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181.
Han J Goncharov V Kaledin LA Komissarov AV Heaven MC 《The Journal of chemical physics》2004,120(11):5155-5163
The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1). These bands originated from the U(5fphi(u)7ssigma(g))O(2) X (3)Phi(2u) and (3)Phi(3u) states. The stronger band systems are attributed to metal-centered 7p<--7s transitions. Threshold ionization measurements were used to determine the ionization potentials of UO and UO(2). These were found to be higher than the values obtained previously from electron impact measurements but in agreement with the results of recent theoretical calculations. 相似文献
182.
183.
用停止-流动分光光度法研究了Eu~(2+)与二甲酚橙(XO)间快速电子转移反应的动力学规律。求得了速控步骤的动力学参数。如反应级数(n=2)、几个不同温度下的速率常数(k_(278 K)=5.7×10~8 L·mol~-·s~(-1), k_(s38 K)=1.01×10~9 L·mol~(-1)·s~(-1))、活化能(E=7.6×10~3 J·mol~(-1)), 以及指前因子(A=1.5×10~(10) L·mol~(-1)·s~(-1)), 并判断出其为溶液中扩散控制型反应。根据实验现象与测试结果, 提出了Eu~(2+)与XO的反应分别在Eu~(2+)相对过量和在XO过量时的反应机理, 并判断了各反应步骤速率常数之间的相对关系。 相似文献
184.
肝素化壳聚糖季铵盐/壳聚糖复合膜抗凝血性能的研究 总被引:13,自引:1,他引:13
以壳聚糖季铵盐,壳聚糖为基本原材料,选用戊二醛为交剂剂及固定剂,制备一种物理机械性能较优的抗凝血材料。探讨了戊二醛及肝素钠两者用量对肝素化程度及血液生的影响。 相似文献
185.
In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm−2. Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts. 相似文献
186.
Chemical shifts of the alcohol and DMF protons in DMF–alcohol mixtures with the mole fraction of alcohol are reported in order to study the hydrogen bond interaction present in the mixtures. The densities of DMF–methanol mixture at 22°C are also measured. Excess volumes and excess chemical shifts are correlated by the Redlich–Kister equation. The relation between excess volumes and excess chemical shifts in the mixtures is discussed. It is found that the maximum excess chemical shifts E(CHO-OH) and E(CH3-OH) are positioned at about mole fraction methanol = 0.57 for the DMF–methanol system, as is V
E. The results show that the NMR spectral method offers a valuable approach to similar future studies of interactions in mixtures. 相似文献
187.
加速剂对化学镀镍层组成与结构的影响 总被引:3,自引:0,他引:3
加速剂对化学镀镍层组成与结构的影响方景礼,武勇,韩克平,张敏(南京大学应用化学研究所配位化学国家重点实验室南京210093)关键词化学镀镍,Ni0P合金,加速剂,硫脲化学镀镍磷合金具有耐蚀性、可焊性、厚度均匀和硬度高等优点,已得到广泛应用。为提高生产... 相似文献
188.
Thermoluminescence glow curves displayed by ethylene-vinyl acetate copolymers after u.v. irradiation at low temperature have been compared to the depolarization thermocurrents (DTC) described in a previous publication, in order to establish a possible correlation between the thermal liberation of the trapped carriers and the intrinsic relaxation phenomena. The detailed analysis of these glow curves has been carried out, either by studying their spectral distributions between 300 and 650 nm, or by the systematic application of the classical method of partial glow and by a method of partial irradiation which consists in irradiating the sample isothermally at different temperatures in several experiments. Two main glow peaks corresponding to distinct spectral emission zones were found. These peaks occur in temperature zones similar to those of appearance of the DTC peaks; the latter were assigned to primary and secondary dipolar relaxations, i.e. α and β type relaxations, respectively. In addition, the β glow peak presents properties comparable with those of the DTC β peak and hence results probably from thermal untrapping, this untrapping being at least partly assisted by short range chain motions in the polymer. The α glow peak, on the other hand, shows little correspondence with the DTC peak and has essentially a superficial origin; it probably arises from two distinct traps associated with impurities or with interface between amorphous and crystalline regions rather than from the polymeric chains themselves. 相似文献
189.
Huang KW Han JH Cole AP Musgrave CB Waymouth RM 《Journal of the American Chemical Society》2005,127(11):3807-3816
Titanium-oxygen bonds derived from stable nitroxyl radicals are remarkably weak and can be homolyzed at 60 degrees C. The strength of these bonds depends sensitively on the ancillary ligation at titanium. Direct measurements of the rate of Ti-O bond homolysis in Ti-TEMPO complexes Cp2TiCl(TEMPO) (3) and Cp2TiCl(4-MeO-TEMPO) (4) (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-MeO-TEMPO = 2,2,6,6-tetramethyl-4-methoxypiperidine-N-oxyl) were conducted by nitroxyl radical exchange experiments. Eyring plots gave the activation parameters, deltaH++ = 27(+/- 1) kcal/mol, deltaS++ = 6.9(+/- 2.3) eu for 3 and deltaH++ = 28(+/- 1) kcal/mol, deltaS++ = 9.0(+/- 3.0) eu for 4, consistent with a process involving the homolysis of a weak Ti-O bond to generate the transient Cp2Ti(III)Cl and the nitroxyl radical. Thermolysis of the titanocene TEMPO complexes in the presence of epoxides leads to the Cp2Ti(III)Cl-mediated ring-opening of the epoxide followed by trapping by the nitroxyl radical. The X-ray crystal structure of the Ti-TEMPO derivative, Cp2TiCl(4-MeO-TEMPO) (4), is reported. DFT (B3LYP/6-31G*) calculations and experimental studies reveal that the strength of the Ti-O bond decreases dramatically with the number of cyclopentadienyl groups on titanium. The calculated Ti-O bond strength of the monocyclopentadienyl complex 2 is 43 kcal/mol, whereas that of the biscyclopentadienyl complex 3 is 17 kcal/mol, a difference of 26 kcal/mol. These studies reveal that the strength of these Ti-O bonds can be tuned over an interesting and experimentally accessible temperature range by appropriate ligation on titanium. 相似文献
190.