全文获取类型
收费全文 | 2176篇 |
免费 | 547篇 |
国内免费 | 190篇 |
专业分类
化学 | 2370篇 |
晶体学 | 42篇 |
力学 | 39篇 |
综合类 | 17篇 |
数学 | 27篇 |
物理学 | 418篇 |
出版年
2024年 | 8篇 |
2023年 | 37篇 |
2022年 | 77篇 |
2021年 | 90篇 |
2020年 | 130篇 |
2019年 | 108篇 |
2018年 | 90篇 |
2017年 | 85篇 |
2016年 | 191篇 |
2015年 | 155篇 |
2014年 | 132篇 |
2013年 | 249篇 |
2012年 | 173篇 |
2011年 | 107篇 |
2010年 | 124篇 |
2009年 | 116篇 |
2008年 | 106篇 |
2007年 | 113篇 |
2006年 | 103篇 |
2005年 | 114篇 |
2004年 | 74篇 |
2003年 | 98篇 |
2002年 | 86篇 |
2001年 | 36篇 |
2000年 | 23篇 |
1999年 | 31篇 |
1998年 | 17篇 |
1997年 | 41篇 |
1996年 | 28篇 |
1995年 | 40篇 |
1994年 | 10篇 |
1993年 | 17篇 |
1992年 | 25篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 13篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1970年 | 1篇 |
排序方式: 共有2913条查询结果,搜索用时 78 毫秒
161.
Cost-effective separation of oil and immiscible organic contaminants from water has become an urgent challenge to protect aquatic and human life from devastating effects. Therefore, it has become imperative to develop super-selective materials for efficiently separating oil from water. In this work, a superhydrophobic surface has been formed that consists of a silane@polystyrene-coated polypropylene fibrous network (silane@PS-PPF) for efficient separation of accidentally spilled oil from water. The superhydrophobic PPFs were designed by a simple, cost-effective two-step process that includes photochemically controlled polymerization of styrene and subsequent dip coating in octadecyltrichlorosilane solution. The hydrophobic surface (CA=129°±4°) of the PS coated PPF after treating with silane was turned into a superhydrophobic body (CA=161°±2°). The achieved silane@PS-PPF fibrous network selectively allowed the fast permeation of the oils and non-polar organic liquids by altogether rejecting water during operation. The separation efficiency for various oils from the contaminated water was 96 to 99%, with a high flux in the range of 7606±312 L m−2h−1 to 9870±151 L m−2h−1. Apart from being used as a filter, the silane@PS-PPF was also used as an oil absorber and has shown an absorption capacity in the range of 1185 to 1535% for various oils. We anticipate that the developed silane@PS-PPF, due to its facile synthetic route, cost-effectiveness, and high performance, can be effectively used in oily wastewater treatment and clean-up of large oil spills from water. 相似文献
162.
以D-木糖为炭源,月桂酸钠为模板剂,硼酸为掺杂剂,通过水热炭化方法制得硼掺杂分级多孔炭球(BPCS)。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N2吸附-脱附测试、X射线光电子能谱(XPS)、顺磁共振波谱(EPR)、傅里叶红外光谱(FT-IR)、拉曼光谱(Raman)、X射线粉末衍射(XRD)、热重(TG)分析对样品进行表征。结果表明:月桂酸钠作为介孔造孔剂的同时,通过与D-木糖间的氢键作用使有机-有机自组装过程自发进行并形成窄尺寸分布(2~5 μm)规整炭球;硼酸在水热中催化炭源脱水降解,并以BC3、BCO2和BC2O的形式掺杂在炭球上,掺硼后炭球与水表面接触角降低,润湿性提高。经CO2活化、月桂酸钠高温分解以及胶质炭球的堆积分别产生微孔(0.5~1.2 nm)、介孔(3.14~35.00 nm)和大孔(60~146 nm)并形成分级结构。当硼酸加入量为0.927 5 g时多孔炭球(BPCS-1)的电化学性能最佳,在6 mol·L-1 KOH三电极体系中电流密度为0.5 A·g-1时,比电容达287.12 F·g-1;两电极体系中电流密度为0.5 A·g-1时比电容达151.34 F·g-1,能量密度达5.3 Wh·kg-1;电流密度为5 A·g-1时进行1 000次充放电循环,电容保持率仍达96.43%。 相似文献
163.
