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921.
L. A. Tomachinskaya I. N. Tret’yakova V. Ya. Chernii G. Ya. Kolbasov V. S. Vorobets S. V. Volkov 《Theoretical and Experimental Chemistry》2008,44(3):139-143
The electronic absorption (EAS) and fluorescence spectra and electrocatalytic and photoelectrochemical characteristics of
mixed-ligand complexes of zirconium(IV) and hafnium(IV) based on phthalocyanines in solutions and in thin films were investigated.
It was established that a significant bathochromic shift of the Q band and redistribution of the intensities in the absorption
bands are observed in the electronic absorption spectra. It was shown that films of the synthesized compounds are promising
for use as photosensitizers and electrochemical sensors for oxygen in solution.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 133–137, May–June, 2008. 相似文献
922.
The electronic absorption spectrum of anthracene-9,10-endoperoxide (APO) has been investigated by means of multiconfigurational multi-state second order perturbation theory on complete active space self-consistent field wavefunctions (MS-CASPT2/CASSCF) and two single reference methods: time-dependent density functional theory (TD-DFT) and coupled cluster of second order (CC2). After testing several active spaces and basis sets, a CAS (14,12) active space together with an ANO-S basis set was found an appropriate choice to describe the vertical singlet and triplet electronic states of APO. Unfortunately, TD-DFT and CC2 methods cannot reproduce the MS-CASPT2 and experimental spectrum. Our MS-CASPT2//CASSCF(14,12)/ANO-S calculations predict a predominant pi*(OO)sigma*(OO) character for the lowest singlet excited state S(1) at 3.85 eV. Accordingly, the lowest singlet state of APO should be responsible for homolysis of the endoperoxide group. The next two absorbing excited states, experimentally proposed to be responsible for singlet oxygen production and therefore connected to the biological interest of APO, have been computed vertically at 4.34 and 4.59 eV and assigned to pi(CC)pi*(CC) and pi*(OO)pi*(CC) transitions, respectively. The vertical triplet electronic spectrum follows the singlet vertical spectrum ordering. The high density of triplet and singlet excited states of different nature within few eV points to the possibility of intersystem crossings between potential energy surfaces of different multiplicity. 相似文献
923.
通过1-芳基含硫(氧)酮肟与相应的拟除虫菊醇卤化物在氢氧化钠和相转移催化剂条件下反应或1-芳基含硫(氧)酮肟与相应的拟除虫菊醇卤化物的三乙基季胺盐在氢氧化钠条件下反应, 合成了1-芳基含硫(氧)酮O-苄基肟醚C1~C96共96个化合物. 它们的结构经质谱, 1H NMR, IR和元素分析确证. 生物活性测定结果表明, 该类化合物对鳞翅目和同翅目害虫表现出显著活性, C74和C93对粘虫、叶蝉的活性[LC50/(mg8226;L-1)]分别为1.4, 0.63和0.31, 1.2. 优于对照药氰戊菊酯. 相似文献
924.
925.
采用一步水热法合成了硼、磷共掺杂铁钴材料(Fe-Co-B-P)。借助扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)等技术对所合成材料的形貌、结构和组成进行表征。利用线性扫描伏安(LSV)、循环伏安(CV)、电化学阻抗谱(EIS)等技术研究材料电化学析氧反应(OER)性能。结果表明,Fe-Co-B-P表面疏松且粗糙,颗粒间有许多空隙。在电流密度为10和100 mA·cm-2时,其过电势分别为278和309 mV,Tafel斜率为24 mV·dec-1,说明该材料具有较优的电催化析氧性能。其在连续进行10 h的计时电位测试过程中,电势基本保持在1.55 V(vs RHE),表明该催化剂具有较好的电化学稳定性。这是由于铁钴双金属与硼、磷非金属之间的协同作用促进了电子的传递。 相似文献
926.
Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane
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Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen cartier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction. Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox re-action decreased over La0.8Sr0.2Fe0.9Co0.1O3 oxide, while LaFeO3 and Lao.sSro.2FeO3 exhibited excellent structural stability and continuous oxygen supply. 相似文献
927.
