全文获取类型
收费全文 | 420篇 |
免费 | 19篇 |
国内免费 | 72篇 |
专业分类
化学 | 460篇 |
晶体学 | 9篇 |
力学 | 3篇 |
综合类 | 2篇 |
物理学 | 37篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 15篇 |
2021年 | 9篇 |
2020年 | 9篇 |
2019年 | 5篇 |
2018年 | 11篇 |
2017年 | 7篇 |
2016年 | 13篇 |
2015年 | 12篇 |
2014年 | 14篇 |
2013年 | 41篇 |
2012年 | 14篇 |
2011年 | 15篇 |
2010年 | 16篇 |
2009年 | 11篇 |
2008年 | 22篇 |
2007年 | 36篇 |
2006年 | 26篇 |
2005年 | 21篇 |
2004年 | 24篇 |
2003年 | 26篇 |
2002年 | 15篇 |
2001年 | 22篇 |
2000年 | 20篇 |
1999年 | 20篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 10篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有511条查询结果,搜索用时 0 毫秒
51.
Thermal decomposition of tetra(piperidinium) octamolybdate tetrahydrate, [C5H10NH2]4[Mo8O26]·4H2O, was investigated in air by means of TG‐DTG/DTA, DSC, TG‐IR and SEM. TG‐DTG/DTA curves showed that the decomposition proceeded through three well‐defined steps with DTA peaks closely corresponding to mass loss obtained. Kinetics analysis of its dehydration step was performed under non‐isothermal conditions. The dehydration activation energy was calculated through Friedman and Flynn‐Wall‐Ozawa (FWO) methods, and the best‐fit dehydration kinetic model function was estimated through the multiple linear regression method. The activation energy for the dehydration step of [C5H10NH2]4[Mo8O26]·4H2O was 139.7 kJ/mol. The solid particles became smaller accompanied by the thermal decomposition of the title compound. 相似文献
52.
氧化铝的改性及其在合成气直接制二甲醚反应中的应用 总被引:7,自引:0,他引:7
采用浸渍法制备了经硼、磷和硫的含氧酸根阴离子改性的γ-Al2O3, 以其为甲醇脱水活性组分,与铜基甲醇合成活性组分CuO-ZnO-Al2O3组成双功能催化剂,并在连续流动加压固定床反应器上考察了催化剂对合成气直接制二甲醚反应的催化性能. 结果表明, SO2-4改性可以显著提高γ-Al2O3的甲醇脱水活性,从而提高产物中二甲醚的选择性和一氧化碳的转化率. 此外,还详细研究了SO2-4改性条件如SO2-4含量、焙烧温度及前驱物种类的影响. 结果表明,当SO2-4含量为10%, 焙烧温度为550 ℃时,二甲醚的选择性及一氧化碳的转化率最高; SO2-4前驱物的种类对其改性效果的影响很小. 相似文献
53.
Shuntaro Matsuta Noriaki Shima Hidenao Kakehashi Akari Ishikawa Ryutaro Asai Atsushi Nitta Misato Wada Shihoko Nakano Hiroe Kamata Yoshio Nishiyama Hirohisa Nagatani Hisanori Imura Munehiro Katagi 《Journal of mass spectrometry : JMS》2020,55(9)
Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs. 相似文献
54.
Reaction steps and mechanisms of the thermal dehydration of lithium metaborate dihydrate were investigated by means of thermoanalytical measurements, high temperature powder X-ray diffractometry, FT-IR spectroscopy, and microscopic observations. The first half of thermal dehydration was characterized by the melting of the sample producing viscous surface layer, the formation of bubbles on the particle surfaces, and the sudden mass-loss taking place by an opportunity of cracking and/or bursting of the bubble surface layer. The second half of the dehydration with a long-tailed mass-loss process in a wide temperature region was divided further into three distinguished reaction steps by the measurements of controlled rate thermal analysis. During the course of the thermal dehydration, four different poorly crystalline phases of intermediate hydrates were observed, in addition to an amorphous phase produced by an isothermal annealing. Just after completing the thermal dehydration, an exothermic DTA peak of the crystallization of β-LiBO2 was appeared at around 750 K. The phase transition from β-LiBO2 to α-LiBO2 was observed in the temperature range of 800-900 K, which subsequently melted by indicating a sharp endothermic DTA peak with the onset temperature at 1101.4 ± 0.6 K. 相似文献
55.
