全文获取类型
收费全文 | 25236篇 |
免费 | 3241篇 |
国内免费 | 1848篇 |
专业分类
化学 | 14514篇 |
晶体学 | 1415篇 |
力学 | 1743篇 |
综合类 | 195篇 |
数学 | 6348篇 |
物理学 | 6110篇 |
出版年
2024年 | 24篇 |
2023年 | 304篇 |
2022年 | 564篇 |
2021年 | 723篇 |
2020年 | 1011篇 |
2019年 | 768篇 |
2018年 | 657篇 |
2017年 | 678篇 |
2016年 | 1135篇 |
2015年 | 1031篇 |
2014年 | 1241篇 |
2013年 | 2042篇 |
2012年 | 1373篇 |
2011年 | 1573篇 |
2010年 | 1230篇 |
2009年 | 1517篇 |
2008年 | 1518篇 |
2007年 | 1669篇 |
2006年 | 1533篇 |
2005年 | 1210篇 |
2004年 | 1133篇 |
2003年 | 980篇 |
2002年 | 788篇 |
2001年 | 701篇 |
2000年 | 676篇 |
1999年 | 567篇 |
1998年 | 550篇 |
1997年 | 481篇 |
1996年 | 423篇 |
1995年 | 309篇 |
1994年 | 273篇 |
1993年 | 231篇 |
1992年 | 202篇 |
1991年 | 160篇 |
1990年 | 138篇 |
1989年 | 111篇 |
1988年 | 103篇 |
1987年 | 85篇 |
1986年 | 88篇 |
1985年 | 69篇 |
1984年 | 68篇 |
1983年 | 28篇 |
1982年 | 35篇 |
1981年 | 41篇 |
1980年 | 29篇 |
1979年 | 33篇 |
1978年 | 48篇 |
1977年 | 48篇 |
1976年 | 46篇 |
1974年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
1.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
2.
In this article, we construct and analyze a residual-based a posteriori error estimator for a quadratic finite volume method (FVM) for solving nonlinear elliptic partial differential equations with homogeneous Dirichlet boundary conditions. We shall prove that the a posteriori error estimator yields the global upper and local lower bounds for the norm error of the FVM. So that the a posteriori error estimator is equivalent to the true error in a certain sense. Numerical experiments are performed to illustrate the theoretical results. 相似文献
3.
4.
在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。 相似文献
5.
Seema Prasad 《Molecular Crystals and Liquid Crystals》2018,665(1):52-63
Molecular structure and vibrational spectroscopic studies of higher homologous series nematogenic p-n-alkylbenzoic acids (nBAC) that have 6 (6BAC) and 7 (7BAC) carbon atoms in the alkyl chain have been investigated using the Density Functional Becke3-Lee-Yang-Parr (B3LYP) level with the basis set 6-31++G (d.p) and Hartree Fock (HF) with the same basis set. The observed vibrational spectra has been resolved and assigned in detail for comparision with both the molecules. These results indicate that DFT and HF values are slightly different at both the levels. A comparision of chemical reactivity such as HOMO (EH), LUMO (EL) energies, energy gap (Eg), ionization energy (I), electron affinity (A), electro negativity (χ), chemical hardness (η), electronic chemical potential (μ), electrophilicity index (ω), and softness (S) has been made. It has been observed that the decrement has occurred in the energy band gap value of isolated molecule with increment in alkyl chain length. This provides valuable information regarding enhancing the stability of liquid crystal materials by maintaining the conductivity. 相似文献
6.
As a new type of quantum dots (QDs), hexagonal boron nitride quantum dots (BNQDs) exhibit promising potential in the applications of disease diagnosis, fluorescence imaging, biosensing, metal ion detection, and so on, because of their remarkable chemical stability, excellent biocompatibility, low cytotoxicity, and outstanding photoluminescence properties. However, the large-scale fabrication of homogeneous BNQDs still remains challenging. In this article, the properties and common fabrication methods of BNQDs are summarized based on the recent research progress. Then, the corresponding yields, morphologies, and fabrication mechanisms of these as-obtained BNQDs are discussed in detail. Moreover, the applications of these as-obtained BNQDs in different fields are also discussed. This article is expected to inspire new methods and improvements to achieve large-scale fabrication of homogeneous BNQDs, which will enable their practical applications in future. 相似文献
7.
煤直接液化油中混合酚的分离研究 《燃料化学学报》2019,47(11):1298-1304
利用分子筛择形特点,对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物,采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变,分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响,以获得高性能固相吸附剂,并将其应用于180-190℃馏分段混合酚分离。结果表明,当分子筛硅铝比为25、粒径为3-5 μm时,分子筛的孔口结构调节效果最优;当正硅酸乙酯的最小用量为0.2 mL/g时,固相吸附剂的吸附量为0.03 g/g,对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化,导致对甲酚选择性的提高。进一步采用HZSM-5(1)吸附剂对真实煤直接液化油混合酚的分离中发现,苯酚和对甲酚的选择性均达到100%。 相似文献
8.
In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation. 相似文献
9.
Mariam Hakami Dr. Geetanjali Deokar Jasmin Smajic Dr. Nitin M. Batra Prof. Pedro M. F. J. Costa 《化学:亚洲杂志》2021,16(11):1466-1474
In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm2-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors. 相似文献
10.