Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。     

油页岩矿物质催化半焦燃烧特性及机理

利用微型流化床反应分析仪（MFBRA）研究了油页岩矿物质催化半焦燃烧特性，重点考察了半焦内部矿物质和外部页岩灰床料对半焦燃烧的催化作用，揭示了流化床反应器中半焦燃烧过程和机理。结果表明：内部矿物质和外部床料对半焦燃烧均具有明显催化作用，而两者共同催化效果最为显著。矿物质中CaO和Fe₂O₃对半焦燃烧具有催化活性，CaO催化作用强于Fe₂O₃。油页岩半焦燃烧反应活化能在60.41~78.97 kJ/mol之间，矿物质的催化作用会明显降低反应活化能。流化床反应器中，矿物质对半焦燃烧的催化作用主要表现在四个反应，即：挥发分裂解和燃烧、半焦表面炭燃烧、半焦内部炭燃烧以及一氧化碳燃烧。     

Rational Design of Metal Nanoframes for Catalysis and Plasmonics

Recently, metal nanoframes have received increased attention due to their unique spatial and physicochemical, e.g., catalytic and plasmonic properties. So far, a variety of synthetic procedures have been developed to fabricate metal nanoframes with different shapes, sizes and compositions. Typical synthesis of metal nanoframes involves two stages: 1) formation of solid nanocrystals and 2) hollowing out the interiors and side faces. In this review, solution‐phase synthetic strategies are summarized, based on galvanic replacement reactions, oxidative etching, the Kirkendall effect, electrodeposition, and template‐assisted growth, as well as one‐pot synthesis. Their potential applications in catalysis and optical sensing are overviewed as well.     

超高压调节酶催化功能及其作用机制

在酶学领域中,超高压和温度类似,作为一种物理学方法,可以用来调节酶催化功能,促使酶的构象发生变化。对超高压调节酶催化功能的原理、影响酶构象的作用机制,以及一些新型研究方法等进行了综述。展望了此项新技术的发展前景。     

Catalytic Evaluation of CuO/[Si]MCM‐41 in Fenton‐like Reactions

CuO/[Si]MCM‐41 catalysts with various Si/Cu molar ratios were prepared and characterized by X‐ray diffraction, nitrogen physisorption, temperature‐programmed reduction by H₂, and UV‐vis and Raman spectroscopy. The effects of copper loading and pH on their activity in the decolorization of methyl orange were studied in a heterogeneous Fenton‐like process. With decreasing Si/Cu ratio, dye decolorization increased from 18 to 75 % at pH 3. CuO/[Si]MCM‐41 catalysts showed 75, 50, and 40 % conversion of methyl orange at pH 3, 5, and 7, respectively. This is a significant improvement to Fenton‐like reactions involving copper, and thus CuO/[Si]MCM‐41 catalysts are quite promising for pollutant degradation.     

Enhanced electron harvesting in next generation solar cells by employing TiO2 nanoparticles prepared through hydrolysis catalytic process

Titanium dioxide (TiO₂) nanoparticles (NPs) were synthesized through solvothermal route by changing the rate of hydrolysis in the catalytic process. In order to change the hydrolysis rate, the concentration of acetic acid, as additive, was varied as 2 M, 3 M and 4 M. The synthesized NPs were examined by various physico-chemical characterization techniques. The powder X-ray diffraction (PXRD) analysis of the NPs reveals only the anatase phase of TiO_2. The spherical shaped morphology of the NPs was observed in the high-resolution transmission electron microscopy (HR-TEM) analysis. The optical behaviour such as absorption, bandgap, diffuse reflectance and photoluminescence (PL) emission of the NPs were studied. The material's nature and behaviors were scrutinized and they were employed as photoanode in dye sensitized solar cell (DSSC) and as electron transport layer (ETL) in carbon-based perovskite solar cell (C-PSC). The charge transfer at the interface of the devices was studied with electrochemical impedance spectroscopy (EIS). The fabricated DSSC and C-PSC show highest power conversion efficiency (PCE) of 6.1% and 10.6%, respectively. The highest current collection was detected in C-PSC and the results are discussed in detail.