全文获取类型
收费全文 | 15602篇 |
免费 | 2577篇 |
国内免费 | 1883篇 |
专业分类
化学 | 11681篇 |
晶体学 | 187篇 |
力学 | 791篇 |
综合类 | 98篇 |
数学 | 1404篇 |
物理学 | 5901篇 |
出版年
2024年 | 53篇 |
2023年 | 279篇 |
2022年 | 523篇 |
2021年 | 579篇 |
2020年 | 659篇 |
2019年 | 652篇 |
2018年 | 577篇 |
2017年 | 481篇 |
2016年 | 778篇 |
2015年 | 733篇 |
2014年 | 874篇 |
2013年 | 1221篇 |
2012年 | 1388篇 |
2011年 | 1359篇 |
2010年 | 938篇 |
2009年 | 940篇 |
2008年 | 1055篇 |
2007年 | 946篇 |
2006年 | 855篇 |
2005年 | 764篇 |
2004年 | 622篇 |
2003年 | 529篇 |
2002年 | 572篇 |
2001年 | 400篇 |
2000年 | 291篇 |
1999年 | 304篇 |
1998年 | 252篇 |
1997年 | 223篇 |
1996年 | 202篇 |
1995年 | 164篇 |
1994年 | 144篇 |
1993年 | 109篇 |
1992年 | 108篇 |
1991年 | 102篇 |
1990年 | 73篇 |
1989年 | 58篇 |
1988年 | 39篇 |
1987年 | 30篇 |
1986年 | 34篇 |
1985年 | 34篇 |
1984年 | 20篇 |
1983年 | 16篇 |
1982年 | 14篇 |
1981年 | 17篇 |
1980年 | 9篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 5篇 |
1971年 | 4篇 |
1936年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A selenium-functionalizedε-caprolactone was synthesized by introducing a phenyl selenide group at the 7-position.A polymer was obtained through the ring-opening polymerization of this monomer in a base/thiourea binary organocatalytic system.A living polymerization process was achieved under mild conditions.The resulting polymers had a controlled molecular weight with a narrow molecular weight distributions and high end-group fidelity.Random copolymers could be obtained by copolymerizing this monomer withε-caprolactone.The thermal degradation temperature of the obtained copolymers decreased with the increasing molar ratio of selenide functionalized monomer in copolymers,while the glass transition temperature increased.In addition,the phenyl selenide side group could be further modified to a polyselenonium salt,which resulted in a polymer with good antibacterial properties.The survival rate of E.coli and S.aureus was only 9%with a polymer concentration of 62.5μg/mL. 相似文献
992.
过渡金属Ni是地球上储量丰富的金属元素, 在加氢脱硫、重整制氢等催化领域应用非常广泛, 但是关于Ni基催化剂在烷烃脱氢方面的研究较少; 因此, 本工作采用不同的方法, 制备了三种结构的Ni基负载催化剂, 即尖晶石分解型、浸渍型和钙钛矿析出型, 并在700 ℃、C2H6-N2气氛中和50 mL•min-1气体流速下, 探索了它们的乙烷脱氢性能. 结果表明: 尖晶石分解型催化剂Ni1-xCuxCr2O4还原后在Cr2O3表面形成Ni-Cu合金颗粒, 能有效钝化Ni的C—C键断裂活性, 提高乙烯的选择性. Ni含量过高时, Ni不能有效地分散而形成大的金属团簇, 造成乙烷过度裂解, 乙烯选择性较低. 浸渍负载型催化剂NixMy/Al2O3 (M为Cu或Ag) 比表面积大, 表面活性位点分散, 但活性金属与载体结合力弱, 在高温下不稳定; Cu或Ag与Ni形成合金, 可有效提高乙烯选择性, Ag较Cu的效果更佳. 钙钛矿析出型催化剂LaCr1-xNixO3(LCNi-100x)在还原气氛中析出均匀细小的Ni颗粒, 其与基体结合力强, 抗积碳性能和稳定性较高; 含15% Ni的LCNi-15还原后(R-LCNi-15)表现出最好的催化性能, 乙烯产率最高(24%), 同时具有较好的抗积碳性能和稳定性以及氧化再生性. 相似文献
993.
The isomorphous title compounds (and the ordered substitutional Rb(14)CsTl(27)) are obtained directly from reactions of the elements in sealed Ta below approximately 330 degrees C. Refinements of single-crystal data for the three established a structure with alternate layers of isolated pentacapped trigonal prismatic Tl(11)(7)(-) (D(3)(h)()) ions and condensed [Tl(16)(8-)] networks that are separated by cations. The condensed layer consists of Tl(11) units that share prismatic edges and are interbridged through waist-capping atoms (Tl(6/2)Tl(3)Tl(2)). (Rb(15)Tl(27): P&sixmacr;2m, Z = 1, a = 10.3248(6) ?, c = 17.558(2) ?.) The rubidium phase is a poor metal (rho(293) approximately 34 &mgr;Omega.cm) and is Pauli-paramagnetic. Extended Hückel band calculations indicate partially filled bands and a non-zero DOS at E(F), consistent with the observed metallic behavior, although appropriate cation tuning or modest anion doping should provide a Zintl phase. The band structure and COOP curves are also used to rationalize the distortion of the Tl(11) unit on condensation and the critical role of the interfragment bonds between waist-capping atoms in stabilizing the layer. 相似文献
994.
