原位DRIFTS研究CH4部分氧化和CO2重整的耦合

8%Ru-5?/γ-Al2O3催化剂对于甲烷的低温活化具有较好的催化活性,在500℃下甲烷、二氧化碳和氧气的耦合反应中,吸热反应二氧化碳重整和放热反应甲烷部分氧化进行耦合强化,使得耦合反应中的甲烷转化率为38.8%。用原位漫反射傅里叶红外光谱法对钌系催化剂耦合甲烷部分氧化和二氧化碳重整反应体系机理进行研究。CO在8%Ru-5?/γ-Al2O3上吸附,表明CO在催化剂表面上波数为2 167 cm-1(2 118 cm-1)和2031 cm-1(2 034 cm-1)处形成孪生态Ru(CO)2和Ce(CO)2吸附物种,而且高温下CO吸附物种很容易从催化剂表面脱附出来。原位漫反射红外实验结果表明甲烷部分氧化反应时催化剂表面上有吸附物种碳酸根、甲酰基(甲酸盐)和一氧化碳的形成,其中表面的甲酰基和甲酸盐物种是甲烷部分氧化反应的主要活性中间物,这些中间活性中间体由甲烷吸附态CHx和催化剂表面的氧吸附态结合而形成的,随后这种中间物种再分解为CO产物;甲烷和二氧化碳重整反应时没有新的吸附物种产生,由此提出重整反应的机理是吸附态的甲烷和二氧化碳在催化剂活性中心上进行活化解离而生成合成气;甲烷、二氧化碳和氧气耦合反应过程中出现新的羟基物种(桥式羟基Ru-(OH)2),耦合反应机理复杂可能是由部分氧化和重整两类反应机理的复合,其中桥式羟基Ru-(OH)2参与了反应的进行。     

The Structure of Hybrid Gels by Drift and NMR Spectroscopies

Hybrid inorganic-organic gels have been prepared by the sol-gel process using tetraethoxysilane (TEOS) as precursor, mixed with a low concentration of polytetrahydrofuran (PTHF), under acid catalysis. The hybrid xerogels were characterized by DRIFTS and Solid State ¹H, ¹³C and ²⁹Si NMR. The DRIFT spectra indicate that the polymer is responsible for decreasing the number of free silanol groups in comparison to pure silica. Solid-state NMR spectra reveal the types of silicate structures formed and the conditions for establishing chemical bonds between the two phases, which are responsible for the silica network flexibility. We have concluded that it is possible to design a hybrid gel with tailored properties, even at very low polymer concentration, by selecting the appropriate preparation route.     

Adsorption Behavior of Nitrogen Monoxide on KxGaxSn8−xO16 Hollandite

Fine powder of K _x Ga _x Sn_8–x O₁₆ hollandite was prepared by the sol-gel process using metal alkoxides, and the adsorption behavior of nitrogen monoxide (NO) on it was examined by temperature programmed desorption (TPD) method and in situ diffuse reflectance fourier transform infrared spectroscopy. Any species other than nitrogen monoxide were not detected in the TPD measurement, and the profile showed three stages between 420 and 880 K which were regarded as the desorption of chemically adsorbed NO _x species. This desorption behavior seems well consistent with the spectral changes in the FT-IR measurement. The absorption band at 1270 cm^–1 was decayed in the first stage from 420 to 640 K, and the bands at 1235 and 1570 cm^–1 in the second stage from 640 and 770 K. In the third stage above 770 K, the strong band at 1340 cm^–1 disappeared. These NO _x species on the hollandite were estimated to have a form of NO₃ ^– in the first and second stages and a form of NO₂ ^– in the third stage, considering the data on adsorption of nitrogen oxides on La₂O₃ and CaO.     

