全文获取类型
收费全文 | 18784篇 |
免费 | 3506篇 |
国内免费 | 5518篇 |
专业分类
化学 | 15142篇 |
晶体学 | 576篇 |
力学 | 1287篇 |
综合类 | 742篇 |
数学 | 2818篇 |
物理学 | 7243篇 |
出版年
2024年 | 15篇 |
2023年 | 159篇 |
2022年 | 576篇 |
2021年 | 546篇 |
2020年 | 553篇 |
2019年 | 696篇 |
2018年 | 527篇 |
2017年 | 766篇 |
2016年 | 707篇 |
2015年 | 1021篇 |
2014年 | 1169篇 |
2013年 | 1513篇 |
2012年 | 1600篇 |
2011年 | 1654篇 |
2010年 | 1525篇 |
2009年 | 1559篇 |
2008年 | 1803篇 |
2007年 | 1553篇 |
2006年 | 1472篇 |
2005年 | 1378篇 |
2004年 | 1098篇 |
2003年 | 836篇 |
2002年 | 873篇 |
2001年 | 802篇 |
2000年 | 737篇 |
1999年 | 440篇 |
1998年 | 303篇 |
1997年 | 229篇 |
1996年 | 206篇 |
1995年 | 177篇 |
1994年 | 180篇 |
1993年 | 153篇 |
1992年 | 148篇 |
1991年 | 99篇 |
1990年 | 115篇 |
1989年 | 98篇 |
1988年 | 99篇 |
1987年 | 78篇 |
1986年 | 61篇 |
1985年 | 49篇 |
1984年 | 35篇 |
1983年 | 35篇 |
1982年 | 29篇 |
1981年 | 27篇 |
1980年 | 18篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 10篇 |
1965年 | 7篇 |
1936年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Weizhao Hu Bibo Wang Xin Wang Hua Ge Lei Song Jian Wang Yuan Hu 《Journal of Thermal Analysis and Calorimetry》2014,117(1):27-38
Ethyl cellulose, a widely used bio-degradable shell material, microencapsulated ammonium polyphosphate (MAPP) was added to the bio-degradable poly(butylene succinate) (PBS) to improve its flame retardancy, compatibility, and thermal stability. The MAPP was well characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), water contact angle, and thermogravimetric (TG) analysis. The SEM results indicate the improved dispersion of MAPP into PBS matrix and the formation of the strong interfacial adhesion between MAPP and PBS than APP. With the incorporation of MAPP and char-forming agent into PBS, the limiting oxygen index of the composite was increased to 35.5 %, and the sample can pass the UL-94 V-0 rating, while the un-microencapsulated counterpart cannot reach the rating. The cone calorimeter test showed that the peak heat release rate was decreased by 46.7 % and the burning time was also prolonged compared to the pure PBS. The increased melt flow index and rheology test indicated the increase of viscosity and the improvement of anti-dripping properties. Moreover, the mechanical properties and thermal stability of MAPP composite were also obviously enhanced after the microencapsulation by mechanical, dynamical mechanical thermal analysis, and TG analysis. 相似文献
992.
用CeO2作为铈源,采用可重复利用的H3PO4及非模板剂的情况下,用低温超声法成功合成了六方结构的CePO4一维纳米线材料。用X-射线粉末衍射(XRD)、透射电镜(TEM)和荧光分光光度计(FL)测试样品的物相结构、微观形貌、颗粒尺寸和发光性能;并研究超声时间和PO3-4/Ce3+摩尔比对产物的形貌和荧光性能的影响。结果表明:实验所做出的样品全部是六方晶系的结构,形貌都为一维纳米线,其纳米线长50~200nm,宽5~40nm左右;不同超声时间和PO3-4/Ce3+摩尔比的纳米线长径比不同,随超声时间的延长和PO3-4/Ce3+摩尔比增大纳米线出现团聚现象,产物在250~300nm处有宽的激发峰,在378nm处有一个发射峰,是属于Ce3+的5d-4f能级跃迁。 相似文献
993.
Metal Oxide‐Coated Three‐Dimensional Graphene Prepared by the Use of Metal–Organic Frameworks as Precursors 下载免费PDF全文
Xianhong Rui Wenhui Shi Prof. Qingyu Yan Prof. Hua Zhang 《Angewandte Chemie (International ed. in English)》2014,53(5):1404-1409
A simple method for the preparation of metal‐oxide‐coated three‐dimensional (3D) graphene composites was developed. The metal–organic frameworks (MOFs) that served as the precursors of the metal oxides were first synthesized on the 3D graphene networks (3DGNs). The desired metal oxide/3DGN composites were then obtained by a two‐step annealing process. As a proof‐of‐concept application, the obtained ZnO/3DGN and Fe2O3/3DGN materials were used in a photocatalytic reaction and a lithium‐ion battery, respectively. We believe this method could be extended to the synthesis of other metal oxide/3DGN composites with 3D structures simply through the appropriate choice of specific MOFs as precursors. 相似文献
994.
The hydration of NaCl has been widely studied and believed to be important for understanding the mechanisms of salt dissolution in water and the formation of ice nucleus, cloud, and atmospheric aerosols. However, understanding on the poly-NaCl ion pair interacting with water is very limited. Here, we investigated the adsorption of water molecules on (NaCl)3, using both theoretical calculations and anion photoelectron spectroscopy measurements. The calculated vertical detachment energies and the experimental ones agree well with each other. Furthermore, we found that, for neutral (NaCl)3(H2O) n (n = 2–7) clusters, the water-doped cuboid and structures formed by adding water molecules on the Na–Cl edges of the cuboid are energetically favored; water molecules preferentially bind to the Na–Cl edge if the NaCl ion pair has larger partial charges than others. We also found the anionic structures are more various compared with neutral ones, and the Na+ and Cl? ions are hydrated more easily in the anionic clusters than in the corresponding neutrals. 相似文献
995.
Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity 下载免费PDF全文
Neng‐Fei Yu Dr. Na Tian Dr. Zhi‐You Zhou Long Huang Jing Xiao Yu‐Hua Wen Prof. Shi‐Gang Sun 《Angewandte Chemie (International ed. in English)》2014,53(20):5097-5101
Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO. 相似文献
996.
Dr. Chunxiu Hua Dr. Xiangpeng Fang Prof. Zhaoxiang Wang Prof. Liquan Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5487-5491
It is well accepted that metallic tin as a discharge (reduction) product of SnOx cannot be electrochemically oxidized below 3.00 V versus Li+/Li0 due to the high stability of Li2O, though a similar oxidation can usually occur for a transition metal formed from the corresponding oxide. In this work, nanosized Ni2SnO4 and NiO/SnO2 nanocomposite were synthesized by coprecipitation reactions and subsequent heat treatment. Owing to the catalytic effect of nanosized metallic nickel, metallic tin can be electrochemically oxidized to SnO2 below 3.00 V. As a result, the reversible lithium‐storage capacities of the nanocomposite reach 970 mAh g?1 or above, much higher than the theoretical capacity (ca. 750 mAh g?1) of SnO2, NiO, or their composites. These findings extend the well‐known electrochemical conversion reaction to non‐transition‐metal compounds and may have important applications, for example, in constructing high‐capacity electrode materials and efficient catalysts. 相似文献
997.
Bin Zhou Yedi Xing Prof. Shu Miao Prof. Mingrun Li Prof. Wen‐Hua Zhang Prof. Can Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12426-12431
A facile colloidal approach to synthesize Ag8(Ge1?x,Snx)(S6?y,Sey) nanocrystals (NCs) in a highly controlled way across the entire compositional ranges (0≤x≤1, 0≤y≤6) has been developed. The NCs exhibit a uniform size distribution, highly crystalline structure, over 1 g scalable synthesis, and tunable band gaps in the range of 0.88–1.45 eV by varying their chemical compositions. The Ag8GeS6 NCs with a band gap of approximately 1.45 eV were employed as a model light harvester to assess their applicability in solar cells by a full solution‐processing device, yielding an efficiency of 0.28 % under AM1.5 illumination, demonstrating their application potential in solar energy utilization. 相似文献
998.
Chemical and Toxicological Investigations of a Previously Unknown Poisonous European Mushroom Tricholoma terreum 下载免费PDF全文
Xia Yin Dr. Tao Feng Prof. Jian‐Hua Shang Yun‐Li Zhao Fang Wang Zheng‐Hui Li Ze‐Jun Dong Prof. Dr. Xiao‐Dong Luo Prof. Dr. Ji‐Kai Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7001-7009
The established tradition of consuming and marketing wild mushrooms has focused attention on mycotoxicity, which has become a global issue. In the present study, we describe the toxins found in a previously unknown poisonous European mushroom Tricholoma terreum. Fifteen new triterpenoids terreolides A–F ( 1 – 6 ) and saponaceolides H–P ( 8 – 16 ) were isolated from the fruiting bodies of the toxic mushroom T. terreum. Terreolides A–C ( 1 – 3 ) possessed a unique 5/6/7 trioxaspiroketal system, whereas terreolides D–F ( 4 – 6 ) possessed an unprecedented carbon skeleton. Two abundant compounds in the mushroom, saponaceolide B ( 7 ) and saponaceolide M ( 13 ), displayed acute toxicity, with LD50 values of 88.3 and 63.7 mg kg?1 when administered orally in mice. Both compounds were found to increase serum creatine kinase levels in mice, indicating that T. terreum may be the cause of mushroom poisoning ultimately leading to rhabdomyolysis. 相似文献
999.
Experimental and Computational Studies of a Multi‐Electron Donor–Acceptor Ligand Containing the Thiazolo[5,4‐d]thiazole Core and its Incorporation into a Metal–Organic Framework 下载免费PDF全文
Felix J. Rizzuto Dr. Thomas B. Faust Dr. Bun Chan Carol Hua Dr. Deanna M. D'Alessandro Prof. Cameron J. Kepert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17597-17605
A ligand containing the thiazolo[5,4‐d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N′‐(thiazolo[5,4‐d]thiazole‐2,5‐diylbis(4,1‐phenylene))bis(N‐(pyridine‐4‐yl)pyridin‐4‐amine ( 1 ), was designed as a donor–acceptor system for incorporation into electronically active metal–organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis‐near‐infrared spectroelectrochemistry (UV/Vis‐NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge‐transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi‐electron donor–acceptor ligand into a new two‐dimensional MOF, [Zn(NO3)2( 1 )] ( 2 ), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1 . Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation. 相似文献
1000.
Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation 下载免费PDF全文
Li‐Hua Tian Jing‐Heng Meng Dr. Xiao‐Nan Wu Dr. Yan‐Xia Zhao Dr. Xun‐Lei Ding Prof. Dr. Sheng‐Gui He Dr. Tong‐Mei Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1167-1175
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation. 相似文献