间二甲苯的离解光电离的实验与理论研究

本文利用同步辐射真空紫外和超声分子束反射式飞行时间质谱系统研究间二甲苯的光电离和离解光电离.通过测定母体离子C_(8)H_(10)^(+)和主要碎片离子(C_(8)H_(9)^(+)和C_(7)H_(7)^(+))的光电离效率谱,确定了母体分子的电离能和主要碎片离子(C_(8)H_(8)^(+)和C_(7)H_(7)^(+))的出现势分别为8.60±0.03 eV,11.76±0.04 eV和11.85±0.05 eV eV.在B3LYP/6-311++G(d,p)水平上优化了两个主要解离通道的反应物、过渡态、中间体和产物的结构,并在G3水平上计算了它们的能量,以及两个主要的离解光电离通道产物C_(7)H_(7)^(+)+CH_(3)和C_(8)H_(9)^(+)+H的能量.结合理论和实验结果,间二甲苯的离解光电离机理主要过程是C-H键或C-C键的离解和氢迁移.

Insight into catalytic properties of Co3O4-CeO2 binary oxides for propane total oxidation

A series of Co3O4-CeO2 binary oxides with various Co/(Ce+Co)molar ratios were synthesized using a citric acid method,and their catalytic properties toward the total oxidation of propane were examined.The activities of the catalysts decrease in the order CoCeOx-70>CoCeOx-90>Co3O4>CoCeOx-50>CoCeOx-20>CeO2.CoCeOx-70(Co/(Ce+Co)=70% molar ratio)exhibits the highest catalytic activity toward the total oxidation of propane,of which the T90 is 310℃(GHSV=120000 mL h^-1 g^-1],which is 25℃ lower than that of pure Co3 O4.The enhancement of the catalytic performance of CoCeOx-70 is attributed to the strong interaction between CeO2 and Co3O4,the improvement of the low-temperature reducibility,and the increase in the number of active oxygen species.In-situ DRIFTS and reaction kinetics measurement reveal that Ce addition does not change the reaction mechanism,but promotes the adsorption and activation of propane on the catalyst surface.The addition of water vapor and CO2 in reactant gas has a negative effect on the propane conversion,and the catalyst is more sensitive to water vapor than to CO2.In addition,CoCeOx-70 exhibits excellent stability and reusability in water vapor and CO2 atmosphere.

East Asian Winter Monsoon record from the environmental sensitive grain size component of QF Old Red Sand, Haitan Island, China

The ＂Old Red Sand＂ is widely distributed along the coast of Fujian Province, China. Most studies have been carried out from as- pects of the origin, age and laterization of the ＂Old Red Sand＂, but this paper focused on reconstructing the history of the Asian Winter Monsoon change. On the basis of granulometric analysis of high-resohition samples, we have obtained environmental sen- sitive grain size component （ESGSC） from the Qingfeng （QF） profile by using the grain size-standard deviation method, which proves that the selected ESGSC is an important climate proxy. The mean grain size of this ESGSC could be used to reconstruct the East Asian Winter Monsoon （EAWM） intensity. As such, the history of the EAWM change since 44.0 ka reconstructed here reveals three main phases based on chronology dates of previous researches： （1） 44.0-25.5 ka B.P., the EAWM is relatively weak but increases gradually with fluctuations; （2） 25.5-15.5 ka B.P., relatively strong with high frequency fluctuations; （3） 15.5-7.1 ka B.P., with a weaker winter monsoon, but during 11-10 ka B.P. is remarkably enhanced. The EAWM recorded by mean grain size of the two neighboring sections have a better repeatability, so the millennial scales oscillation should be a reliable signal of the EAWM intensity. The climate recorded by ESGSC of the QF ＂Old Red Sand＂ compared to 6-80 of Huhi Cave stalagmites and Greenland GISP2 ice cores shows a good consistency, especially in detail, the YD event and four Heinrich events are all recorded, but the signal of D-O cycles was relatively weak.

Microfossil evidence of rice cultivation on the Southeast China Coast 7500 years ago

Located on the southeast coast of China,Fujian is an important junction for the spread and migration of agriculture and populations from mainland Asia to Taiwan and the Island Southeast Asia.Research on the emergence of agriculture and its relationship with the regional environmental context is key to understanding the evolution of ancient human-land interactions in the coastal zone of China.This paper presents a detailed microfossil analysis of the Dapingding site,which is located in the lower reaches of the Min River on the southeast coast of China.We found a large number of phytoliths produced in rice stems and leaves from the cultural layers of this site,dated to 7,500 cal.a BP.In addition,we found rice husk impressions and rice phytoliths in the pottery sherds of these cultural layers.Among these phytoliths,rice bulliform phytoliths with≥9 fish-scale patterns indicating the degree of rice domestication,accounted for 44%.This percentage is much higher than the established standard for wild rice bulliform phytoliths with fish-scale patterns,suggesting that rice cultivation had already occurred on the southeast coast of China approximately 7,500 years ago.Subsequently,the starting time of agricultural activity on the southeast coast of China was pushed from 5,000 to 7,500 years ago.Comparing the regional history of sea level and coastline changes in the early to mid-Holocene,we suggest that the emergence of early rice cultivation in Southeast China was associated with high sea levels in the midHolocene and the last transgression in the Fuzhou Basin.The’Fuzhou Bay’,formed by the retreating coastline and transgression driven by high sea levels,may have provided a sea channel for the southward movement of northern rice farmers.