Thermal behaviors of deactivation catalysts for synthesizing 2, 3, 5-trimethylhydroquinone

The thermal behaviors of the deposits on supported noble metal catalysts for synthesizing 2, 3, 5-trimethylhydroquinone by DSC were studied. The results show that the supported Pd catalysts have two exothermic peaks at around 312 ℃ and 435 ℃ in the DSC thermograms, respectively, while the supported Pt catalysts have one exothermic peak at approximately 345 ℃. Therefore, it is supposed that the adsorptive states of deposits on supported Pt catalysts and supported Pd catalysts are different, which may be one reason leading to the stability difference between supported Pt catalysts and supported Pd catalysts.     

碳纳米纤维负载Pd—Pt催化剂的萘加氢抗硫性能

催化生长的碳纳米纤维经过的浓硝酸和浓硫酸液在不同的温度下进行了氧化处理．采用等体积浸渍的方法制备了碳纳米纤维负载的Pt、Pd和Pd-Pt催化剂．碳纤维表面引入的含氧基团的性质通过红外光谱进行了研究;用动态H2-化学吸附的方法研究了催化剂上金属颗粒的分散程度．催化剂的性能用萘加氢反应进行测试．随着碳纳米纤维表面氧化处理温度的升高引入的含氧基团数量增多,有利于金属的分散．碳纳米纤维负载的Pd-Pt催化剂具有非常好的活性和耐硫性．     

电催化剂及其对甲酸氧化的电催化性能

采用氨水调节的微波多元醇法合成了Pd/C和Pd2Pt/C催化剂,并使用透射电镜(TEM)和X-射线衍射(XRD)对催化剂的微观结构和形貌进行了表征.结果显示,在微波合成的电催化剂中Pd和Pd2Pt纳米粒子具有均匀的粒径,并高度分散在XC-72纳米碳载体上,Pd和Pd2Pt纳米粒子的平均粒径分别为54 和49 nm. 电化学测试结果显示,甲酸在Pd/C催化剂上氧化的起始电位和峰电位大大低于Pt/C催化剂,这是由于甲酸在Pd/C和Pt/C催化剂上不同的氧化途径引起的.结果还显示,甲酸在Pd2Pt/C催化剂和Pd/C催化剂上氧化的起始电位相同,而且在024和080 V有两个分别对应于甲酸在Pd和Pt催化剂的氧化, 说明微波合成的Pd/C和Pd2Pt/C催化剂对甲酸的氧化具有良好的电催化性能.     

负载贵金属的层柱分子筛抗硫中毒性能研究

以苯为模型化合物研究了负载贵金属的层柱分子筛（ＰＬＣ）催化剂在苯加氢反应中的抗硫性能。考察了在Ａｌ－ＣＬＭ和Ａｌ－ＣＬＢ上负载Ｐｔ或Ｐｄ的单金属催化剂和负载双金属Ｐｔ和Ｐｄ催化剂的抗硫性能，不同的Ｐｔ／Ｐｄ比对催化剂抗硫性能的影响。结果表明，Ｐｔ（Ｐｄ）／ＰＬＣ的抗硫性能远远低于Ｐｔ（Ｐｄ）／γ－Ａｌ２Ｏ３催化剂的抗硫性能；Ｐｔ／ＰＬＣ抗硫性能优于Ｐｄ／ＰＬＣ的抗硫性能；Ｐｔ（Ｐｄ）／Ａｌ－ＣＬＭ的抗硫性能优于Ｐｔ（Ｐｄ）／Ａｌ－ＣＬＢ催化剂的抗硫性能；Ｐｔ－Ｐｄ／ＰＬＣ的抗硫性能较单金属催化剂的抗硫性能得到明显改善，且Ｐｔ／Ｐｄ比对其抗硫性能有重要影响，当含Ｐｔ的质量分数为０．３％，含Ｐｄ的质量分数为０．９％时，Ｐｔ－Ｐｄ／Ａｌ－ＣＬＭ催化剂的抗硫性能最佳。     

Formation and Characterization of Pd, Pt and Pd-Pt Alloy Films on Polyimide by Catalyst-Enhanced Chemical Vapor Deposition

Platinum, palladium and their alloy films on polyimide were formed by catalyst-enhanced chemical vapor deposition （CVD） in the carrier gas （N2, O2） at 220-300℃ under reduced pressure and normal pressure. The deposition of palladium complexes [ Pd（（η3-allyl）（hfac） and Pd（hfac）2 ] gives pure palladium film, while the deposition of platinum needs the enhancement of palladium complex by mixing precursor platinum complex Pt（COD）Me2 and palladium complex in the same chamber. The co-deposition of Pd and Pt metals was used for the deposition of alloy films. During the CVD of palladium-platinum alloy, the Pd/Pt atomic ratios vary under different co-deposition conditions. These metal films were characterized by XPS and SEM, and show a good adhesive property.     

