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81.
On the Criteria of Instability for Electrochemical Systems   总被引:7,自引:0,他引:7  
LI  Ze-Lin REN  Bin 等 《中国化学》2002,20(7):657-662
Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).  相似文献   
82.
量热法测定;量热法研究氯化铒与甘氨酸配合物的标准生成焓  相似文献   
83.
一种新型吡嗪铱(Ⅲ)配合物的合成及其磷光性质   总被引:2,自引:0,他引:2  
利用5-甲基-2,3-二苯基吡嗪(MDPP)和水合三氯化铱(IrCl3•H2O),合成了一种新型吡嗪铱配合物Ir (MDPP)2 (acac).通过1H NMR、元素分析和质谱方法对配合物结构进行了表征,并研究了配合物的吸收光谱和光致发光光谱.结果表明,配合物Ir (MDPP)2(acac)在393和528 nm处存在单重态1MLCT(金属到配体的电荷跃迁)和三重态3MLCT的吸收;在588 nm 处有较强的金属配合物三重态的磷光发射,是一种绿色磷光材料.  相似文献   
84.
A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethyleyclotrisilazane lithium salts(D3^NLi)and zirconium tetrachloride(ZrCl4).In the presence of N,N,N’,N’-tetramethyl ethylene diamine(TMEDA),polyorganozircosilazane was obtained in high yield.  相似文献   
85.
Mixed ionic-electronic conductors in the family of LaxSr1–xCoyFe1–yO3–δ have been widely studied as cathode materials for solid oxide fuel cells (SOFCs). However, the long-term stability was a concern. Here we report our findings on the effect of a thin film coating of La0.85Sr0.15MnO3–δ (LSM) on the performance of a porous La0.6Sr0.4Co0.2Fe0.8O3–δ (LSCF) cathode. When the thicknesses of the LSM coatings are appropriate, an LSM-coated LSCF electrode showed better stability and lower polarization (or higher activity) than the blank LSCF cathode without LSM infiltration. An anode-supported cell with an LSM-infiltrated LSCF cathode demonstrated at 825 °C a peak power density of ~1.07 W/cm2, about 24% higher than that of the same cell without LSM infiltration (~0.86 W/cm2). Further, the LSM coating enhanced the stability of the electrode; there was little degradation in performance for the cell with an LSM-infiltrated LSCF cathode during 100 h operation.  相似文献   
86.
We have developed an unprecedented Pd‐catalyzed formal hydroalkylation of alkynes with hydrazones, which are generated in situ from naturally abundant aldehydes, as both alkylation reagents and hydrogen donors. The hydroalkylation proceeds with high regio‐ and stereoselectivity to form (Z)‐alkenes, which are more difficult to generate compared to (E)‐alkenes. The reaction is compatible with a wide range of functional groups, including hydroxy, ester, ketone, nitrile, boronic ester, amine, and halide groups. Furthermore, late‐stage modifications of natural products and pharmaceutical derivatives exemplify its unique chemoselectivity, regioselectivity, and synthetic applicability. Mechanistic studies indicate the possible involvement of Pd‐hydride intermediates.  相似文献   
87.
The established tradition of consuming and marketing wild mushrooms has focused attention on mycotoxicity, which has become a global issue. In the present study, we describe the toxins found in a previously unknown poisonous European mushroom Tricholoma terreum. Fifteen new triterpenoids terreolides A–F ( 1 – 6 ) and saponaceolides H–P ( 8 – 16 ) were isolated from the fruiting bodies of the toxic mushroom T. terreum. Terreolides A–C ( 1 – 3 ) possessed a unique 5/6/7 trioxaspiroketal system, whereas terreolides D–F ( 4 – 6 ) possessed an unprecedented carbon skeleton. Two abundant compounds in the mushroom, saponaceolide B ( 7 ) and saponaceolide M ( 13 ), displayed acute toxicity, with LD50 values of 88.3 and 63.7 mg kg?1 when administered orally in mice. Both compounds were found to increase serum creatine kinase levels in mice, indicating that T. terreum may be the cause of mushroom poisoning ultimately leading to rhabdomyolysis.  相似文献   
88.
The SmF_(2.01)was synthesized by reducing SmF_3 in H_2 stream.As it was doped inKM_gF_3 and KCaF_3.there was emission of Sm~(2+) in KMgF_3 but no emission of Sm~(2+) inKCaF_3 was observed.  相似文献   
89.
In continuation of our research on diterpenoids in the Isodon species, several newcompounds"' were obtained from the leaves oflsodon xerophilus (C. Y. Wu et H. W. Li)H. Hara (Labiatae), a perennial shrub native to Yunnan province. Further fractionation ofthe EtOAc extract led to the isolation of tWo new enl-kauranoids, xerophilusin E (l) andxerophilusin F (2). This paper deals with the structUral elucidation of the newcompounds.Xerophilusin E (l), a minor constitUent, was obtained as p…  相似文献   
90.
AsatheraPeuticherbusedintraditionalChinesemedicine,TerminaliachebulaisconventionallygrowninGuangdong,Guangxi,andtheYunnanprovinceofChina.Itsripefruitisefficaciouslycurativewhenusedintreatingdiarrheaandhoarsenessofthethroatandcanalsobeusedasanastringenttobringabouthemostasisortoremovesomepathogenic"internalheat"ortoxicelementsfromwithinhumanphysique'.SeveralstudiesonhydroIysabletanninswithchebuloylgrouphavebeenreportedsofar2.AspartofaprogramforasystematicstudyofTchebula,wehavesuccessfullyis…  相似文献   
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