO₃催化剂,在固定床反应器中催化甲醇脱氢制备无水甲醛,考察催化剂的组成和反应条件等对催化反应的影响,采用XRD、TG-DTG、N₂吸附-脱附、SEM和CO₂-TPD等对催化剂进行表征。结果表明,以B₂O₃为助催化剂采用机械研磨混合法改性的Na₂CO₃催化剂,增加了催化剂的比表面积,在(10～30) nm增加了大量的孔道,平均孔径达18.44 nm,比表面积为1.65 m²·g^-1,且B₂O₃分布均匀,改性后的催化剂碱性降低,在催化甲醇脱氢制备无水甲醛的反应中,催化活性明显高于Na₂CO₃催化剂,表明B₂O₃改性Na₂CO₃催化剂能提高甲醇转化率和甲醛选择性。在B₂O₃/Na₂CO₃催化剂中B₂O₃质量分数为30%、甲醇进料质量分数为26%、反应温度为650 ℃和甲醇重时空速为2.94 h^-1条件下,甲醇转化率达59.97%,甲醛选择性达83.28%。     

Al2O3-瓷釉复合陶瓷涂层冲蚀磨损性能研究

利用搪瓷涂层的制备工艺在Q235A钢表面制备Al2O3-瓷釉复合陶瓷涂层,研究了瓷釉粒度、Al2O3陶瓷颗粒的粒度和体积分数对复合涂层耐冲蚀磨损性能的影响。结果表明:过渡层原料瓷釉粒度为16μm时获得涂搪性较好;硬质耐磨相的加入可显著提高复合涂层的耐冲蚀性能;本实验中在45°冲蚀角、15 MPa冲蚀气压、2.2 kg冲砂量的冲蚀实验条件下Al2O3粒度为50μm、体积分数为30%时涂层具有很好的耐冲蚀性,是无硬质相搪瓷层的4倍。     

石墨表面Si-SiC-TaB2抗烧蚀复合涂层的制备及性能研究

为了提高碳材料的抗烧蚀性能，以石墨块作为基体，SiC(d₅₀=10μm)、B₄C(d₅₀=50μm)、TaC(d₅₀=3μm)为主要原料，采用料浆法结合反应熔渗Si在石墨材料表面制备了Si-SiC和Si-SiC-TaB₂涂层，研究了涂层的物相组成、显微结构和元素分布，考察了Si-SiC-TaB₂复合涂层在室温至1 600℃的抗热震性能，并通过等离子火焰烧蚀试验(2 350℃分别烧蚀120和1 980 s)测试了涂层对石墨材料高温下的抗烧蚀防护性能。结果表明：Si-SiC-TaB₂复合涂层结构致密，涂层中SiC和TaB₂陶瓷颗粒与Si无明显界面；在1 600℃热震循环20次后，涂层试样的质量基本逐渐增加，具有良好的抗热震性能；Si-SiC-TaB₂复合涂层试样烧蚀1 980 s后质量增加，表面覆盖了含有Ta₂O₅和SiO₂的Ta...     

多孔竹炭负载SnO2的制备及其电化学性能研究

多孔竹炭为无定形碳,具有丰富的孔结构,孔径分布在1~6 nm之间,且具有较大的孔体积(1.21 cm³/g)。本文以多孔竹炭为载体,采用溶胶-凝胶法制得B₂O₃-SnO₂/C复合材料。SEM和TEM结果显示SnO₂和B₂O₃均匀分布在多孔竹炭表面。多孔竹炭和B₂O₃有效缓冲SnO₂可逆反应的体积变化,提高SnO₂的循环稳定性。将B₂O₃-SnO₂/C复合材料作为负极组装成锂离子半电池,进行电化学性能测试,在1 C(1 C=372 mA/g)倍率下充放电循环200次结束后仍然保留649.9 mAh/g的放电比容量,放电比容量保留率为58.6%。B₂O₃-SnO₂/C复合材料充放电过程受扩散和电容两种行为控制,电容控制的贡献率随着扫描速率的增大而增大。     

TiO2与SiO2掺杂对Al2O3相转变的研究

通过球磨混合法,制备TiO₂、SiO₂和TiO₂+SiO₂掺杂的Al₂O₃粉体,经不同温度煅烧后进行X射线衍射(XRD)测试,比较研究这三种掺杂对Al₂O₃粉体相转变温度的影响。研究结果表明,TiO₂、SiO₂掺杂对γ-Al₂O₃向α-Al₂O₃的相转变均有促进作用。在掺杂质量分数为0.5%的情况下,二者可分别使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低100 ℃和125 ℃。而TiO₂+SiO₂复合掺杂对γ-Al₂O₃向α-Al₂O₃相转变的促进作用优于TiO₂、SiO₂单独掺杂。TiO₂、SiO₂的质量分数均为0.3%时,复合掺杂可使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低150 ℃。此外,还对TiO₂、SiO₂和TiO₂+SiO₂掺杂促进Al₂O₃粉体相转变的机理作了简单分析。     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