贵金属纤维催化剂的CH4催化燃烧活性

为了得到活性高、成本低的CH4催化燃烧催化剂,制备了一种Pt、Pd负载在硅铝纤维棉载体上的催化剂,考察了CH4催化燃烧的活性及抗老化性能,研究了载体的组成、预处理方法及贵金属负载量对催化剂活性的影响.结果表明:利用淄博华岩耐火纤维公司生产的高铝型纤维棉作为载体制备的催化剂的活性最好;载体预处理方法影响催化剂活性,其中用质量分数为1%的盐酸常温浸泡30 min得到的纤维载体最佳;当负载的Pt的质量分数为1.5%,负载的Pd的质量分数为2%时,催化剂活性最好,1.5%Pt/Z3催化剂的CH4完全转化温度为600℃,2%Pd/Z3催化剂的CH4完全转化温度为450℃;2%Pd/Z3催化剂在800℃经过100 h老化后,其t50仅提高了50℃,该催化剂具有良好的抗老化性能.     

桂北宝坛地区满洞铜镍硫化物矿床铂族元素地球化学特征及其对矿床成因的制约

桂北宝坛地区铜镍硫化物矿床块状矿石和浸染状矿石之间的成因联系尚存争议,对其开展研究为提高该地区铜镍硫化物矿床成因认识和下一步深部找矿勘探都具有重要意义。通过分析满洞铜镍硫化物矿床矿石和赋矿岩石铂族元素(PGE)特征,探讨桂北宝坛地区铜镍硫化物矿床成因。结果表明:满洞铜镍硫化物矿床矿石和赋矿岩石铂族元素总含量普遍较低,且与硫化物含量成明显正相关关系,铂族元素相对于Ni和Cu明显亏损; 不同种类矿石和岩石原始地幔标准化铂族元素蛛网图总体表现为弱分异,Pd/Ir值为0.93～15.41; 然而其相对Pt含量明显不同,块状矿石呈现强烈Pt亏损,浸染状矿石Pt呈弱富集,赋矿岩石无Pt异常; 矿石和岩石Cu/Pd值((10.38～1 830.00)×10³)均远大于原始地幔(6 500),表明该矿床深部存在早期硫化物熔离作用,造成岩浆在浅部再次硫化物熔离时亏损铂族元素; 含铂矿物在单硫化物固溶体结晶之前从硫化物熔体中直接结晶,之后硫化物熔体在构造作用下沿裂隙迁移固结形成块状矿石,从而造成块状矿石Pt亏损。     

Montmorillonite supported titanium/antimony catalyst: Preparation,characterization and immobilization

Montmorillonite supported titanium(Ti-MMT) or antimony catalyst(Sb-MMT) has been a hot area of research on preparing polyethylene terephthalate/montmorillonite(PET/MMT) nanocomposites by in situ polymerization. So removal of Ti or Sb from Ti-MMT or Sb-MMT is not expected during in situ polymerization. Studies on immobilization of Ti or Sb on Ti-MMT or Sb-MMT are seldom reported. In this work, a series of montmorillonite supported catalysts of titanium(Ti-MMT) or antimony(Sb-MMT) and cointercalated montmorillonite of titanium and antimony(Ti/Sb-MMT) were prepared by(1) the reaction of sodium bentonite suspension with intercalating solution containing titanium tetrachloride and/or antimony chloride, and(2) drying or calcinating the products at different temperature(100, 150, 240, 350 and 450 ℃). The physicochemical properties of these MMT supported catalysts were studied by X-ray diffraction(XRD), fourier transform infrared spectroscopy(FT-IR), inductively coupled plasma optical emission spectrometer(ICPOES), N 2 adsorption/desorption isotherms, UV-visible diffuse reflectance spectroscopy(UV-vis) and transmission electron microscopy(TEM). The immobile character of Ti or Sb on MMT supported catalysts was evaluated by a two-step method in deionized water or ethylene glycol. Several results were obtained, i e,(a) during the preparation, with an increase in drying or calcinating temperature, the amount of titanium and/or antimony species remained on these MMT supported catalysts decreased,(b) the experiments about immobile character of Ti or/and Sb showed that with an increase in drying or calcinating temperature, the immobilization of Ti and/or Sb species remained on these MMT supported catalysts increased gradually,(c) Ti-MMT calcinated at 450 ℃ had the biggest pore volume, which means Ti-MMT had the best adsorption application prospect.     

