二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶 凝胶法以磷钼酸 (MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2 催化剂 .使用ICP、XRD、TG DTA、IR、TPD MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能 .杂多钼酸盐与TiO2 通过O2 -在TiO2 表面发生了键合 .在 6 2 3K下 ,杂多阴离子仍保持原有的Keggin结构 .CO2 在Lewis酸位Ni(Ⅱ )和Lewis碱位Ni-O -Mo的桥氧协同作用下生成CO2 卧式吸附态Ni(Ⅱ )←O - (CO)← (O--Ni) .丙烯有多种吸附态在催化剂上吸附 .在 5 6 3K、1MPa和空速 15 0 0h-1的反应条件下 ,丙烯的摩尔转化率为 3.2 % ,产物MAA选择性为 95 % .     

Preparation of Phosphoric-Carboxylic Cation Exchangers from Wood Cellulose

Phosphorus-containing cellulose cation exchangers were synthesized by reaction of wood cellulose with orthophosphoric acid and the ternary polymer from glycidylmethacrylate, styrene, and maleic anhydride. The effects of the ratio of reactants, temperature, and duration of the reaction on the phosphorylation and exchange capacity of the modified cellulose material were studied.     

Synthesis of β-phenyl-δ,ε-unsaturated amino acids and stereoselective introduction of side chain groups into [4,3,0]-bicyclic β-turn dipeptides

(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings.     

离子束合成钇硅化物的结构及红外谱特征

将稀土金属钇离子注入到n型单晶Si(111)中制备出钇硅化物埋层.利用x射线衍射、卢瑟福背散射和傅里叶红外吸收谱测量分析了样品的结构、原子的埋层分布和振动模式.结果表明，Y离子在注入过程中已与基底中的Si原子形成了YSi2结构相.真空下的红外光辐照处理促使YSi2择优取向生长，埋层中Si与Y的平均原子浓度比由24下降为20，与六方YSi2的化学计量比一致.还给出了钇硅化物的特征红外吸收谱.     

C2（a 3Πu）+NO 的反应机理研究

在G2 (CC ,MP2 )理论水平上研究了C2 (a3 Πu)自由基与NO分子的反应 .计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种反应机理 :由NO中的O原子进攻C2 自由基形成CCON中间体的CCON机理和NO中的N进攻C2 自由基形成CCNO中间体的CCNO机理 ,分析了对应与这两种反应机理的五个可能的反应通道 ,得出了由NO中的N原子进攻3 C2 自由基 ,生成中间体CCNO自由基 ,最终得到产物CN +CO的通道是最有利的通道 .     

时间分辨红外发射光谱法对自由基反应的研究

在过去的 15年中 ,傅立叶变换红外发射光谱法广泛应用于研究气相自由基反应 .Sloan首先研究了O(1D)的反应 ,随后Leone和Hancock研究了O(3 P)的反应 .此后 ,孔繁敖和朱起鹤等研究了小自由基 ,包括CH、CH2 、CH3 、C2 H3 、C2 H5、C2 H、C3 H3 和C3 H5与O2 、NO、N2 O、NO2 等分子的反应。在红外光谱中观察到各个反应的初生产物和初步反应通道 ,和从头算的理论研究结合起来 ,这些反应的机理已基本弄清 .     

An Improved Synthesis of Retinoic Acid from β-Ionone

A convenient and large-scale preparation of retinoic acid 1 from β-ionone in five steps with 38% overall yield is described.The key steps are the epoxidization of 2 with a new methylated agent and the condensation 4 with tetraethyl methylenediphophonate in one-pot procedure to prepare 6.     

Effect of secondary electrons from latent tracks created in YBCO by swift heavy ion irradiation

Swift heavy ions (SHI) with electronic energy loss exceeding a value of 14.4 keVnm⁻¹ create amorphized latent tracks in YBCO type superconductors. In the low fluence regime of an ion beam where tracks do not overlap, a decrease of the superconducting transition temperature as probed through resistivity studies, is not expected due to availability of percolating current paths. The present study however shows T_c decrease by about 1–3 K in thin films of YBCO when irradiated by 250 MeVAg ions at 79 K at a fluence of 5×10¹⁰–1×10¹² ionscm⁻². The highest fluence used in the present study is three times less than the fluence where track overlapping becomes significant. The T_c tends to increase towards the preirradiation value on annealing the films at room temperature. To explain this unusual result, we consider the effect of ion irradiation in inducing materials modification not only through creation of amorphized latent tracks along the ion path, but also through creation of atomic disorder in the oxygen sublattice in the Cu–O chains of YBCO by the secondary electrons. These electrons are emitted radially from the tracks during the passage of the SHI. Considering the correlation between the charge state of copper and its oxygen coordination, we show in particular that the latter process is a consequence of the inelastic interaction of the SHI induced low-energy secondary electrons with the YBCO lattice, which result in chain oxygen disorder and T_c decrease.     

Si微电阻桥温度分布与热传导特性的显微Raman光谱研究

采用显微Raman光谱方法对红外目标模拟器中重掺杂Si微电阻桥单元的热传导特性进行研究，根据Si桥的实际特性建立相应的Raman散射模型，通过测量Raman峰位的移动得到高功率激光辐照下测量点的温度.对Si桥桥面分别进行了沿某些特殊线段的逐点线扫描和覆盖全部桥面的面扫描，得到各点的温升及其分布.用基于有限元分析的软件结合Si桥结构参数对各测量点的温升进行了模拟计算，其结果在热导分布的基本趋势上与实验相一致.实验细致地揭示了热导分布的局域起伏，反映出实际器件的不均匀性，为改进器件设计、优化器件性能提供了实验依据. 关键词： Raman光谱 Si桥 温度分布 热导     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003