全文获取类型
收费全文 | 5519篇 |
免费 | 103篇 |
国内免费 | 367篇 |
专业分类
化学 | 4637篇 |
晶体学 | 71篇 |
力学 | 30篇 |
综合类 | 1篇 |
数学 | 11篇 |
物理学 | 848篇 |
无线电 | 391篇 |
出版年
2024年 | 3篇 |
2023年 | 120篇 |
2022年 | 57篇 |
2021年 | 56篇 |
2020年 | 95篇 |
2019年 | 93篇 |
2018年 | 134篇 |
2017年 | 149篇 |
2016年 | 110篇 |
2015年 | 108篇 |
2014年 | 236篇 |
2013年 | 208篇 |
2012年 | 699篇 |
2011年 | 321篇 |
2010年 | 302篇 |
2009年 | 284篇 |
2008年 | 322篇 |
2007年 | 399篇 |
2006年 | 299篇 |
2005年 | 263篇 |
2004年 | 247篇 |
2003年 | 205篇 |
2002年 | 148篇 |
2001年 | 141篇 |
2000年 | 131篇 |
1999年 | 128篇 |
1998年 | 125篇 |
1997年 | 89篇 |
1996年 | 100篇 |
1995年 | 80篇 |
1994年 | 60篇 |
1993年 | 54篇 |
1992年 | 66篇 |
1991年 | 52篇 |
1990年 | 40篇 |
1989年 | 22篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有5989条查询结果,搜索用时 15 毫秒
91.
The effects of M3O3 (M = Al, Sc etc.) in Cu-ZnO-M2O3 catalysts on methanol synthesis at low pressure were studied with ESR, XPS and TPR spectroscopy. The results of ESR showed that the generation of monovalent cationic defects was because the valence state and electronic charge on the ZnO lattice lost their balance as M3+ doped into ZnO. The induced effect by Sc3+ is stronger than that by Al3+. The results of XPS and TPR indicated that the amount and stabilization of Cu+ on the surface of reduced copper-based catalyst and its catalytic activity were affected by the monovalent cationic defects on the surface of ZnO. 相似文献
92.
Hong-Chang Yao Song Gao Li-Min Zheng Xin-Quan Xin 《Journal of solid state chemistry》2004,177(12):4557-4563
Hydrothermal reactions of copper (II) nitrate with 1-hydroxycyclohexanephosphonic acid [C6H10(OH)PO3H2] or Δ1-cyclohexenephosphonic acid [C6H9PO3H2] have resulted in three new copper phosphonates, namely, Cu(C6H10(OH)PO3)(H2O)2 (1), Cu(C6H10(OH)PO3) (2) and Cu(C6H9PO3)(H2O) (3). Compound 1 has a dinuclear structure in which two {CuO5} square pyramids are bridged by two {CPO3} tetrahedra through corner sharing. The dimers are connected through intermolecular hydrogen bonds, forming supramolecular layers. Both compounds 2 and 3 show layer structures typical for metal mono-phosphonates, in which the inorganic metal-containing layers are separated by cyclohexane or cyclohexene groups. The magnetic studies show that ferromagnetic interactions are mediated between copper centers in compound 1. In compounds 2 and 3, antiferromagnetic interactions are dominant. 相似文献
93.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
94.
文中直接取硫酸样品3ml于装有约10ml水的25ml比色管中,加入碘化钾溶液2ml,用水稀至刻度。加入甲基异丁酮5ml,萃取lmin,分层后,在有机相中测定铅、镉、铜含量;在水相中测定锌含量。方法的加标回收率为98.9%~103%,精密度1.8%~4.3%,标准曲线法和标准加入法结果相近,倍比试验结果亦相吻合,方法快速简便、准确,适合于工业中的快速分析。 相似文献
95.
将40只雄性SD大鼠随机分成两组,采用猪油(L)或玉粮米油(M)加胆固醇饲料诱导出大高血脂模型后,再分出两组、分别加入亚硒酸钠(L-Se,M-Se),观察大鼠补硒后血清中锌铜、锌、钙、镁等元素的变化。结果表明,高血脂大鼠补硒后血 锌的含量明显下降,铜/锌比值长高。相关分析显示:血硒水平与血清锌含量呈负相关,各组大鼠血清铜、钙、镁的浓度未观察到显著性差异。 相似文献
96.