中空Pd/C催化剂的合成及其对甲酸氧化电催化性能

为了提高Pd/C催化剂对甲酸电化学氧化的电催化性能和降低催化剂的成本,以XC-72碳为载体,通过金属置换反应制备中空结构的Pd/C催化剂,并用X-射线衍射（XRD）,透射电镜（TEM）和X-射线电子散射能谱（EDX）对催化剂微观形貌和结构进行表征.结果显示中空Pd纳米粒子的平均直径为27.3 nm, 电化学活性比表面积为116 m²/g,远远高于用硼氢化钾还原制备的实心Pd/C催化剂的.中空的Pd/C催化剂对甲酸氧化的电催化活性显著高于实心Pd/C催化剂,同时中空Pd/C催化剂的催化活性稳定性也优于实心Pd/C催化剂.     

Preparation process and characterization of new Pt/stainless steel wire mesh catalyst designed for volatile organic compounds elimination

A novel 0.1% Pd-0.05% (mass fraction) Pt/stainless steel wire mesh catalyst was prepared for volatile organic compounds (VOCs) elimination. The catalyst was synthesized by stainless steel wire mesh as support and then treated by anodic oxidation technology to develop a porous membrane on the support. During the anodic oxidation process, various electrolytes were used to investigate the formation of porous membrane. And the catalytic performance of the catalysts was tested by using toluene and acetone combustion as model reaction. The temperatures of complete toluene and acetone conversion were decreased to 180 °C and 240 °C, respectively. The morphologies of the stainless steel wire mesh supports and catalysts were characterized by means of scanning electron microscopy (SEM) and temperature-programmed reduction (TPR).     

纳米PdNi催化剂对乙醇的催化氧化

通过使用柠檬酸三钠作为金属稳定剂,NaBH₄作为还原剂制备了不同比例的碳负载型PdNi催化剂,用XRD手段对催化剂进行了表征.电化学结果表明,PdNi（2:1）催化剂对乙醇电催化氧化活性明显优于其他比例合金催化剂的电催化活性.     

Supporting of nickel(II) acenaphthenediimine with free amino group for ethylene polymerization

Bis (4-(4-amino-3, 5-diethylbenzyl)-2, 6-diethylphenylimino) acenaphthene] dichloronickel (NiLCl₂) was prepared and supported on SiO₂ modified by methyl trichlorsilane(S-1) and on SiO₂-MgCl₂/TiCl₄ (S-2) respectively. Two supported catalysts S-1 and S-2 used as catalysts for ethylene polymerization were studied and the influences of various polymerization conditions, including the polymerization temperature, cocatalysts, Al/Ni molar ratio on the catalytic activity, branching degree and branch length of PE were also investigated. The experimental results show that the supported catalysts exhibit higher catalytic activity for ethylene polymerization, the highest catalytic activity of S-1 using AlEt₂Cl as cocatalyst at 50°C, reaching 5.8×10⁵gPE/molNi··h, and needed lower Al/Ni molar ratio compared to homogeneous analogue.     

Spark Plasma Sintering Preperties of Ultrafine Ti （ C, N）-based Cermet

Ultrafine Ti( C, N)-based cermet was sintered by SPS from 1050℃ to 1450℃ and its sintering properties, such as porosity, mechanical properties and phase transformation , were investigated by optical microscopy ( OM ), scanning electron microscopy (SEM), X-ray diffraction ( XRD ), and differential scanning calorimeter (OSC). It is found that the spark plasma sintering properties of Ti ( C, N )-based cermet differ from those of conventional vacuum sintering. The liquid phase appearance is at least lower by 150℃ than that in vacuum sintering. The porosity decreases sharply belove 1200℃ and reaches minimum at 1200℃ , and afterwards it almost keeps invariable and no longer increases. SPS remarkably accelerates the phase transformation of Ti ( C, N )-based cermet and it has a powerful ability to remorse oxides in Ti( C, N)-based cermets. Above 1350℃, denitrification occurred. Fresh graphite phase formed above 1 430℃ . Both the porosity and graphite are responsible for the poor TRS.     

Effect of cobalt loading on reducibility, dispersion and crystallite size of Co／Al2O3 Fischer-Tropsch catalyst

Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction (XRD), temperature programmed reduction (TPR), hydrogen temperature programmed desorption (H2-TPD) and O2 titration. Co-support compound formation can be detected in catalyst system by XRD.For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O3 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3 O4 crystallites (reduction at 320 ““C) and cobalt oxidealumina interaction species (reduction at above 400℃). Increasing Co loading results in the increase of Co3 O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.     