溶胶-凝胶法制备掺杂二氧化钛薄膜及其光电性能研究

运用溶胶-凝胶法制备玻璃、陶瓷材料,具有低温、均匀、高纯、溶液铸塑等独特的优点,已引起科研人员的极大兴趣^[1]。二氧化钛是一种具有良好的光学性能的半导体材料,并已被广泛地研究。     

Recent advances in the use of graphene-family nanoadsorbents for removal of toxic pollutants from wastewater

Adsorption technology is widely considered as the most promising and robust method of purifying water at low cost and with high-efficiency. Carbon-based materials have been extensively explored for adsorption applications because of their good chemical stability, structural diversity, low density, and suitability for large scale production. Graphene – a single atomic layer of graphite – is the newest member in the family of carbon allotropes and has emerged as the “celeb” material of the 21st century. Since its discovery in 2004 by Novoselov, Geim and co-workers, graphene has attracted increased attention in a wide range of applications due to its unprecedented electrical, mechanical, thermal, optical and transport properties. Graphene's infinitely high surface-to-volume ratio has resulted in a large number of investigations to study its application as a potential adsorbent for water purification. More recently, other graphene related materials such as graphene oxide, reduced graphene oxide, and few-layered graphene oxide sheets, as well as nanocomposites of graphene materials have also emerged as a promising group of adsorbent for the removal of various environmental pollutants from waste effluents. In this review article, we present a synthesis of the current knowledge available on this broad and versatile family of graphene nanomaterials for removal of dyes, potentially toxic elements, phenolic compounds and other organic chemicals from aquatic systems. The challenges involved in the development of these novel nanoadsorbents for decontamination of wastewaters have also been examined to help identify future directions for this emerging field to continue to grow.     

Organometallic chemistry in the melt phase

In this review organometallic chemistry reactions in the melt phase are described. As will be indicated this is a viable approach to make new and known complexes. Examples from the literature highlighting procedures used to generate melts and results that have been obtained in this area of synthesis are described. Clearly there will be limitations to the use of the melt phase, and these limitations are also discussed.     

Spectroscopic study of the surface oxidation of mechanically activated sulphides

Surfaces of chalcopyrite CuFeS₂, sphalerite ZnS, pyrite FeS₂ and galena PbS modified by mechanical activation have been studied by means of infrared (IR) spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray photoelectron spectroscopy (XPS). The different oxidation species were identified on mechanically disordered surfaces of the minerals. The mechanochemical surface oxidation increases with the time of mechanical activation. The sulphides under study are partially covered with oxidised sulphates and carbonate species. They are distinguished by an affinity to the formation of surface compounds. According to the affinity of sulphides for mechanochemical S²⁻→S⁶⁺ surface oxidation the decreasing rate was observed in the following order: FeS₂>PbS>CuFeS₂>ZnS. The ratio between bivalent and hexavalent form of sulphur depends on the degree of mechanochemical surface oxidation of the sample under study.     

海盐颗粒物表面的NO_2非均相反应

为了深入理解沿海城市大气环境中NO2和海盐颗粒物的非均相反应规律,本研究使用漫反射红外傅立叶变换光谱(DRIFTS)比较研究了0%和20%相对湿度(relative humidty,RH)下NO2在湿海盐颗粒物表面的非均相反应.动力学测量表明硝酸盐的生成对NO2是二级反应,并且0%和20%相对湿度条件下,NO2分子浓度为1.96×1015molcules·cm-3时,反应增长阶段反应摄取系数分别为(5.51±0.19)×10-7和1.26×10-6.结果还显示相对湿度在30%以下时,海盐表面MgCl2·6H2O、CaCl2·2H2O所在点位通过释放结合水和吸附水汽,在海盐表面形成液态水的斑点,增强了反应持续能力.因此氯化钠表面非均相反应的研究可能会低估海盐颗粒物的非均相反应活性.     

甲醛在TiO_2颗粒物表面的非均相反应

使用漫反射红外傅里叶变换光谱(DRIFTS)原位反应器研究了甲醛在TiO2颗粒物表面的非均相反应,结合离子色谱定量分析了反应的主要产物甲酸盐,甲酸盐是由中间产物二氧亚甲基进一步氧化生成.研究了温度和紫外光照对反应的影响,结果表明升高温度和紫外光照可提高反应速率,推测了暗反应和紫外光照下甲醛在TiO2表面的非均相反应机制.结果表明常温下甲醛在TiO2颗粒物表面的反应级数接近2级,初始反应摄取系数为(0.5～5)×10-8([HCHO]:1×1013～2×1014molecule·cm-3),是甲醛浓度的一次函数,同时测定了表观活化能.