J. Borrs R. Carballo A. Castieiras M. C. Gmez‐Conde M. C. Fernndez‐Vidal J. Nicls 《无机化学与普通化学杂志》2005,631(11):2221-2226
Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′‐bis(carboxymethyl)dithiooxamide], ALADTO [N,N′‐bis(carboxyethyl)dithiooxamide], VALDTO [N,N′‐bis(1‐carboxy‐2‐methylpropyl)dithiooxamide] and LEUDTO [N,N′‐bis(1‐carboxy‐3‐methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with ?J values greater than 300 cm?1. Thermal decomposition behaviour of the complexes was studied by thermogravimetry. 相似文献
97.
Bright orange (CuBr)3P4Se4 is obtained from the reaction of CuBr, P, and Se in stoichiometric amounts (CuBr : P : Se = 3 : 4 : 4). The composition and the crystal structure of the compound were determined from single crystal X‐ray diffraction data. Lattice constants are a = 33.627(2) Å, b = 6.402(1) Å, c = 19.059(1) Å, β = 90.19(3) °, V = 4103.2(3) Å3, and Z = 12. The compound crystallizes in a structure that is related to (CuI)3P4Se4. Cages of β‐P4Se4 are stacked along the b‐axis and are separated by columns of copper(I) bromide. However, the coordination of the β‐P4Se4 cage molecules to the copper atoms in the CuBr columns in (CuBr)3P4Se4 is quite different from (CuI)3P4Se4. The monoclinic compound (space group: P21, no. 4) has an almost orthorhombic metric in combination with a threefold superstructure in [100]. Structural aspects of (CuBr)3P4Se4 are discussed with respect to the heavier homologue (CuI)3P4Se4. 相似文献
98.
本文研究了Cu(Ⅱ)-PEG(聚乙二醇-2000)-Zincon(锌试剂)-(NH4)2SO4体系的析相光度法并应用于测定Cu(Ⅱ)。最宜酸度为pH5.5~8.5(KH2PO4-K2HPO4)缓冲溶液)其络合物的最大吸收位于610nm,表观摩尔吸光系数为4.0×10^4L.mol^-1.cm^-1,Cu(Ⅱ)浓度在0~1.5mg/L范围内服从比尔定律,铜与Zincon形式组成为1:2的稳定的蓝色络 相似文献
99.
Microchip capillary electrophoresis (μCE) with amperometric detection at Cu electrode benefited fast separation and direct detection of carbohydrates. The working electrode of 50-μm Cu wire attached nearly against the channel outlet—4 μm, where it benefited collecting detection current and suppressing overwhelming noise. The use of alkaline medium was essential to separating and detecting carbohydrates, which dissociated into the sensitive alcolate anions. The 10-cm serpentine chip, though lengthening the migration time, it provided better efficiency. Sucrose, cellobiose, glucose, and fructose migrated from the outlet in 400 s +2000 V. The linear calibration plots ranging from 10 to 1000 μM with regression coefficients better than 0.996 were obtained. The injection-to-injection reproducibility of 1.24% (n=7) for glucose in peak current and 0.6% for migration times were excellent. The detection limit was low, down to 2.3 μM for glucose (S/N=3) or 27.6 attomole in mass detection. 相似文献
100.
Montserrat Barquín María J. Gonzlez Garmendia Liher Larrínaga Elena Pinilla María R. Torres 《无机化学与普通化学杂志》2005,631(11):2210-2214
The complexes of copper formato with pyrazine and dimethylpyrazines: Cu(HCOO)2(pyrz) ( 1 ), Cu2(HCOO)4(pyrz) ( 2 ), Cu2(HCOO)4(2,3‐Me2pyrz) ( 3 ), Cu2(HCOO)4(2,5‐Me2pyrz) ( 4 ), and Cu2(HCOO)4(2,6‐Me2pyrz)2 ( 5 ) have been synthesized and characterized by chemical analysis and IR and electronic spectro scopies. The three‐dimensional structure of compound 1 consists of –Cu–pyrz–Cu–pyrz– chains joined by bridging formate groups coordinated, in configuration syn‐anti, to two copper atoms. The coordination around the copper atom is orthorhombic with two Cu–O distances of 2.374(1) Å, two Cu–O of 1.952 Å and two Cu–N of 2.080 Å. Compound 5 is formed by molecular dimers with the [Cu2(μ‐HCOO)4] unit, two copper atoms and four syn‐syn fomate groups, and two ligands coordinated to the copper atoms in the axial positions. In compounds 2 and 3 chains of [Cu2(μ‐HCOO)4] dimers with pyrz or 2,3‐Me2pyrz as bridging ligands are formed. The EPR signal of 1 is orthorhombic (g = 2.23, 2.20 and 2.06). In the EPR spectra of 2 – 5 compounds the triplet (S = 1) signals are observed. The g?, g∥ and D values are been calculated. 相似文献