Hydroxyapatite bioceramic coatings prepared by hydrothermal-electrochemical deposition method

The hydroxyapatite(HA) ceramic coating was successfully prepared on Ti6Al4V alloy by the hydrothermal-electrochemical deposition method with constant voltage model. The phases of deposits were analyzed by X-ray diffraction. The releationship between crystallinity and depositing temperature was discussed. The microstructures of hydroxyapatite coating were observed by scanning electron microscope. The experimental results showed that the phases, crystallinity and morphologies of deposits were influenced by depositing temperature(100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃, respectively). The special hydrothermal environment can lower the crystallization temperature of HA. The crystallinity of HA increases firstly and then decreases with the increase of temperature. There is little hydroxyapatite deposited on the Ti6Al4V surface when the depositing temperature is 100 ℃. The HA deposition increases with the increase of the depositing temperature. And the HA morphologies are influenced by the depositing temperature.     

PtRu/C和PtNi/C催化剂合成及其对甲醇氧化的电催化性能

采用微波多元醇法合成PtRu/C和PtNi/C催化剂,利用透射电镜（TEM）和X-射线衍射仪（XRD）对催化剂的微观结构和形貌进行了表征.结果表明,在催化剂中PtRu和PtNi合金纳米粒子的平均粒径分别为2.7和3.0 nm,粒径均匀,并高度均匀地分散在碳载体上.电化学测试结果表明,与Pt/C催化剂相比,PtRu/C和PtNi/C催化剂对甲醇的电化学氧化具有更低的起始电位和更稳定的极化电流,说明PtRu/C和PtNi/C催化剂对甲醇氧化具有更稳定的电催化性能和更好的抗CO中毒性能.这是由于合金催化剂中的Ru和Ni可以在较低的电位下与其表面吸附水形成含氧物种,使Pt表面吸附的CO等中间物氧化为CO2,避免了催化剂的CO中毒.     

低温浸渍还原法制备负载型Pd基纳米催化剂的电催化性能研究

采用改进的浸渍还原法在低温下制备了Pd_2Ni_3/C纳米催化剂.TEM图像显示,催化剂的粒径较小,且均匀分散在碳载体表面;XRD图谱可以看出,Pd(111)衍射峰由于Ni的掺杂效应发生宽化,说明采用这种方法合成的Pd-Ni/C催化剂粒径较小;电化学测试表明,Pd_2Ni_3/C具有较高的甲酸电催化活性和稳定性.     

固定床催化合成N,N,N′,N′-四甲基乙二胺的研究

通过自制备的金属负载型催化剂,以二甲胺和乙二醇为原料,在气固固定床反应器中合成了N,N,N′,N′-四甲基乙二胺.以γ-Al2O3为载体,Cu、Ni、Cr、Zn等金属为活性组分,通过浸渍法制备了3种二元金属负载型催化剂:Cu-Ni型、Cu-Zn型、Cu-Cr型.在相同条件下对3种催化剂的催化性能进行了考察,对乙二醇转化率及四甲基乙二胺的选择性进行了分析,结果表明:Cu-Ni型催化剂的催化效果最佳.通过平行实验对反应温度、胺醇的物质的量比及体积空速进行了研究,获得了较优的条件区间范围.根据平行实验结果,采用响应面实验设计方法(DesignEx-pert软件)对反应条件进行了优化,获得了最优的反应条件:以Cu-Ni为活性组分的催化剂进行催化,反应温度为204.81℃,胺醇的物质的量比为5.27,体积空速为0.29h-1,最佳产率可以达到79.84%.     

High-temperature phase transition and the activity of tobermorite

The high-temperature phase transition of tobermorite was investigated by TGA/DSC, X-ray diffraction and Infrared spectroscopy(IR), respectively. The experimental results showed that Si-OH bonds were cleaved at 724 ℃ and dehydroxylation occured at the same time, implying that the crystal structure of tobermorite was broken. As a result, the dehydroxylation tobermorite was metastable state, exhibiting obviously hydrolysis activity. The suspension was alkaline and Ca2+ ions content reached a maximum value 4.76% after heat treatment at 724 ℃. The dehydroxylation tobermorite had potential reactive activity due to the strong hydrolysis activity. The disordered structure recombined to wollastonite, and the crystal structure became ordering and stable at 861 ℃. Finally, 2M-wollastonite structure can be found in the sample as the temperature reached up to 1 000 ℃.     

Selective catalytic reduction of NO with NH3 over sol-gel-derived CuO-CeO2-MnOx/γ-Al2O3 catalysts

Granular CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH₃ and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts is 300–400 °C. The catalysts maintain nearly 100% NO conversion at 350 °C. The °C NH₃ oxidation experiments show that both NO and N₂O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH₃, which improves the denitrification activity at low temperature. The over-oxidation of NH₃ at high temperature is the main cause leading to a decrease in the NO conversion. The NH₃ and NO desorption experiments show that NH₃ and NO can be adsorbed on CuO-CeO₂-MnO _x /γ-Al₂O₃ granular catalysts. The transient response of NH₃ and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process. Foundation item: Projects (50776037, 50721005) supported by the National Natural Science Foundation of China