全文获取类型
收费全文 | 685篇 |
免费 | 98篇 |
国内免费 | 240篇 |
专业分类
化学 | 535篇 |
晶体学 | 8篇 |
力学 | 28篇 |
综合类 | 1篇 |
数学 | 172篇 |
物理学 | 279篇 |
出版年
2023年 | 18篇 |
2022年 | 28篇 |
2021年 | 36篇 |
2020年 | 33篇 |
2019年 | 20篇 |
2018年 | 16篇 |
2017年 | 20篇 |
2016年 | 26篇 |
2015年 | 34篇 |
2014年 | 40篇 |
2013年 | 75篇 |
2012年 | 103篇 |
2011年 | 77篇 |
2010年 | 67篇 |
2009年 | 65篇 |
2008年 | 54篇 |
2007年 | 67篇 |
2006年 | 59篇 |
2005年 | 41篇 |
2004年 | 27篇 |
2003年 | 19篇 |
2002年 | 27篇 |
2001年 | 10篇 |
2000年 | 7篇 |
1999年 | 17篇 |
1998年 | 16篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 1篇 |
排序方式: 共有1023条查询结果,搜索用时 31 毫秒
11.
电镀烧结法制备Ti/SnO2-Sb2O4电极的研究 总被引:1,自引:0,他引:1
The Ti/SnO2-Sb2O4 electrode has been prepared by the electroplate-sinter method. The effect of SbCl3 adding amount and sintering temperature on its electrode lifetime and oxygen evolution potential were investigated by means of EDX, SEM and XRD analysis. The results indicated that the electrode appeared the best performance when the SbCl3 adding amounts was 0.2g and the sintering temperature was 550℃. In optimized conditions Ti substrate was entirely covered by SnO2-Sb2O4 and the combinations among them were tight. Due to the use of electroplate method, the electrical conductivity, the oxygen evolution potential and the electrode lifetime were increased, so the elec-tro-catalytic activity and the electrochemical stability of the prepared electrode were found to be superior. 相似文献
12.
Supermolecular compounds of glycine monosubstituted heteropolytungstates isomer with Keggin structure βi-K6-n(HGly)n[SiW11M(H2O)O39]·xH2O (M=Co2+, Ni2+; βi=β2, β3) were synthesized and characterized by means of elementary analysis, IR, UV, TG-DTA, X-ray diffraction, polarography and CV. The results indicate that glycin combines the electrostatic effect with heteropolytungstates isomer. The heteropoly anion still remains its Keggin structure in supermolecular compounds. The electrochemical behavior of the compound in 1 mol·L-1 HAc-NaAc shows that two redox waves correspond to two two-electron processes attributing to the reduction of [SiW11Co(H2O)O39]6-. Steady-state fluorescence spectrum shows two intenser fluorescence emission peaks in 447 nm and 486 nm appeared after the supermolecular compound being excited by the excitation wavelength in 274 nm. 相似文献
13.
《Radiation Physics and Chemistry》2006,75(8):832-836
Radiation produced by a relativistic charged particle in matter is described in terms of the radiation energy loss. It allows us to take into account the matter absorption and derive energy-angular distributions of the emitted photons for different particle trajectories. The Doppler radiation produced by laser pulses in matter and the influence of multiple scattering on the angular distribution of radiation are considered. The radiation in left-handed materials is discussed. 相似文献
14.
手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应 总被引:2,自引:0,他引:2
合成了三种新的含C2-对称轴的手性胺醇(PhOHCHCH2)2NCH2C6H4R (R=OCH3, L1; R=CH3, L2; R=Cl, L3), 将其与无水氯化稀土LnCl3•4THF (Ln=La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L=L1, L2, L3; Ln=La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L1/SmCl3•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%. 相似文献
15.
Monoamino substituted asymmetrical phthalocyanine zinc(Ⅱ), 2-amino-9,10,16,17,23,24-hexapentyloxy phthalocyanine zinc(Ⅱ), was synthesized by statistical condensation and characterized by elemental analysis, UV-Vis, IR and TOF-MS. The aggregative behavior was studied in DMF, THF and CH2Cl2. The results show that it is not aggregateve in DMF and THF, whereas form dimer in CH2Cl2 at 8 × 10-7~8 × 10-6 mol·L-1. The equilibrium constant for the dimer was calculated at the same time, indicating that the less polar solvent is unfavorable for the presence of the monomer. 相似文献
16.
The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD(T) methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO+CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO+HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO+ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations. 相似文献
17.
A novel 1-D Cd(Ⅱ) coordination polymer, [Cd(p-BDOA)·2H2O]n(I) ( p-BDOA2-=benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR, PL, TG and X-ray single crystal diffraction. The Crystal crystallizes in monoclinic system, the space group is C2/c, with the crystal cell parameters a=1.175 1(1) nm, b=0.551 0(1) nm, c=1.827 7(2) nm, β=96.14(2)°, and V=1.176 6(3) nm3,, Mr=372.60, R=0.045 9, wR=0.127 9. The Cd(Ⅱ) ion has a trigonal prism coordination configuration that defined by four carboxyl O atoms from two different p-BDOA2- ligands and two water molecules. Adjacent Cd(Ⅱ) ions are linked by carboxylate groups with the bidentate coordination mode, giving rise to a chain structure with the adjacent Cd…Cd distance of 1.526 3(5) nm. Furthermore, such chains are linked by hydrogen bonds to form supramolecular network. The results of PL and TG show that the complex exhibits intense fluorescent emissions and its chain skeleton is thermally stable up to 419 K. CCDC: 220443. 相似文献
18.
Ce4+-Ce3+循环体系引发淀粉与丙烯酰胺接枝共聚合反应动力学研究 总被引:16,自引:1,他引:16
The cyclic initiating system of Ce4+ - Ce3+ - Ce4+, in which the product of reduced ion Ce3+ forming from Ce4+ after initation being oxidized again to the original oxidizing ion Ce4+ is examined. The characters of process of the graft copolymerisation using the cyclic initiating system is compared with the ones using ceric and persulphate individually. When using the cyclic systerm as initator, it was more effective to graft polymerise acylamide onto starch and a rather high proportion of graft copolymer was made as opposed to using persulphate individually. 相似文献
19.
本文研究带有五次项的非线性Schrödinger方程初边值问题的有限差分法,其中方程中二阶偏导数项的系数、五次项的系数及初值满足下面的条件(1.6).针对此问题,我们研究了一个守恒差分格式,在条件(1.6)下,差分解的$L^{\infty}$模先验估计被得到.在此基础上,我们得到了差分解最优$L^2$模的误差估计. 相似文献
20.
The three-photon absorption effect (3PA) of two novel symmetrical charge transfer fluorene-based molecules (abbreviated as BASF and BMOSF) has been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 84 × 10−78 and 114 × 10−78 cm6 s2, respectively. The geometries and electronic excitations of these two molecules are systematically studied by PM3 and ZINDO/S methods. The relationships between 3PA cross-sections and intramolecular charge transfer are discussed micromechanically. The experimental and theoretical results have shown that the larger intramolecular charge transfer, which was characterized by the charge density difference between the ground state (S0) and the first excited state (S1), the greater enhancement of the 3PA cross-sections. 相似文献