全文获取类型
收费全文 | 9463篇 |
免费 | 1808篇 |
国内免费 | 1045篇 |
专业分类
化学 | 6692篇 |
晶体学 | 84篇 |
力学 | 567篇 |
综合类 | 52篇 |
数学 | 1106篇 |
物理学 | 3815篇 |
出版年
2024年 | 11篇 |
2023年 | 225篇 |
2022年 | 218篇 |
2021年 | 344篇 |
2020年 | 401篇 |
2019年 | 377篇 |
2018年 | 374篇 |
2017年 | 303篇 |
2016年 | 523篇 |
2015年 | 444篇 |
2014年 | 562篇 |
2013年 | 760篇 |
2012年 | 939篇 |
2011年 | 918篇 |
2010年 | 632篇 |
2009年 | 612篇 |
2008年 | 627篇 |
2007年 | 532篇 |
2006年 | 502篇 |
2005年 | 407篇 |
2004年 | 311篇 |
2003年 | 233篇 |
2002年 | 196篇 |
2001年 | 163篇 |
2000年 | 182篇 |
1999年 | 211篇 |
1998年 | 164篇 |
1997年 | 157篇 |
1996年 | 175篇 |
1995年 | 142篇 |
1994年 | 119篇 |
1993年 | 90篇 |
1992年 | 99篇 |
1991年 | 56篇 |
1990年 | 73篇 |
1989年 | 54篇 |
1988年 | 26篇 |
1987年 | 28篇 |
1986年 | 37篇 |
1985年 | 38篇 |
1984年 | 13篇 |
1983年 | 16篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
Wei Fang Dr. Fangyi Liang Dr. Zhengwen Cao Frank Steinbach Prof. Dr. Armin Feldhoff 《Angewandte Chemie (International ed. in English)》2015,54(16):4847-4850
To combine good chemical stability and high oxygen permeability, a mixed ionic‐electronic conducting (MIEC) 75 wt % Ce0.85Gd0.1Cu0.05O2?δ‐25 wt % La0.6Ca0.4FeO3?δ (CGCO‐LCF) dual‐phase membrane based on a MIEC–MIEC composite has been developed. Copper doping into Ce0.9Gd0.1O2?δ (CGO) oxide enhances both ionic and electronic conductivity, which then leads to a change from ionic conduction to mixed conduction at elevated temperatures. For the first time we demonstrate that an intergranular film with 2–10 nm thickness containing Ce, Ca, Gd, La, and Fe has been formed between the CGCO grains in the CGCO‐LCF one‐pot dual‐phase membrane. A high oxygen permeation flux of 0.70 mL min?1 cm?2 is obtained by the CGCO‐LCF one‐pot dual‐phase membrane with 0.5 mm thickness at 950 °C using pure CO2 as the sweep gas, and the membrane shows excellent stability in the presence of CO2 even at lower temperatures (800 °C) during long‐term operation. 相似文献
102.
采用两步法将不同尺寸的silicalite-1分子筛纳米晶种通过自组装合成了一系列有序介孔silicalite-1分子筛。首先将强碱性的silicalite-1前驱体分别加热不同时间得到纳米晶种,然后在类似合成SBA-15的强酸性条件下组装成有序的介孔材料。合成条件的剧烈变化阻止了分子筛晶种的继续长大,并在三嵌段共聚物模板的诱导下组装成有序介孔材料。这种“自下而上”的方法制备有序介孔分子筛同时包含微孔和介孔。氮气吸脱附结果表明所制备的介孔分子筛材料均表现了很大的比表面积(730 m2/g以上)。 相似文献
103.
采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO2/β-PbO2,扫描电镜结果表明电极呈现由β-PbO2小晶体组成的菜花状微观形貌.所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命.用正交实验优化了电化学降解2-氯酚的实验条件.在最优的实验条件(2-氯酚初始浓度50 mg/L,电解质0.1 mol/L Na2SO4,温度35oC,阳极电流密度20 mA/cm2)下电化学降解180 min后,2-氯酚的去除率达100%.动力学结果表明, Ti/α-PbO2/β-PbO2电极上2-氯酚的电化学氧化符合准一级动力学过程. 相似文献
104.
