全文获取类型
收费全文 | 161篇 |
免费 | 4篇 |
国内免费 | 34篇 |
专业分类
化学 | 191篇 |
综合类 | 2篇 |
物理学 | 6篇 |
出版年
2023年 | 3篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 1篇 |
2017年 | 2篇 |
2016年 | 1篇 |
2015年 | 1篇 |
2014年 | 8篇 |
2013年 | 11篇 |
2012年 | 12篇 |
2011年 | 6篇 |
2010年 | 11篇 |
2009年 | 12篇 |
2008年 | 12篇 |
2007年 | 11篇 |
2006年 | 15篇 |
2005年 | 15篇 |
2004年 | 15篇 |
2003年 | 7篇 |
2002年 | 10篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 5篇 |
1998年 | 8篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
排序方式: 共有199条查询结果,搜索用时 296 毫秒
1.
A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TG), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectroscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)6·12H2O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H2O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H2O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of well-defined and stable redox peaks with the formal potential of E0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lgaNa+), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na+ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA) and ascorbic acid (AA), and the electrocatalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0–10.0 mmol·L?1 (for DA) or 0.5–20.0 mmol·L?1 (for AA). 相似文献
2.
Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant … 相似文献
3.
An ordinary plating solution for indium hexacyanoferrate (InHCF) thin film deposition, mainly composed of equal concentrations
of In3+ and [Fe(CN)6]3–, usually forms precipitates rapidly when either concentration is higher than few millimolar. This contributes to the plating
solution's instability. Moreover, electrodeposited capacities are limited accordingly. In this work, the plating solution's
stability and the electrodeposition of InHCF were greatly enhanced by adding a large amount of K+ and/or H+. It was found that a 10-mM plating solution added with 1 M HCl and 1 M KCl could be stored as fresh over a one-week period,
whereas an unmodified plating solution became useless within a couple of minutes. Also, such cationic additions, especially
adding H+, increased the electrodeposited capacity ca. 18 times at least, as compared with that obtained from the unmodified plating
solution. Furthermore, related enhancing mechanisms were proposed and verified. To sum up, this study offers a means for better
InHCF electrodeposition and should promote the applications of InHCF films.
Electronic Publication 相似文献
4.
5.
纳米CoHCF修饰电极的制备及其对血红蛋白的电化学测定研究 总被引:1,自引:0,他引:1
A cobalt hexacyanoferrate (CoHCF) nanoparticle (size ca. 60 nm) chemically modified electrode (CME) was fabricated and the electrochemical behavior of hemoglobin (Hb) at this nanosized CoHCF CME was studied. In comparison with a bare glassy carbon electrode (GCE) and a general CoHCF CME electrodeposited in a traditional manner, the present nanosized CoHCF CME performed efficiently electrocatalytic reduction for Hb with relatively high sensitivity, stability, and longlife, Combined with liquid chromatography (LC), the nanosized CoHCF CME was used as the electrochemical detector of Hb in the established flow injection analysis-electrochemical determination (FIA-ECD) system. The peak current was a linear function of concentrations in the range from 2.5×10^-8 to 5.0×10^-6mol/L for Hb, with detection limit of 1.4×10^-8 mol/L. The FIA-ECD system has been successfully applied to assess the Hb content of clinic blood samples with advantages of sensitiveness, speediness, easy control and small sample-consumption. 相似文献
6.
A thin film of manganese hexacyanoferrate (MnHCF) was electrochemically formed on a glassy carbon (GC) electrode to prepare a chemically modified electrode (CME). The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ(CN)6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy (SEM), which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes. 相似文献
7.
M.?H.?Pournaghi-AzarEmail author H.?Nahalparvari 《Journal of Solid State Electrochemistry》2004,8(8):550-557
The use of a zinc substrate as an electrode and the modification of its surface by means of a thin film of platinum-doped nickel hexacyanoferrate (Pt-NiHCF) were developed. The modification conditions of the zinc surface including the electroless deposition of metallic nickel on the electrode surface from NiCl2 solution, chemical derivatization of the deposited nickel to the NiHCF film in 0.5 M K3[Fe(CN)6] solution, and electrochemical penetration of metallic platinum into the modified film are described. The modified zinc electrodes prepared under optimum conditions show a well-defined redox couple due to the [NiIIFeIII/II(CN)6]1–/2–
system. The effects of pH, the alkali metal cation, and the anion of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied in detail. The diffusion coefficients of hydrated alkali metal cations in the film (D), the transfer coefficient (), and the transfer rate constant for the electron (ks) were calculated in the presence of some alkali metal cations. The electrocatalytic activity of the modified electrode for methanol oxidation was demonstrated. The stability of the modified electrode under various experimental conditions was investigated. 相似文献
8.
六氰合铁酸铜钴在蜡浸石墨电极表面的电化学沉积 总被引:3,自引:0,他引:3
首次报道了电化学沉积的混合金属六氰合铁酸盐修饰电极作为电流型传感器的研究。针对六氰合铁酸盐修饰电极在中性和碱性条件下的不稳定性,采用混合金属电沉积的方法,成功地提高了电极的稳定性,所得到的修饰电极在 pH 4~10之间均表现出良好的稳定性。该电极的响应时间(t95%)为 0.5s,并对Fe3+/Fe2+电对表现出良好的电催化作用。催化氧化峰电流与Fe2+的浓度在1.0×10-4~6.5×10-2mol/L范围内呈很好的线性关系,检测下限为 1.4×10-6mol/L。 相似文献
9.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
10.
Thomas Schareina 《Journal of organometallic chemistry》2004,689(24):4576-4583
Benzonitriles are easily accessible via palladium-catalyzed cyanation of aryl halides using potassium hexacyanoferrate(II) as cyanide source. This method is applicable on both activated and deactivated aryl and heteroaryl bromides and activated chlorides giving the corresponding benzonitriles in good to excellent yield. Advantageously, the used cyanating agent is non-toxic and cheap. The presented catalyst system is rather simple and it is not necessary to add expensive phosphines, making the novel method also attractive for industrial applications. 相似文献