全文获取类型
收费全文 | 2561篇 |
免费 | 105篇 |
国内免费 | 408篇 |
专业分类
化学 | 2359篇 |
晶体学 | 43篇 |
力学 | 15篇 |
综合类 | 8篇 |
数学 | 8篇 |
物理学 | 641篇 |
出版年
2024年 | 2篇 |
2023年 | 32篇 |
2022年 | 44篇 |
2021年 | 50篇 |
2020年 | 75篇 |
2019年 | 66篇 |
2018年 | 46篇 |
2017年 | 79篇 |
2016年 | 96篇 |
2015年 | 92篇 |
2014年 | 123篇 |
2013年 | 155篇 |
2012年 | 172篇 |
2011年 | 195篇 |
2010年 | 157篇 |
2009年 | 202篇 |
2008年 | 164篇 |
2007年 | 185篇 |
2006年 | 160篇 |
2005年 | 124篇 |
2004年 | 118篇 |
2003年 | 123篇 |
2002年 | 100篇 |
2001年 | 84篇 |
2000年 | 76篇 |
1999年 | 60篇 |
1998年 | 60篇 |
1997年 | 36篇 |
1996年 | 34篇 |
1995年 | 32篇 |
1994年 | 28篇 |
1993年 | 22篇 |
1992年 | 19篇 |
1991年 | 19篇 |
1990年 | 14篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有3074条查询结果,搜索用时 15 毫秒
81.
在pH5.0的NaOAc-HOAc缓冲溶液中,过量的硝酸银完全沉淀叶酸,用原子吸收光谱法测定剩余的硝酸银,间接计算出叶酸的含量。方法简单快速,回收率在98%~104%之间,相对标准偏差为2.4%。 相似文献
82.
硫酸溶液中Ag+离子对Mn2+离子阳极氧化的催化作用 总被引:2,自引:0,他引:2
Anodic oxidation of Mn2+ and Ag+ ions and anodic oxidation of Mn2+ ion on platinum electrode in H2SO4 solution catalyzed by Ag+ ion are studied by using RRDE and triangle voltammetry techniques. Mn2+ ion is oxidized on the anode surface with adsorped OH group to form a certain compound containing Mn3+, which causes Mn2+difficult to be oxidized directly on anode. Near the potential of oxygen evolution from H2O decomposition, Ag+ ion is oxidized to form Ag2+ ion. This is the main reaction on anode because of its reversability. At higher potential silver oxide is formed on the anode. The oxide catalyzes the decomposition of H2O strongly. The anodic oxidation of Mn2+ion catalyzed by Ag+ takes place and Ag2+ ion and silver oxide are no longer the product of Ag+ anodic oxidation when Mn2+ exists in solution at the potential for Ag+ anodic oxidation. It is confirmed that the catalysis reaction is homogeneous and very fast. 相似文献
83.
《Electroanalysis》2005,17(19):1727-1733
A study of three electrode substrates namely gold, platinum and silver, for arsenic detection via anodic stripping voltammetry is reported. Hitherto it has been accepted that gold is the most suitable metallic surface for use in this context, as suggested by Forsberg and co‐workers (Forsberg, G.; O'Laughlin, J. W.; Megargle, R. G. Anal. Chem. 1975, 47, 1586.). We revisit these experiments and find that by switching from hydrochloric acid to nitric acid the oxidation of silver that had previously masked the arsenic stripping signal at this surface is shifted considerably enough to allow a clear, analytically reliable As(III) stripping signal to be detected. In contrast to silver and gold platinum is found to have poor performance as an electrode substrate for arsenic detection. Using ASV a LOD of 6.3×10?7 M is found for As(III) detection at a silver electrode, similar to that which we have previously reported at a gold electrode (A. O. Simm, C. E. Banks and R. G. Compton. Electroanalysis, 2005, 17, 335.) The use of ultrasound was then investigated to further reduce the LOD, which was found to be 1.4×10?8 M. Apart from reduced cost of silver it also has an added advantage over gold in that it has a higher hydrogen reduction overvoltage enabling a 100 mV more negative deposition potential to be used before the onset of hydrogen evolution when compared to a gold electrode. 相似文献
84.
Voltammetry of immobilized microparticles was used to study the electrochemistry of the raw pigments that produce the metallic lustre on ceramics after a successful firing. To study this influence of the mixture components on the reduction properties to achieve the metallic lustre, 14 mixtures of illitic clay, Fe2O3, HgS, CuO and AgNO3 were prepared and studied in different media. Iron oxide improves the yield of the reduction of the metals and cinnabar helps a closer reduction of silver to copper reduction and prevents the Ag? Cu alloying because of the formation of silver–mercury adducts. The presence of one of the metals influences the peak position of the other metal. The use of vinegar as diluting agent is not casual, because in this media the reduction of silver takes place at a potential closer to the copper. This electroanalytical technique allowed to distinguish between powders of different composition and offered some information about the role of the components in the reduction of copper and silver and the selection of vinegar to prepare the raw pigment suspensions. 相似文献
85.