Resistance of sodium polyphosphate-modified fly ash/calcium aluminate blend cements to hot H2SO4 solution

Sodium polyphosphate-modified Class F fly ash/calcium aluminate blend (SFCB) cements were prepared at room temperature and their resistance to hot acid erosion was evaluated by submerging them in H₂SO₄ solution (pH 1.6) at 90°C. Sodium polyphosphate preferentially reacted with calcium aluminate cement (CAC) to form amorphous Ca(HPO₄).xH₂O and Al₂O₃.xH₂O gel, rather than fly ash. These amorphous reaction products, which bound the partially reacted and unreacted CAC and fly ash particles into a coherent mass, were responsible for strengthening and densifying the SFCB specimens at room temperature, playing an essential role in mitigating their acid erosion. In these cements, the extent of acid erosion depended primarily on the ratio of fly ash/CAC; namely, those with a higher ratio underwent a severe erosion. This effect was due to the formation of a porous structure, which allowed acid to permeate the cement easily, diminishing the protective activity of Ca(HPO₄).xH₂O and Al₂O₃.xH₂O gel against H₂SO₄.     

Preferential oxidation of CO over CuO/CeO2 and Pt-Co/Al2O3 catalysts in micro-channel reactors

Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO₂ and Al₂O₃ on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO₂ catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al₂O₃ catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al₂O₃ catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O₂/CO ratio due to the oxidation of H₂ which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO₂ showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O₂/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al₂O₃, CuO/CeO₂), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX.     

Co3O4/CeO2 composite oxides for methane emissions abatement: Relationship between Co3O4–CeO2 interaction and catalytic activity

Co₃O₄/CeO₂ composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co₃O₄) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co₃O₄ and CeO₂ were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out.

An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co₃O₄ in correspondence of Co₃O₄–CeO₂ containing 30% by weight of Co₃O₄. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co₃O₄ phase and promoting the efficiency of the Co³⁺–Co²⁺ redox couple. The presence in the sample Co₃O₄(30 wt.%)–CeO₂ of a high relative amount of Ce³⁺/(Ce⁴⁺ + Ce³⁺) as detected by XPS confirms the enhanced oxygen mobility.

The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co₃O₄ phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co₃O₄ and Co₃O₄(30 wt.%)–CeO₂, performing the tests in the presence of 5 vol.% H₂O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H₂O + 5 vol.%O₂ in He) of the Co₃O₄(30 wt.%)–CeO₂ sample was also performed. All the results confirm the superiority of this composite oxide.     

铈硅包覆金红石型钛白粉及光催化性研究

采用溶胶-凝胶法,制备了铈硅包覆金红石型钛白粉,通过正交实验考察了浆液浓度、分散剂用量和两种包膜剂含量对铈硅包覆金红石型钛白粉性能的影响。采用Nano-ZS型粒度仪、扫描电镜（SEM）、透射电镜（TEM）和能谱（EDS）等测试手段,对金红石型钛白粉的Zeta电位、表面形貌和元素进行了表征。结果表明：在水浴温度为80 ℃左右、转速为600 r/min、浆液质量浓度为400 g/L、分散剂质量分数为0.1%、二氧化铈质量分数为3%、二氧化硅质量分数为4%的条件下,金红石型钛白粉表面包覆了两层均匀而致密的二氧化硅和二氧化铈膜;罗丹明B光催化降解实验证实,铈硅包覆明显改善了金红石型钛白粉的光催化屏蔽性。     

Catalytic reduction of SO2 over supported transition-metal oxide catalysts with C2H4 as a reducing agent

This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO₂ with C₂H₄ as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C₂H₄/SO₂, and pretreatment are all important factors affecting catalyst activity. Fe₂O₃/γ-Al₂O₃ was found to be the most active catalyst among six γ-Al₂O₃-supported metal oxide catalysts tested. With Fe₂O₃ as the active species, of the supports tested, CeO₂ is the most suitable one. Using this Fe₂O₃/CeO₂ catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C₂H₄/SO₂ is 1:1, and the catalyst presulfidized by H₂+H₂S exhibits a higher performance than those pretreated with H₂ or He. Although the feed concentrations of C₂H₄:SO₂ being 3000:3000 ppm provide a higher conversion of SO₂, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C₂H₄ temperature-programmed desorption (C₂H₄-TPD) and SO₂-TPD desorption patterns illustrate that Fe₂O₃/CeO₂ can adsorb and desorb C₂H₄ and SO₂ more easily than can Fe₂O₃/γ-Al₂O₃. Moreover, the SO₂-TPD patterns further show that Fe₂O₃/γ-Al₂O₃ is more seriously inhibited by SO₂. These findings may properly explain why Fe₂O₃/CeO₂ has a higher activity for the reduction of SO₂.