995.
基于半刚性的配体3′,5′-di(1H-1,2,4-triazol-1-yl)-(1,1′-biphenyl)-3,5-dicarboxylic acid (H2DTBDA)和硝酸钴制备了一个柔性超微孔的金属有机骨架{[Co(DTBDA)]·4H2O}n (FJI-H35),并对该材料的结构进行了系统的表征。FJI-H35活化以后可以发生自适应的结构转变,使得孔径从0.43 nm收缩到0.37 nm。气体吸附测试表明FJI-H35可以从氮气和甲烷中选择性捕获二氧化碳,具有很高的吸附选择性和相对低的吸附焓。突破实验进一步证实FJI-H35可以从二氧化碳/氮气(15∶85,V/V)和二氧化碳/甲烷(50∶50,V/V)混合气中高效选择性捕获二氧化碳。 相似文献
996.
Du Jinzhou Dong Wenming Wang Xiangke Tao Zuyi 《Journal of Radioanalytical and Nuclear Chemistry》1996,203(1):31-36
The effect of different solid components of calcareous soil on the retention of Sr was investigated by using batch technique and selective extraction method. The sorption and desorption isotherms of Sr on the untreated calcareous soil and the three treated soils were determined at 20°C, pH 7.8±0.2 and in the presence of 0.001 M CaCl2. It was found that all isotherms are linear and that the sorption of Sr on the calcareous soil can be described by a reversible sorption process and the sorption mechanism is mainly ion exchange. 相似文献
997.
化学工业生产中,用氢气为还原剂,通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物,而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径,但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb2O5(PVP: 聚乙烯吡咯烷酮)催化剂,该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应,系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能,在最优条件下,5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。 相似文献
998.
Rechargeable Mg batteries (RMBs) are advantageous large-scale energy-storage devices because of the high abundance and high safety, but exploring high-performance cathodes remains the largest difficulty for their development. Compared with oxides and sulfides, selenides show better Mg-storage performance because the weaker interaction with the Mg2+ cation favors fast kinetics. Herein, nanorod-like FeSe2 was synthesized and investigated as a cathode for RMBs. Compared with microspheres and microparticles, nanorods exhibit higher capacity and better rate capability with a smaller particle size. The FeSe2 nanorods show a high capacity of 191 mAh g−1 at 50 mA g−1 and a good rate performance of 39 mAh g−1 at 1000 mA g−1. Ex situ characterizations demonstrate the Mg2+ intercalation mechanism for FeSe2, and a slight conversion reaction occurs on the surface of the particles. The capacity fading is mainly because of the dissolution of Fe2+, which is caused by the reaction between Fe2+ and Cl− of the electrolyte during the charge process on the surface of the particles. The surface of FeSe2 is mainly selenium after long cycling, which may also dissolve in the electrolyte during cycling. The present work develops a new type of Mg2+ intercalation cathode for RMBs. More importantly, the fading mechanism revealed herein has considered the specificity of Mg battery electrolyte and would assist a better understanding of selenide cathodes for RMBs. 相似文献
999.
Dr. Lanjie Lei Prof. Chao Zhao Dr. Xiaofei Zhu Mr. Shuai Yuan Dr. Xing Dong Dr. Yinxiu Zuo Prof. Hong Liu 《Electroanalysis》2022,34(2):415-422
We report on a nonenzymatic electrochemical sensor for wearable glucose monitoring in interstitial fluid. The sensor exhibited acceptable selectivity and reliability for continuous glucose detection for up to 30 days. The sensor tip is coated with polyurethane, and the biocompatibility of the tip is investigated by tissue staining. A fully integrated wearable glucose monitoring system is developed with a wireless connection with a smartphone. The test results are in agreement with reference methods. So, we believe the sensor is promising for the development of a continuous glucose monitoring system and diabetes management. 相似文献
1000.
Ting Li Hui Dong Yuanqiang Hao Yintang Zhang Shu Chen Maotian Xu Yanli Zhou 《Electroanalysis》2022,34(6):956-965
Near-infrared (NIR) light-driven photoelectrochemical (PEC) sensing is a highly promising analytical technique, especially for in situ bioanalysis, due to the deep penetration capability and minimal invasiveness of NIR light. In this mini review, we provide a brief overview of recently developed NIR PEC sensors, focusing on NIR light-responsive materials and the representative applications of this type of PEC sensor. Future perspectives for NIR PEC sensors are also described. 相似文献