全文获取类型
收费全文 | 1071篇 |
免费 | 169篇 |
国内免费 | 297篇 |
专业分类
化学 | 913篇 |
晶体学 | 37篇 |
力学 | 8篇 |
综合类 | 5篇 |
数学 | 3篇 |
物理学 | 571篇 |
出版年
2023年 | 16篇 |
2022年 | 27篇 |
2021年 | 40篇 |
2020年 | 48篇 |
2019年 | 60篇 |
2018年 | 45篇 |
2017年 | 74篇 |
2016年 | 70篇 |
2015年 | 64篇 |
2014年 | 80篇 |
2013年 | 121篇 |
2012年 | 117篇 |
2011年 | 96篇 |
2010年 | 74篇 |
2009年 | 101篇 |
2008年 | 85篇 |
2007年 | 68篇 |
2006年 | 67篇 |
2005年 | 66篇 |
2004年 | 42篇 |
2003年 | 31篇 |
2002年 | 33篇 |
2001年 | 16篇 |
2000年 | 18篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 7篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1987年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1537条查询结果,搜索用时 15 毫秒
31.
Yuanyuan Guo Limin Chen Ding Ma Daiqi Ye Bichun Huang 《Journal of Energy Chemistry》2013,22(4):591-598
Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H2 at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst. 相似文献
32.
Mehrnoush Tamimi Majid M. Heravi Masoud Mirzaei Vahideh Zadsirjan Nahid Lotfian Hossein Eshtiagh‐Hosseini 《应用有机金属化学》2019,33(9)
A facile, efficient and eco‐friendly catalytic protocol was developed for the synthesis of medicinally important pyran‐annulated heterocycles via multicomponent reaction (MCR). Cyclocondensation of differently substituted aromatic aldehydes, malononitrile/ethyl cyanoacetate and various β‐dicarbonyl compounds in the presence of Ag3[PMo12O40]?nH2O as heterogeneous catalyst, in EtOH–H2O, afforded diverse pyran‐fused chromene analogues. The merits observed for this approach were it being conducted via MCR, using commercially available or easily accessible starting materials in the presence of a green and easily separable heterogeneous and reusable catalyst, and affording high yields of desired products in very short reaction times with high purity in one‐pot fashion, thus providing a superior alternative approach for the synthesis of pyran‐annulated heterocycles. 相似文献
33.
A protocol for the direct cross coupling of trialkylsilyl‐alkynes bearing electron‐withdrawing groups and aryl halides using a Pd/Ag catalytic system is described. The procedure allows the straightforward synthesis of a variety of alkynylphosphonates and aryl propiolates derivatives in good yields. 相似文献
34.
AHMED Khan MUHAMMAD Asghar MOHAMMED Yaqoob MASOOD Ahmed Siddiqui SAMAR Ali 《高等学校化学研究》2021,37(3):629-638
Asensitive and selective method employing chemiluminescence(CL) coupled with flow injection(FI) is reported for nalbuphine hydrochloride(NAL) assay in pharmaceutical formulations. The enhancement effect of NAL on the CL reaction between tris(2,2'-bipyridyl)ruthenium(II) chloride-diperiodatocuprate(III) {Ru[(bpy)3]2+-Cu(III) complex} in acidic medium is used as analytical measurement. The optimal conditions of the CL reaction were sulfuric acid 1.0×10-3 mol/L, Ru[(bpy)3]2+ 7.5×10-5 mol/L, Cu(III)/Ag(III) complexes 4.0×10-4/5.0×10-4 mol/L, sample loop volume of 120 μL and flow rate of 2.5 mL/min. The sensitivities of the method in terms of detection(S/N=3) and quantification(S/N=10) limits are 5×10-4 and 0.001 ppm(1 ppm=1 mg/L), respectively. The linear response of the instrument in the form of CL intensity with respect to NAL concentration is over the range 0.001-15.0 ppm(R2=0.9999) with relative standard deviation from 0.8% to 3.2% and injection throughput of 120 injection/h. The applications of the method include the quantitative analysis of NAL in pharmaceutical injection samples. Variations and the average results of the proposed method are not signi-ficantly different from the results of a reported method by applying F- and paired student t-test. The most likely CL reaction mechanism is written in accordance with spectrophotometric and CL studies. 相似文献
35.
