全文获取类型
收费全文 | 1011篇 |
免费 | 77篇 |
国内免费 | 910篇 |
专业分类
化学 | 1892篇 |
晶体学 | 27篇 |
力学 | 6篇 |
综合类 | 11篇 |
物理学 | 62篇 |
出版年
2024年 | 6篇 |
2023年 | 11篇 |
2022年 | 41篇 |
2021年 | 47篇 |
2020年 | 56篇 |
2019年 | 45篇 |
2018年 | 56篇 |
2017年 | 42篇 |
2016年 | 63篇 |
2015年 | 49篇 |
2014年 | 43篇 |
2013年 | 88篇 |
2012年 | 88篇 |
2011年 | 66篇 |
2010年 | 60篇 |
2009年 | 70篇 |
2008年 | 79篇 |
2007年 | 65篇 |
2006年 | 90篇 |
2005年 | 88篇 |
2004年 | 92篇 |
2003年 | 88篇 |
2002年 | 69篇 |
2001年 | 71篇 |
2000年 | 65篇 |
1999年 | 64篇 |
1998年 | 62篇 |
1997年 | 69篇 |
1996年 | 53篇 |
1995年 | 55篇 |
1994年 | 47篇 |
1993年 | 47篇 |
1992年 | 22篇 |
1991年 | 6篇 |
1990年 | 11篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1983年 | 2篇 |
1959年 | 1篇 |
排序方式: 共有1998条查询结果,搜索用时 15 毫秒
41.
O. de la Iglesia M. Pedernera R. Mallada Z. Lin J. Rocha J. Coronas J. Santamaría 《Journal of membrane science》2006,280(1-2):867-875
MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O2 selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material. 相似文献
42.
微波辐射下LaNaY沸石的水热交换反应 总被引:8,自引:0,他引:8
报道微波辐射应用于NaY沸石与La(NO_3)_3溶液的离子交换反应,结果表明微波辐射可提高La ̄+的交换度,缩短交换时间。 相似文献
43.
邻对苯二酚的合成方法 总被引:4,自引:1,他引:4
用自制的钛硅沸石TS-1为催化剂,对H2O2存在下苯酚直接羟基化合成邻、对苯二酚的反应条件,主要影响因素及机理进行了探讨,发现该民传统的合成方法相比,反应的选择性及转化率较高,工艺简单,成本低和污染少。 相似文献
44.
A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with NH4^ exchange by using ammonium salt and calcinations (procedure Ⅰ), or with NH4 exchange followed by treatment with acid (procedure Ⅱ). The coordination state of Si and A1 atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD,EDX,^29Si and ^27Al MAS NMR, Ag^ ion exchange and Ne adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and A1 atoms,the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure Ⅱ possesses high ion exchange capacity, open and perfect pore system, and high thermal stability. 相似文献
45.
The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson’s disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)5RuIIIORuIV(NH3)4ORuIII(NH3)5]6+ (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2×10−4 and 1.0×10−2 mol l−1 (r=0.9988) with a detection limit of 8.5×10−5 mol l−1. The variation coefficient for a 1.0×10−3 mol l−1 L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. 相似文献
46.
47.
Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents (OSDAs), which are chronically hazardous to humans and the environment. It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis. Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO2/Al2O3 ratios of 6.5–6.8. The prepared Y zeolite samples exhibited outstanding (hydro)thermal stability at ultrahigh temperature owing to the higher SiO2/Al2O3 ratio. The XRF, SEM, 29Si-NMR and 13Na+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite, while the feed molar fraction of Na+ is a crucial determinant for the framework SiO2/Al2O3 ratio and the crystal morphology. 相似文献
48.
SHEN Jian-Ping MA Jun SUN Tie JIANG Da-ZhenDepartment of Chemistry Jilin University Changchun Jilin ChinaMIN En-ZeResearch Institute of Petroleum Processing Beijing China 《中国化学》1995,13(2):124-130
The effects of alkali metals (Na+,K+) on the exchange degree of Hβ zeolite under different conditions and the conversion of α(or β)-methylnaphthalene over the alkalized zeolites were studied. The results showed that the H+ of Hβ zeolite is totally replaced by the Na+ of NaCl solution, while partially exchanged by the K+ of KC1 solution, there is an exchange equilibrium between the H+ and K+ for Hβ zeolite (Si/Al=17.23) and the value of equilibrium is 88.39. The exchange degree also increases with increasing the Si/Al of the samples. It was suggested that these resluts are attributed to the electrostatic field in the pore of Hβ zeolite and the nature of zeolite and the properties of alkali metal. The isomerization of α(or β)-methylnaphthalene is the main reaction over the samples and it is more favour on the proper acid-base sites of KHβ zeolite. 相似文献
49.
应用ONIOM计算方法研究了MCM-22分子筛超笼12元环上存在两个酸性位时的酸强度及其与骨架铝之间距离的关系,并研究了乙烯和苯分子吸附的规律.计算采用52T簇模型和B3LYP/6-31G**/MNDO方法.结果表明,存在两个酸性位且两个骨架铝之间间隔1个骨架硅时,酸强度比孤立的酸性位明显降低;当间隔的硅原子数增加时,酸强度呈上升趋势,间隔3个以上骨架硅时,其酸强度与孤立的酸性位几乎没有差别.对于乙烯的吸附,当两个骨架铝之间间隔1~4个骨架硅时,其吸附能几乎没有差别(31~35 kJ/mol);对于苯的吸附,当两个骨架铝之间间隔1个骨架硅时,其吸附能有所提高,因为两个桥羟基同时对苯分子产生氢键吸附作用.当两个骨架铝之间的距离增大时,苯的吸附能几乎相同(21~29 kJ/mol).若两个乙烯分子或苯分子同时吸附在双酸性位上,其吸附能与单个分子在孤立酸性位吸附时几乎没有差别.应用自然键轨道计算分析了吸附配合物的电子结构,进一步探明了乙烯和苯在分子筛酸性位上吸附的本质. 相似文献
50.
应用分子力学和量子力学联合的ONIOM2(B3LYP/6-31G(d,p):UFF)计算方法研究了H-ZSM-5分子筛上乙烯二聚反应的机理. 用40T簇模型模拟ZSM-5分子筛位于孔道交叉点的酸性位,对乙烯二聚过程的分步反应和协同反应两种机理进行了考察. 对于分步反应机理,乙烯分子首先通过π-氢键作用在酸性位形成稳定的吸附络合物,再进一步发生质子化并生成乙醇盐中间体,随后乙醇盐与第二个乙烯分子发生碳-碳键结合形成丁醇盐产物. 第一步质子化和第二步碳链聚合的活化能分别为152.88和119.45 kJ/mol, 表明乙烯质子化反应为速控步骤. 对于协同反应机理,乙烯质子化、碳-碳键和碳-氧键生成同时进行,生成丁醇盐,反应的活化能为162.30 kJ/mol, 略高于分步反应机理中的速控步骤. 计算结果表明这两种反应机理之间存在相互竞争. 相似文献