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41.
NO2气相硝化金刚烷的计算研究 总被引:3,自引:0,他引:3
运用密度泛函理论(DFT)和半经验MO-PM3方法研究了NO2气相硝化金刚烷反应机理. 计算结果表明, NO2不能直接取代金刚烷H; 在B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G* 较高水平下, 对三个可能机理的反应势垒(Ea)的精确计算表明, 该反应的决速步骤为NO2中O和N进攻1-H的竞争过程, 且1-硝基金刚烷为主要产物. NO2中O进攻1-H决速反应过程中, 分子几何、原子自然电荷及IR光谱变化表明, C—H键的断裂和N—H键的形成是一个协同过程; 参与新键形成和旧键断裂原子C(1), H(11), O(28), O(29)和N(27)的原子自然电荷及与其相关的键长、键角有明显的变化. 反应过程中体系偶极矩的变化表明, 极性溶剂能降低反应势垒, 有利于反应的进行. 相似文献
42.
CrOx/ SBA-15介孔催化剂上丙烷在二氧化碳气氛中脱氢反应的研究 总被引:2,自引:0,他引:2
The structure and catalytic properties based on Chromium Oxide supported on mesoporous SBA-15 for oxidative dehydrogenation of propane by CO2 have been studied by using X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and propane pulsing experiments in the absence of gas-phase O2. It has been shown that propane conversion and propene yield increase with Cr loadings. The propane conversion and propene yield on CrOx(Cr: 10wt%)/SBA-15 catalyst for oxidative dehydrogenation of propane by CO2 at 550 ℃ reach 24.8% and 21.8%, respectively .The results of ESR, UV-Vis DRS and propane pulsing experiments indicate that CrⅢ in the CrOx/ SBA-15 catalyst is the main active species in oxidative dehydrogenation of propane by CO2 and CrⅥ, CrⅤ is inactive in dehydrogenation. 相似文献
43.
The sequence distribution and the terminal structures of poly-1,3-pentadiene chains obtained by rare earth catalyst and effect of polymerization temperature on microstructure of the polymer have been investigated by ~(13)C-NMR method. According to experimental results it was supposed that terminal active growing chain of the polymer would be four types of anti- and syn-η~3-allyl structures. When polymerization temperature was reduced, the content of cis-1,4-poly-1,3-pcntadiene increases. It can be explained by isomerization between anti- and syn-η~3-allyl. The process forming trans-1,2 unit instead of 3,4-unit were also described. 相似文献
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46.
Reactivity Ratios of Diethyldiallylammonium Chloride with Acrylamide or Acrylic Acid 总被引:1,自引:0,他引:1
Li Hua LIU Zhi Qiang LIU Zhu Qing GONG 《中国化学快报》2006,17(11):1523-1526
The compositions of copolymers of diethyldiallylammonium chloride (DEDAAC) with acrylamide (AM), acrylic acid (AA) or sodium acrylic acid (NaAA) at low conversion were determined by elemental analysis, and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method. The results showed that the reactivity ratios rDE and rAM are 0.31 and 5.27 for DEDAAC with AM, rDE and rAA are 0.28 and 5.15 for DEDAAC with AA, and rDE and rNaAA are 0.40 and 3.97 for DEDAAC with NaAA, respectively. The copolymerizations for DEDAAC with AM, AA or NaAA are non-ideal copolymerization and the products are random copolymers. 相似文献
47.
In the reaction of methane and carbon dioxide to C2 hydrocabons under non-equilibrium plasma, methane conversion was decreased,but selectivity of C2 hydroxarbons was increased when using La2O3/γ-Al2O3 as catalyst. So the yield of C2 hydrocarbons was higher than using plasma alone. The synergism of La2O3/γ-Al2O3 and plasma gave methane conversion of 24.9% and C2 yield of 18.1%. The distribution of C2 hydrocarbons changed when Pd-La2O3/γ-Al2O3 was used as catalyst,the major C2 product was ethylene. 相似文献
48.
Hai Bing LI Yuan Yin CHEN* Shu Ling GONG Department of Chemistry Wuhan University Wuhan 《中国化学快报》2002,13(3)
Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a… 相似文献
49.
The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary. 相似文献
50.
以醋酸乙烯酯(VAc)和甲基丙烯酸甲酯(MMA)为单体, 采用半连续种子乳液聚合法制备了无规共聚物聚(醋酸乙烯酯-甲基丙烯酸甲酯)[P(VAc-MMA)], 并以此聚合物为基体制备了聚合物电解质. 用红外光谱(FTIR)、核磁共振氢谱(1H NMR)、扫描电镜(SEM)、差热/热重分析(DSC/TG)、X射线衍射(XRD)、机械性能测试和电化学交流阻抗等方法对聚合物和聚合物电解质的性质进行了研究. 测试结果表明: VAc和MMA聚合生成P(VAc-MMA); 聚合物膜含有大量微孔结构, 利于离子传输; 聚合物电解质膜具有优良的热稳定性和机械强度; 25 ℃下, 最高的离子电导率达到了1.27×
10-3 S•cm-1; 离子电导率随着温度的升高而迅速增加, 电导率-温度曲线符合Arrhenius方程. 相似文献