Ag decoration on TiO2 is favorable to absorption of visible light and wider absorption range. Ag nanoparticles playing the role of electron receivers on TiO2 surface enhance photodegradation. However, excess Ag nanoparticles caused reduced specific surface area of photocatalysts and increased probability of charge recombination, resulting in lower photocatalytic efficiency. In this study, the influence of various Ag decoration concentrations on photocatalytic activity was investigated. Surface treatment by nitric acid after Ag decoration was performed to avoid excessive Ag deposition. The extent of Ag elimination and its impacts on photocatalytic activity were also explored. An optimum Ag content in the photocatalyst was achieved and photocatalytic efficiency was obviously improved. It was found that the number of calcination times affected the crystallinity and stability of photocatalysts. Better photocatalytic efficiency could be obtained after twice calcinations. 相似文献
36.
Silver,iron, and nickel immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 MNPs catalyzed one‐pot five‐component reactions for the synthesis of tetrahydropyridines by tandem condensation of amines,aldehydes, and methyl acetoacetate 下载免费PDF全文
In this study, Ag, Ni2+, and Fe2+ immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 nanoparticles (γ‐Fe2O3@HAp‐Ag, γ‐Fe2O3@HAp‐Ni2+, and γ‐Fe2O3@HAp‐Fe2+) as a new and reusable Lewis acid magnetic nanocatalyst was successfully synthesized and reported for an atom economic, extremely facile, and environmentally benign procedure for the synthesis of highly functionalized tetrahydropyridines derivatives 4a‐t is described by one‐pot five‐component reaction of 2 equiv of aldehydes 1 , 2 equiv of amines 2 , and 1 equiv of methyl acetoacetate 3 in EtOH at room temperature in good to high yields and short reaction time. The presented methodology offers several advantages such as easy work‐up procedure, reusability of the magnetic nanocatalyst, operational simplicity, green synthesis avoiding toxic reagents and solvent, mild reaction conditions, and no tedious column chromatographic separation. 相似文献
37.
Preparation of high‐activity AgBr/Ag3PO4 photocatalyst based on hexadecyltrimethylammonium bromide and mechanism of photocatalytic enhancement 下载免费PDF全文
A high‐activity AgBr/Ag3PO4 heterojunction photocatalyst was synthesized based on hexadecyltrimethylammonium bromide. Its microspheres were characterized using X‐ray diffractometry, transmission electron microscopy and ultraviolet–visible diffuse reflectance spectroscopy. The new photocatalyst with high photocatalytic activity exceptionally outperforms pure Ag3PO4 and AgBr in methyl orange degradation. The enhancement of photocatalytic activity is attributed to the efficient separation of electron–hole pairs. In this photocatalytic reaction, h+ and ?O2? are the main reactive species that induce visible‐light‐driven degradation. 相似文献
38.
Rachida M’chaar Abdelaziz Sabbar Mouloud El Moudane Noureddine Ouerfelli 《哲学杂志》2020,100(11):1415-1438
ABSTRACT By applying the geometric models and the theoretical equation, the surface tension, the molar volume and the density were studied. The empirical calculations were carried out in temperature range 623?K?≤?T?≤?1123?K. Only few thermophysical properties were estimated for eight quinary alloys: Sn3.55Ag0.5Cu3Bi3Sb, Sn3.48Ag0.5Cu3Bi5Sb, Sn3.48 Ag0.5Cu5Bi3Sb, Sn3.40 Ag0.5Cu5Bi5Sb, Sn3.53Ag1Cu3Bi3Sb, Sn3.46Ag1Cu3Bi5Sb, Sn3.46Ag1Cu5Bi3Sb, Sn3.38Ag1Cu5Bi5Sb. The results show that surface tension and density have a linear appearance for all temperatures. We have also studied the influence of the composition and temperature in the studied alloys. The obtained theoretical results are compared with the experimental ones and with the conventional Pb–Sn welds. 相似文献
39.
Anshu Dandia Shyam L. Gupta Aayushi Indora Pratibha Saini Vijay Parewa Kuldeep S. Rathore 《Tetrahedron letters》2017,58(12):1170-1175
We have synthesized and characterized Ag NPs decked GO composite and studied its role as reusable catalyst for the ‘ON WATER’ chemoselective synthesis of pyranodipyrazolones via the reaction of different carbonyl compounds with 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one. This method illustrates significant selectivity for pyranodipyrazolones over arylmethylene bispyrazolols and arylmethylenepyrazolones. Synergistic effect of heterogenic nature of water with reactants and Ag NPs/GO had profuse outcome on reaction as indicated by high TOF (18.03 × 10?5 mol g?1 min?1). Furthermore, catalyst was recycled for 7-times without significant loss of activity. 相似文献
40.
The physicochemical properties of Ag nanoparticles have been determined by the nature of the used chemical reductors. The reported procedures describe the reduction of silver ions using N‐Phenylbenzohydroxamic acid (PBHA) and ascorbic acid individually. The influencing factors including cationic, anionic, zwitterionic and nonionic surfactants and pH have also been investigated in detail. 相似文献