WenXing Chen Fan Liu WangYang Lü XiaoYuan Shen YuYuan Yao MinHong Xu 《中国科学B辑(英文版)》2008,51(6):570-576
A novel reactive metallophthalocyanine derivative,zinc tetra(2,4-dichloro-1,3,5-triazine)aminophthalo-cyanine(Zn-TDTAPc),was prepared and immobilized on poly(N-isopropylacrylamide)(PNIPAAm) by covalent bonding to obtain a thermosensitive polymer(Zn-TDTAPc-g-PNIPAAm).Compared with zinc tetraaminophthalocyanine(Zn-TAPc),Zn-TDTAPc-g-PNIPAAm exhibits excellent solubility in water and in most organic solvents.Furthermore,it has a special thermosensitive property in water and the lower critical solution temperature(LCST) is 34.1℃.It was found that both dissolved and precipitated Zn-TDTAPc-g-PNIPAAm present high photoactivity evidenced by the experiment of photocatalytic degra-dation of 1,3-diphenylisobenzofuran(DPBF) in the presence of Zn-TDTAPc-g-PNIPAAm.These proper-ties suggest that it can be used potentially in photodynamic therapy(PDT). 相似文献
928.
Hydrogen generation through thermal chemical water splitting technology has recently received in- creasingly international interest in the nuclear hydrogen production field. Besides the main known sulfur-iodine (S-I) cycle developed by the General Atomics Company and the UT3 cycle (iron, calcium, and bromine) developed at the University of Tokyo, the thermal cycle based on metal oxide two-step water splitting methods is also receiving research and development attention worldwide. In this work, copper ferrite was prepared by the co-precipitation method and oxygen-deficient copper ferrite was synthesized through first and second calcination steps for the application of hydrogen production by a two-step water splitting process. The crystal structure, properties, chemical composition and δ were investigated in detail by utilizing X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal analysis (DTA), atomic absorption spectrometer (AAS), ultraviolet spectrophotometry (UV), gas chro- matography (GC), and so on. The experimental two-step thermal chemical cycle reactor for hydrogen generation was designed and developed in this lab. The hydrogen generation process of water splitting through CuFe2O4-δ and the cycle performance of copper ferrite regeneration were firstly studied and discussed. 相似文献
929.
In this paper, the powder microelectrode technique was employed in studying the voltametric response of the O2/2− couple, which demonstrated a nearly reversible redox process at an acetylene black powder microelectrode in N,N-dimethylformamide
(DMF). A well-developed steady state current plateau for the electrochemical reduction of oxygen was obtained in this system.
The electron transfer number (n) and heterogeneous electron transfer rate constant k
s were measured by steady-state voltametric response, and the results were 1.08, 3.4 × 10−3 cm s−1, respectively. Additionally, the scavenging activity of O2− with biological antioxidant (ascorbic acid) was evaluated by cyclic voltammetry; IC50 came to 5 × 10−4 mol/l.
Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 8, pp. 1040–1044.
The text was submitted by the authors in English. 相似文献
930.
C. A. C. Sequeira D. M. F. Santos P. S. D. Brito 《Russian Journal of Electrochemistry》2008,44(7):852-856
The electrocatalysis of the oxygen reduction reaction by lanthanum-strontium manganate La0.5Sr0.5MnO3 (LSM) has been studied by cyclic voltammetry using the rotating ring-disc electrode technique (RRDE) in alkaline medium.
From the ring-disc data and other kinetic parameters it was concluded that the oxygen reduction occurs by dissociative chemisorption
at low overpotentials. At higher overpotentials, the formation of hydrogen peroxide (HO2− in this case) on the electrocatalyst has been observed. The apparent exchange current density for oxygen reduction on LSM
has been found to be 2 × 10−7 A cm−2, while the corresponding Tafel slope is 0.100 V per decade. The possible reaction mechanism for electroreduction of oxygen
on this oxide catalyst has been discussed.
Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 7, pp. 919–923.
The text was submitted by the authors in English. 相似文献