全文获取类型
收费全文 | 624篇 |
免费 | 67篇 |
国内免费 | 165篇 |
专业分类
化学 | 761篇 |
晶体学 | 9篇 |
综合类 | 12篇 |
数学 | 1篇 |
物理学 | 73篇 |
出版年
2024年 | 2篇 |
2023年 | 12篇 |
2022年 | 19篇 |
2021年 | 19篇 |
2020年 | 50篇 |
2019年 | 32篇 |
2018年 | 22篇 |
2017年 | 27篇 |
2016年 | 29篇 |
2015年 | 29篇 |
2014年 | 27篇 |
2013年 | 61篇 |
2012年 | 54篇 |
2011年 | 47篇 |
2010年 | 34篇 |
2009年 | 36篇 |
2008年 | 34篇 |
2007年 | 36篇 |
2006年 | 29篇 |
2005年 | 36篇 |
2004年 | 26篇 |
2003年 | 27篇 |
2002年 | 19篇 |
2001年 | 17篇 |
2000年 | 18篇 |
1999年 | 20篇 |
1998年 | 12篇 |
1997年 | 12篇 |
1996年 | 8篇 |
1995年 | 8篇 |
1994年 | 13篇 |
1993年 | 5篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有856条查询结果,搜索用时 17 毫秒
31.
A facile,one-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide has been achieved under microwave-assisted conditions.The reactions can be smoothly completed within a total 10 min through a two-step procedure,including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide. 相似文献
32.
33.
Tomohiro Takano Chutiparn Lertvachirapaiboon Yasuo Ohdaira Akira Baba Keizo Kato 《Molecular Crystals and Liquid Crystals》2019,685(1):93-99
AbstractGas sensing by using the transmission surface plasmon resonance (T-SPR) technique was demonstrated. Polyacrylic acid (PAA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor A) responded to ammonia; however, it exhibited a strong humidity dependence. Polyvinyl alcohol (PVA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor B) as the sensing material was also prepared and it mainly responded to humidity. The T-SPR properties of Sensors A and B were observed simultaneously by a stacking arrangement that enabled us to obtain the responses by using a single spectrophotometer. The ammonia concentration under various humidity conditions could be accurately obtained by simultaneous measurement of Sensors A and B. 相似文献
34.
《Analytical letters》2012,45(4):389-404
Abstract A model is proposed which addresses the factors involved in the axial light attenuation of a coated waveguide (collector/sensor) whose polymer coating has been sensitized to ammonia. The experimental results appear to corroborate the model predictions of high sensitivity (ppb) and independence of sample flow on the collector/sensor. Concentration and relative humidity both determine the slopes of the transmission curves, the latter factor of which can be reduced to a second order effect by controlling the relative humidity in the sample holder. 相似文献
35.
《Analytical letters》2012,45(3):179-184
Abstract Inhibition of instantaneous current due to the reduction at the mercury electrode of Co(NH3)6 3+ ions by the addition of acridine hydrochloride are presented in terms of orientations of the adsorbed organic additive. Unusual catalytic effects at high cathodic potentials were observed and are discussed. 相似文献
36.
37.
A Cu(I) generated in situ from CuSO4·5H2O/sodium ascorbate catalyzed cross‐coupling reaction of aryl halides with aqueous ammonia for the synthesis of primary aromatic amines has been developed. Key to the success included the application of aqueous ammonia under a homogeneous condition. 相似文献
38.
合成了蜂窝状的分级多孔碳,并以多孔碳为载体通过浸渍-化学还原法制备碳载镍(Ni/C)作为催化氨硼烷水解制氢的催化剂。采用XRD、BET、SEM、Raman、TEM等手段对样品进行了表征并研究了Ni/C室温催化性能。结果显示,多孔碳比表面积高达737 m2·g-1,具有部分石墨化结构;负载的非晶态镍纳米颗粒平均粒径约为10 nm,均匀分布在碳基材。碳载镍对氨硼烷水解反应具有良好的催化活性,镍负载量为30wt%时催化性能最佳,298 K温度下放氢速率达到1 304.67 mL·min-1·g-1,活化能为29.1 kJ·mol-1,并且具备一定的催化稳定性,表明Ni/C可作为一种廉价高效的催化剂应用于催化氨硼烷水解制氢。 相似文献
39.
采用盐酸回流法和氨水沉淀法合成了氧化铝载体,并通过络合真空浸渍法制备了不同来源氧化铝负载的Pt-Sn-K/γ-Al2O3催化剂。利用N2物理吸附、CO脉冲吸附、H2程序升温还原、NH3程序升温脱附、热重等手段对Pt-Sn-K/γ-Al2O3催化剂进行了表征,以异丁烷脱氢为探针反应研究了氧化铝载体对该催化剂脱氢性能的影响。结果表明,与由盐酸回流法合成的载体制备的催化剂相比,采用氨水沉淀法合成的氧化铝载体制备的Pt-Sn-K/γ-Al2O3催化剂表面具有较小的Pt颗粒和较弱的酸性分布,其脱氢活性及异丁烯选择性更优。14 d的连续运行数据显示,由氨水沉淀合成的载体制备的催化剂,其抗积炭能力更强,反应后催化剂的积炭石墨化程度更低,因而具有更好的稳定性;在该催化剂上,异丁烷初始转化率为56.67%,14 d后仍能达到34.71%,异丁烯初始选择性为80%,7 d后维持在94%左右。 相似文献
40.
Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage 下载免费PDF全文
Sateesh Bandaru Niall J. English Andrew D. Phillips J.M.D. MacElroy 《Journal of computational chemistry》2014,35(12):891-903
Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H2 release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η6‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc. 相似文献