Synthesis and characterization of MCM-41-supported nano zirconia catalysts

Series of MCM-41 supported sulfated Zirconia (SZ) catalysts with different loadings (2.5–7.5% wt.) were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.     

Enhancing cation exchange capacity of chars through ozonation

The use of ozone to increase the cation exchange capacity (CEC) of two chars produced from pyrolysis of Douglas fir (Pseudotsuga menziessii) and a control bituminous coal activated carbon (AC) is reported. Chars were produced from the wood fraction of Douglas fir (DFWC) and the bark (DFBC) at 500 °C using an auger driven reactor with a nitrogen sweep gas under mild vacuum. Five ozone treatment times, ranging from 5 min to 60 min, were investigated. The initial properties of each char were found to differ significantly from the other samples in terms of surface area, proximate composition, and elemental composition. DFWC did not show significant mass loss or temperature variation during ozone treatment; however, after 1 h of oxidation both DFBC and AC samples resulted in 20% and 30% mass loss, respectively, and reactor temperatures in excess of 60 °C. Analysis of the pore size distribution of each treatment shows that ozone treatment did not significantly affect small micropores after 30 min of treatment for any material, but did reduce the apparent surface area of mesopores. Increases in carboxylic groups were identified with ozone treatment and found to correlate strongly with changes in measured CEC. The formation of lactone was found to correlate positively with reactor temperature during oxidation. These results indicate that the properties of chars, including surface area, pore structure, and chemical composition, as well as reactor conditions strongly affect the ozone oxidation of chars.     

红外光谱法用于快速测定车用柴油酸度等性质的研究

针对车用柴油酸度等性质测定过程繁琐，采用衰减全反射样品池测定车用柴油的红外光谱，用偏最小二乘法（PLS）建立红外光谱测定车用柴油酸度、密度、闪点和凝点的4个校正模型，验证标准误差分别为0.46 mg/(100 mL),0.77kg/m3,2.60 ℃,2.77 ℃，该方法符合标准方法再现性要求。与标准方法相比，该方法具有无需预处理、操作简单、测量快速、重复性好等优点。     

SO4^2-／ZrO2固体超强酸的制备及其催化合成ETBE的研究

采用沉淀一浸渍法制备了负载型SO4^2-／ZrO2固体超强酸催化剂，运用IR、XRD等方法表征所制备催化剂的物化性质。结果表明，所制备的催化剂具有固体超强酸催化剂的特征，酸性与焙烧温度有关，适当提高焙烧温度有利于样品酸强度的提高，但焙烧温度过高会导致脱硫；浸渍液H2SO4浓度高有利于提高催化剂的硫含量，但是浓度过高，会在催化剂上形成硫酸盐，从而降低催化剂的比表面积和酸性。采用制备的催化剂气相催化乙醇与叔丁醇合成乙基叔丁基醚反应，乙基叔丁基醚的选择性为54．71％。     

Cd-ZSM-5沸石催化剂的制备、表征和芳构化催化性能

采用离子交换、浸渍和混合三种方法制备镉改性ZSM-5沸石催化剂,考察了改性方法和镉含量对催化剂的表面酸性和Cd状态以及芳构化性能的影响。结果表明,加入镉降低了B酸性,Cd~(2+)与沸石结合形成了L_(1612)酸中心,其生成量取决于改性方法和Cd含量,并与芳构化活性提高有直接关系。     

Sulfated zirconia catalysts: Are Brønsted acid sites the source of the activity?

The thermal decomposition products of pyridinium sulfate differ from those of pyridinium sulfate supported on zirconia which in turn differs from that of pyridine adsorbed on a sulfated zirconia. Unsupported pyridinium sulfate decomposes to produce pyridine and sulfuric acid, and these subsequently react to produce oxides of carbon and sulfur. Zirconia that is sulfated and then exposed to pyridine does not release detectable amount of pyridine during heating in an inert gas; rather the pyridine undergoes oxidation reduction reactions simultaneously to release CO₂ and sulfur compounds. Pyridinium sulfate supported on zirconia decomposes upon heating to release pyridine and sulfuric acid, which reacts with the zirconia. The desorption of pyridine in one case and only CO₂/SO_x in the other case suggests that sulfated zirconia does not contain Brønsted acidity that can form pyridinium sulfate.     

新型重整催化剂的研究——Pt／L中沸石酸碱性的作用

Ｐｔ／ＫＬ、Ｐｔ／ＢａＫＬ及Ｐｔ／ＨＬ上的铂与沸石的酸碱位发生相互作用，导致催化剂上存在不同电子状态和粒度分布的铂位，从而产生有着完全不同催化作用、不同抗硫性能的两类催化剂，即以碱性沸石为载体的“单功能”催化剂和以酸性沸石为载体的“双功能”催化剂。在Ｐｔ／ＫＬ、Ｐｔ／ＢａＫＬ催化剂上，存在着对硫敏感的具有环化脱氢功能和对硫不敏感的仅具有脱氢功能的两类铂活性位。     

Measurement of the Metal Surface Acidity/Electronegativity of Pt(110)

In previous work, it has been found that a hydrogen-covered Pt(110) surface is acidic, but quantification of the acidity has not yet been done. In this paper a spectroscopic method is developed to measure the acidity of a metal surface for the first time. The technique involves measuring the intensity of the N–H stretch from the C₅H₄XNH⁺ that forms when hydrogen coadsorbs with pyridine, 2-fluoropyridine and 3-fluoropyridine. The Bethe approximation is then used to estimate the metal surface acidity/electronegativity (MSAEL). The proton affinity/MSAEL of Pt(110) has been determined to be 907 ± 4 kJ/mol at high coverage. This is the first time the MSAEL has been measured on a metal surface. Implications for fuel cell catalysis are discussed.     

温度、酸度对大曲酒产、质量的影响

本文从温度、酸度对大曲酒产、质量的影响，揭示大曲酒夏季＂掉排＂的主要原因为高温、高酸环境抑制了酿酒酵母的发酵，降低了酿酒酵母的发酵力，从而影响了大曲酒的产、质量。     

TiO_2载体表面酸性的研究

利用NH_3吸附和吡啶吸附红外技术研究TiO_2的制备条件对其表面酸性的影响。结果表明,用NH_3水中和TiCl_4溶液方法制备的TiO_2(A)表面有较强的L酸中心,中和条件对表面酸性中心数目和强度有显著影响。由TiOSO_4水解方法制备的TiO_2(B)表面具有较强的L酸中心和较弱的B酸中心,引入不同添加剂可有效地调变TiO_2载体表面的酸性。