Maksymilian Ignaczak Andrzej Grzejdziak Barbara Olejniczak 《Monatshefte für Chemie / Chemical Monthly》1989,120(6-7):515-527
Summary The conditional protonation constants (=0.1) for 2,2:6,2-terpyridine, logK
1=4.93, logK
2=3.69, were determined by thepH-metric method. The compositions of complexes of Ag2+ and Ag+ ions with 2,2:6,2-terpyridine (tp) were studied and equilibria of the complex formation process were described. The values of conditional complex formation constants are as follows: for Ag(tp)
2
+
:log01=5.79, log02=9.68, for Ag(tp)
2
2+
:log02=25.31, while the conditional constant of the Ag(tp)NO3 precipitate formation is:K
SO=2.45·104. Using coulometric and chronovoltamperometric measurements, the redox systems being formed in the complex solutions of Ag(II) and Ag(I) were determined and described including their formal potentials.
Komplexibildungsgleichgewichte und Redoxpotentiale des Systems Ag(II)/Ag(I) in Gegenwart von 2,2:6,2-Terpyridin in Wasser
Zusammenfassung Mit Hilfe derpH-metrischen Methode wurden die konditionalen Protonationskonstanten (=0.1) von 2,2:6,2-Terpyridin bestimmt: logK 1=4.93, logK 2=3.69. Es wurde auch die Zusammensetzung der Komplexe von Ag(II) und Ag(I) mit 2,2:6,2-Terpyridin(tp) bestimmt sowie die Gleichgewichte der komplexbildung beschrieben. Die Werte der Konditionalkomplexbildungskonstanten sind: für Ag(tp) 2 + :log01=5.79, log02=9.68, für Ag(tp) 2 2+ :log02=25.31 und für das Löslichkeitsprodukt Ag(tp)NO3:K SO –1 =4.08·10–5. Die in Komplexlösungen von Ag(II) und Ag(I) vorliegenden Redoxsysteme wurden mittels cyclischer Voltametrie und Coulometrie untersucht und die Formalpotentialwerte dieser Systeme in Wasser bestimmt.相似文献
86.
Ruibiao Fu 《Journal of solid state chemistry》2004,177(12):4626-4631
A new silver organodiphosphonate, [Ag4(O3PCH2CH2PO3)] (1), has been synthesized and characterized by X-ray diffraction, IR, TGA-DSC, electricity measurement and element analysis. 1 crystallizes in the monoclinic space group P2(1)/n (a=6.0115(16) Å, b=8.630(2) Å, c=8.462(2) Å, β=97.693(4)°, Z=2, R1=0.0604, wR2=0.1450). 1 contains one-dimensional channels and a three-dimensional Ag?Ag interacted substructural net. TGA and XRD indicate little weight loss up to 300 °C and little structure change after heated at 170 °C for 2 h, respectively. The grain interior conductivity of 1 increases continuously from 50 to 170 °C. Results of EHT calculations show that under thermal or optical excitation the conductivity of 1 is mainly due to transfer of π antibonding electrons of -PO3 group through O atom to Ag 5s orbital, which also leads to enhancement of Ag?Ag interactions and promotes formation of Ag?Ag substructural net. 相似文献
87.
Carlos Rodríguez-Abreu Massimo Lazzari Dharmesh Varade Masaya Kaneko Kenji Aramaki Manuel Arturo López Quintela 《Colloid and polymer science》2007,285(6):673-680
The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations
in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates
that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer
in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside
the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally,
viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles
with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent;
namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献
88.
《Electroanalysis》2006,18(2):127-130
The voltammetric behavior of 2‐methyl‐4,6‐dinitrophenol was investigated by differential pulse voltammetry (DPV) at a nontoxic mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.2 to 1 μmol L?1. 相似文献
89.
The silver iodate(VII), Ag5IO6, was obtained by reacting a stoichiometric mixture of Ag2O and KIO3, at elevated oxygen pressure, adding a small portion of distilled water. The synthesis was done at 673 K and 270 MPa of oxygen pressure. The crystal structure was solved by direct methods based on single crystal diffraction data ( , Z = 6, a = 5.9366(1), c = 32.1471(6) Å, 323 independent reflections, R1 = 2.31 %). According to conductivity measurements, Ag5IO6 is semiconducting with a specific resistance of 0.08 Ωcm at 300 K. The activation energy was determined as 7.4(1) meV in the temperature range of 220 – 300 K, and 4.3(1) meV in the temperature range of 90 – 180 K. The optical band gap for Ag5IO6 is 1.4 eV. Ag5IO6 is diamagnetic with a magnetic susceptibility of ?4.4×10?4 emu/mol. 相似文献
90.
N,N-二(仲辛基)乙酰胺萃淋树脂吸萃银的性能及萃合物组成的研究 总被引:1,自引:0,他引:1
N,N_二(仲辛基)乙酰胺(N_(503))萃淋树脂是酰胺类萃淋树脂.本文报道了该树脂在弱酸性体系中对银的静态分配系数,温度、树脂用量、振荡时间对吸附银的影响,测定了树脂吸附银的饱和容量及树脂的含氮量,由此确定吸萃物的组成比,并用红外光谱探讨了该树脂吸附银的机理. 相似文献