基于第一性原理, 系统地研究了Ben (n=1~3)对B12团簇结构的调控. 结果表明: 团簇BeB12全局极小结构为Cs对称性准平面结构, 而Be2B12和Be3B12最稳定的结构均为笼状结构, 对称性分别为Cs和C2v. 随着Ben (n=1~3)原子数的增加, 团簇B12由准平面结构过渡到笼状结构, 且Be倾向内嵌在B12笼状结构表面的B7或B8单元环中, 通过离子和共价作用形成稳定Be&B7和Be&B8单元, 从而稳定笼状结构. 自然键轨道(NBO)分析表明, 团簇Cs BeB12, Cs Be2B12, C2v Be3B12内部存在电子转移情况, Be原子2s轨道上失去电子, Be—B键主要以离子作用为主, 同时也存在共价作用. 成键分析显示Cs Be2B12和C2v Be3B12的π键遵循球状芳香性2(n+1)2 (n=1)电子计数规则, 表明该团簇具有球状芳香性. 预测了三个结构的红外和拉曼光谱, 为以后的合成实验和数据表征提供了理论基础. 相似文献
164.
Nature of Bonding in Bowl‐Like B36 Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location 下载免费PDF全文
The bowl‐shaped C6v B36 cluster with a central hexagon hole is considered an ideal molecular model for low‐dimensional boron‐based nanosystems. Owing to the electron deficiency of boron, chemical bonding in the B36 cluster is intriguing, complicated, and has remained elusive despite a couple of papers in the literature. Herein, a bonding analysis is given through canonical molecular orbitals (CMOs) and adaptive natural density partitioning (AdNDP), further aided by natural bond orbital (NBO) analysis and orbital composition calculations. The concerted computational data establish the idea of concentric double π aromaticity for the B36 cluster, with inner 6π and outer 18π electron counting, which both conform to the (4n+2) Hückel rule. The updated bonding picture differs from existing knowledge of the system. A refined bonding model is also proposed for coronene, of which the B36 cluster is an inorganic analogue. It is further shown that concentric double π aromaticity in the B36 cluster is retained and spatially fixed, irrespective of the migration of the hexagonal hole; the latter process changes the system energetically. The hexagonal hole is a destabilizing factor for σ/π CMOs. The central hexagon hole affects substantially fewer CMOs, thus making the bowl‐shaped C6v B36 cluster the global minimum. 相似文献
165.
Zifeng Wang Zijie Tang Qi Xue Yan Huang Yang Huang Minshen Zhu Zengxia Pei Hongfei Li Hongbo Jiang Chenxi Fu Chunyi Zhi 《Chemical record (New York, N.Y.)》2016,16(3):1204-1215
Nanomaterials with layered structures, with their intriguing properties, are of great research interest nowadays. As one of the primary two‐dimensional nanomaterials, the hexagonal boron nitride nanosheet (BNNS, also called white graphene), which is an analogue of graphene, possesses various attractive properties, such as high intrinsic thermal conductivity, excellent chemical and thermal stability, and electrical insulation properties. After being discovered, it has been one of the most intensively studied two‐dimensional non‐carbon nanomaterials and has been applied in a wide range of applications. To support the exploration of applications of BNNSs, exfoliation, as one of the most promising approaches to realize large‐scale production of BNNSs, has been intensively investigated. In this review, methods to yield BNNSs by exfoliation will be summarized and compared with other potential fabrication methods of BNNSs. In addition, the future prospects of the exfoliation of h‐BN will also be discussed. 相似文献
166.