56.
A. Yamazaki Y. Inoue M. Koike T. Sakamoto R. Otsuka 《Journal of Thermal Analysis and Calorimetry》1993,40(1):85-97
Thomsonite with ideal chemical composition and with an ordered framework structure was synthesised hydrothermally from zeolite Na?A, which was ground to X-ray amorphous, with 0.05 mol dm?3 CaCl2 solution at 200°C. The dehydration behaviour of the prepared thomsonite was examined by TG-DTA. It was revealed that thomsonite lost most of zeolitic water below 450°C in three steps at about 180°, 340° and 390°C. The peak profiles of, the two higher-temperature endotherms were sharp and similar, and the weight loss at each step was approximately equal. 相似文献
57.
Iker AGIRREZABAL-TELLERIA Cristina GARCíA-SANCHO Pedro MAIRELES-TORRES Pedro Luis ARIAS 《催化学报》2013,34(7):1402-1406
The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism. Lewis acid sites promote the formation of xylulose, while Br nsted acid sites are required to further dehydrate the sugar to furfural. Amberlyst 70 in water/toluene at 175 ℃ showed lower activity but gave a higher furfural yield. Using N2 as the stripping agent considerably improved the furfural yield and product purity in the stripped stream. Catalyst stability was also studied. 相似文献
58.
A facile and efficient method for dehydration of aldoximes into nitriles using N-(p-toluenesulfonyl) imidazole (TsIm) is described. In this method, aldoximes were refluxed with TsIm in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) in dimethylformamide (DMF) to afford the corresponding nitriles in good yields. This methodology is highly efficient for various structurally diverse aldoximes including aromatic, heteroaromatic, and aliphatic oximes. A plausible mechanism for the conversion of aldoxime into nitriles using TsIm/DBU is explained. 相似文献
59.
The thermal dehydration of copper(II) acetate hydrate has been studied between 353 and 406 K, over a range of humidities.
The dehydration is controlled by nucleation-and-growth kinetics at low temperatures, with an activation energy of 154 kJ·mol−1, which changes to contracting-disc kinetics at higher temperatures with a lower activation energy of 76 kJ·mol−1. Frequency factors have also been derived; the value for the high temperature process is low (107s−1) and that for the low temperature step is high (1017s−1). Optical microscopy has been used to clarify the bulk kinetics; there is evidence for a reactive layer at the surface of
the decomposing solid.
In celebration of the 60th birthday of Dr Andrew K. Galwey 相似文献
60.
A. Coetzee M. E. Brown D. J. Eve C. A. Strydom 《Journal of Thermal Analysis and Calorimetry》1994,41(2-3):357-385
Both isothermal and programmed temperature experiments have been used to obtain kinetic parameters for the dehydrations and
the decompositions in nitrogen of the mixed metal oxalates: FeCu(ox)2·3H2O, CoCu(ox)2·3H2O and NiCu(ox)2·3.5H2O, [ox=C2O4]. Results are compared with those reported for the thermal decompositions of the individual metal oxalates, Cuox, Coox·2H2O, Niox·2H2O and Feox·2H2O. X-ray photoelectron spectroscopy (XPS) was also used to examinee the individual and the mixed oxalates.
Dehydrations of the mixed oxalates were mainly deceleratory processes with activation energies (80 to 90 kJ·mol−1), similar to those reported for the individual hydrated oxalates. Temperature ranges for dehydration were broadly similar
for all the hydrates studied here (130 to 180°C).
Decompositions of the mixed oxalates were all complex endothermic processes with no obvious resemblance to the exothermic
reaction of Cuox, or the reactions of physical mixtures of the corresponding individual oxalates.
The order of decreasing stability, as indicated by the temperature ranges giving comparable decomposition rates, was NiCu(ox)2>CoCu(ox)2>FeCu(ox)2, which also corresponds to the order of increasing covalency of the Cu−O bonds as shown by XPS.
In celebration of the 60th birthday of Dr. Andrew K. Galwey 相似文献