采用浸渍法制备了不同V2O5担载量的V2O5/MO-Al2O3(M = Mg, Ca, Sr, Ba)催化剂,钒物种的前驱体为偏钒酸铵.对制备的催化剂进行了一系列表征,并对催化剂上正丁烷选择性氧化脱氢制取丁烯进行了反应研究.表征结果(包括比表面积、X射线衍射、傅里叶红外光谱、氢气程序升温还原和拉曼光谱)显示,不同碱土金属元素掺杂的催化剂显示不同的钒价态信息和催化性能.其中掺杂Ca, Sr, Ba的催化剂,正钒酸盐相很难被还原,因此催化剂的氧化还原循环难以建立,导致以上三种催化剂在正丁烷氧化脱氢反应中活性较低.然而, Mg掺杂的催化剂却显示出较高的催化活性和选择性.实验结果表明:在Mg掺杂的载体上担载5% V2O5的催化剂上600°C时可获得高达30.3%的正丁烷转化率和64.3%的烯烃总选择性.这与V2O5担载量为5%时,在获得高度分散的钒氧化合物物种时可使MgO晶相稳定存在密切相关. 相似文献
105.
文章合成了Lu(NO3)3(C2H5O2N)4.H2O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。 相似文献
106.
From Polymer to Monomer: Cleavage and Rearrangement of Si‐O‐Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure 下载免费PDF全文
Yujing Zuo Zhiming Gou Jinfeng Cao Zhou Yang Haifeng Lu Prof. Shengyu Feng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):10972-10977
Polymerization reactions are very common in the chemical industry, however, the reaction in which monomers are obtained from polymers is rarely invesitgated. This work reveals for the first time that oxone can break the Si‐O‐Si bond and induce further rearrangement to yield an ordered cyclic structure. The oxidation of P1 , which is obtained by reaction of 2,2′‐1,2‐ethanediylbis(oxy)bis(ethanethiol) (DBOET) with 1,3‐divinyl‐1,1,3,3‐tetramethyldisiloxane (MMVi), with oxone yielded cyclic crystallized sulfone–siloxane dimer ( P1‐ox ) after unexpected cleavage and rearrangement of the Si‐O‐Si bond. 相似文献
107.
Chain‐Growth Click Polymerization of AB2 Monomers for the Formation of Hyperbranched Polymers with Low Polydispersities in a One‐Pot Process 下载免费PDF全文
Yi Shi Robert W. Graff Xiaosong Cao Xiaofeng Wang Haifeng Gao 《Angewandte Chemie (International ed. in English)》2015,54(26):7631-7635
Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB2 monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed CuI, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83. 相似文献
108.
Jiajia Yang Yun Li Jincheng Wang Xiaoli Sun Syed Mazhar Shah Rong Cao Jiping Chen 《Analytica chimica acta》2015
Bisphenol A (BPA) imprinted sponge mesoporous silica was synthesized using a combination of semi-covalent molecular imprinting and simple self-assembly process. The molecularly imprinted sponge mesoporous silica (MISMS) material obtained was characterized by FT-IR, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption measurements. The results show that the MISMS possessed a large specific surface area (850.55 m2 g−1) and a highly interconnected 3-D porous network. As a result, the MISMS demonstrated a superior specific adsorption capacity of 169.22 μmol g−1 and fast adsorption kinetics (reaching equilibrium within 3 min) for BPA. Good class selectivity for BPA and its analogues (bisphenol F, bisphenol B, bisphenol E and bisphenol AF) was also demonstrated by the sorption experiment. The MISMS as solid-phase extraction (SPE) material was then evaluated for isolation and clean-up of these bisphenols (BPs) from sediment samples. An accurate and sensitive analytical method based on the MISMS–SPE coupled with HPLC–DAD has been successfully established for simultaneous determination of five BPs in river sediments with detection limits of 0.43–0.71 ng g−1 dry weight (dw). The recoveries of BPs for lyophilizated sediment samples at two spiking levels (50 and 500 ng g−1 dw for each BP) were in the range of 75.5–105.5% with RSD values below 7.5%. 相似文献
109.
Dong Cao Huogao Huang Ming Hu Lin Cui Fanglan Geng Ziyu Rao Hongyun Niu Yaqi Cai Yuehui Kang 《Analytica chimica acta》2015
Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200–800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio < 0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7 > O/C ratio > 0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM molecules identified by MALDI may be aromatic or condensed aromatic compounds with special groups which are liable to absorb electron from other molecules to generate free radical anions during MALDI ionization. 相似文献
110.