J. C. Raines J. P. Schmidt J. P. Burelbach H. K. Fauske 《Journal of Thermal Analysis and Calorimetry》2006,85(1):53-55
Hydrogen
peroxide is a very versatile oxidizing agent, and it is also environmentally
compatible considering that the products of its exothermic decomposition are
oxygen and water.When kept in a clean temperature-controlled environment,
the self-reaction (decomposition) rate is extremely low. However, it is well
known that even a small amount of contamination will dramatically increase
the reaction rate. This paper describes the use of the fast thermal activity
interpreter (FTAI) instrument to examine the chemical reactivity of commercially
available 50% hydrogen peroxide at two different temperatures (30 and 40°C)
both with and without contamination. The results show that at 30°C a small
amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide
by a factor of 50. When the temperature is increased to 40°C, the reaction
rate is further increased by almost a factor of four. The implication for
reactivity management is that at this contamination level most practical vessel
sizes would require emergency venting capability.
An evaluation
was then performed to determine the emergency venting requirement for the
safe transportation or storage of the contaminated hydrogen peroxide. It was
determined that for quantities of the material less than 5 gallons, conventional
breather vents would be sufficient to accommodate the gas evolved. However,
for larger quantities, a safety relief device would be needed. For example,
for a 400-gallon tote bin at 40°C the required minimum vent area is estimated
to be 4.3 in2, corresponding to a minimum vent
diameter of 2.3 inches. 相似文献
167.
Ti0.26Zr0.07V0.24Mn0.1Ni0.33Bx(x=0~0.10)系列合金均有V基固溶体相和C14型Laves相两相组成。添加B可提高Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金的放电容量,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.1合金电极在60 mA·g-1电流放电时的放电容量达到476.7 mAh·g-1。B的添加不同程度地降低了合金的高倍率放电性能,使合金电极表面上电化学反应的电荷转移电阻(R ct)显著增加,交换电流密度(I0)显著降低。添加B可显著改善Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金电极的高温放电性能,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.025合金电极在343 K高温下其放电容量达到525.6 mAh·g-1。 相似文献
168.
169.
Mehdi Zamani Hossein A. Dabbagh Hossein Farrokhpour 《International journal of quantum chemistry》2013,113(20):2319-2332
The capability of the B20O30 nanocapsule to store H2, N2, CO, CO2, NH3, CH4, and Cl2 molecules on the outer surface and inside of the cage was investigated using Monte Carlo simulations, long‐range and dispersion corrected density functional theory, and Møller–Plesset second‐order perturbation theory. Also, Monte Carlo simulations were employed to investigate the adsorption behavior of larger number of guest molecules inserted into and onto the larger B80O120 and B20O30@B80O120 cages. Absolute localized molecular orbitals energy decomposition analysis was used to describe the nature of intermolecular interactions in these endohedral and exohedral complexes. It is found that the hydrogen and ammonia gases are diffused to the inside of spherical B20O30 capsule, while other guest molecules prefer to interact with the outer surface of spherical and pyramidal capsules. For B80O120, up to 26 H2 and 11–14 N2, CO, CO2, NH3, and CH4 molecules are stored inside the capsule. The residual molecules are adsorbed on the outer surface of nanocapsule. © 2013 Wiley Periodicals, Inc. 相似文献
170.
Song WL Wang P Cao L Anderson A Meziani MJ Farr AJ Sun YP 《Angewandte Chemie (International ed. in English)》2012,51(26):6498-6501
Boron nitride nanosheets were dispersed in polymers to give composite films with excellent thermal transport performances approaching the record values found in polymer/graphene nanocomposites. Similarly high performance at lower BN loadings was achieved by aligning the nanosheets in poly(vinyl alcohol) matrix by simple mechanical stretching (see picture). 相似文献