全文获取类型
收费全文 | 4982篇 |
免费 | 631篇 |
国内免费 | 1541篇 |
专业分类
化学 | 5955篇 |
晶体学 | 118篇 |
力学 | 71篇 |
综合类 | 27篇 |
数学 | 6篇 |
物理学 | 977篇 |
出版年
2024年 | 2篇 |
2023年 | 80篇 |
2022年 | 106篇 |
2021年 | 203篇 |
2020年 | 297篇 |
2019年 | 225篇 |
2018年 | 224篇 |
2017年 | 218篇 |
2016年 | 311篇 |
2015年 | 298篇 |
2014年 | 297篇 |
2013年 | 527篇 |
2012年 | 432篇 |
2011年 | 379篇 |
2010年 | 315篇 |
2009年 | 339篇 |
2008年 | 338篇 |
2007年 | 356篇 |
2006年 | 328篇 |
2005年 | 327篇 |
2004年 | 268篇 |
2003年 | 246篇 |
2002年 | 185篇 |
2001年 | 116篇 |
2000年 | 98篇 |
1999年 | 114篇 |
1998年 | 82篇 |
1997年 | 61篇 |
1996年 | 49篇 |
1995年 | 66篇 |
1994年 | 46篇 |
1993年 | 36篇 |
1992年 | 42篇 |
1991年 | 29篇 |
1990年 | 20篇 |
1989年 | 12篇 |
1988年 | 14篇 |
1987年 | 10篇 |
1986年 | 14篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有7154条查询结果,搜索用时 15 毫秒
51.
D. N. Dybtsev M. P. Yutkin E. V. Peresypkina A. V. Virovets Y. Hasegawa H. Nishihara V. P. Fedin 《Russian Chemical Bulletin》2007,56(9):1782-1786
The reaction of Co(NO3)2·6H2O with 1,3,5-benzenetricarboxylic acid (H3btc, trimesic acid) in DMF at 100 °C afforded the coordination polymer [Co3(dmf)6(btc)(Hbtc)(H2btc)]··9H2O (1) (dmf is N,N′-dimethylformamide, DMF). According to the X-ray diffraction study, the metal-organic coordination polymer is composed of
planar honeycomb (6,3) networks, in which the organic benzenetricarboxylate anions and the inorganic Co2+ cations play a role of three-connected nodes. Disordered water molecules are intercalated between the layers. A study of
the magnetic properties showed the presence of a weak antiferromagnetic coupling between the Co2+ ions (S = 3/2).
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1723, September, 2007. 相似文献
52.
铜基催化剂的结构、物性及其对混合碳四选择加氢反应的催化性能 总被引:2,自引:0,他引:2
用XRD,XPS,SEM和H2-TPR等手段研究了铜基负载型催化剂的结\r\n构和物性及其对混合碳四加氢脱炔的催化性能.结果表明,在负载铜催\r\n化剂中加入一定量的Co可提高催化剂的加氢脱炔活性,而Co含量较少时\r\n加入少量的Ce也能提高催化剂的活性和选择性.Cu和Co之间存在着相互\r\n协同作用,使得活性组分在催化剂表面偏析,CuO在催化剂表面呈非晶\r\n相分散状态,催化剂颗粒粒径变小,催化剂更容易被还原,从而改善了\r\n催化剂的催化性能. 相似文献
53.
Vapor pressure,speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317°C 总被引:2,自引:0,他引:2
Oleh Weres 《Journal of solution chemistry》1995,24(5):409-438
The system H2O-B2O3-Na2O has been studied experimentally at 277 and 317°C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317°C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B= 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios. 相似文献
54.
WU Lian-Bin HU Zi-Qiang LAI Guo-Qiao② 《结构化学》2006,25(5)
1 INTRODUCTION The chemical behavior of metal complexes with Schiff base ligand has attracted much attention be- cause of their catalytic activity in some industrial[1, 2] and biochemical processes[3~5]. As some metal com- plexes have shown the catalytic activity in some polymerization reactions[2, 6], we are recently inte- rested in polymerizartion of organo-silicon com- pounds catalyzed by Schiff base complexes of tran- sition metals. A series of Schiff base complexes have been prepare… 相似文献
55.
采用柠檬酸络合-有机模板剂分解法制备了(La+Co)/(La+Co+Zr)原子比为0.5的La-Co-Zr-O催化剂,并与传统的共沉淀法制备的La-Co-Zr-O催化剂进行比较. N2物理吸附结果表明,采用模板剂法制备的催化剂样品具有较大的比表面积(96.6~117.6 m2/g)和十分均匀的孔径(3.5~4.3 nm); X射线衍射、X射线光电子能谱和X射线吸收精细结构表征结果一致表明,催化剂中活性组分主要为高分散的Co3O4微晶(粒径为23~33 nm), 模板剂法制备的催化剂中所有组分的分散性均优于共沉淀法制备的催化剂. 程序升温还原实验结果表明,采用聚乙二醇辛基苯基醚与十六烷基三甲基溴化铵为混合模板剂制备的催化剂中Co3O4更容易被还原. Co-O 键的活动度与催化剂催化氧化反应的活性密切相关. 相似文献
56.
主体分子六次甲基四胺与客体分子二氯化六水合钴(Ⅱ)和结晶水包结物的研究 总被引:1,自引:0,他引:1
用X射线单晶衍射分析法研究主体分子六次甲基四胺与客体分子二氯化六水合钴(Ⅱ)和结晶水包结物晶体结构。其分子式为[(CH2)6N4]2·[(Co(H2O)6]Cl2·4H2O,Mr=59038。晶体属三斜晶系,空间群为P1。晶胞参数:3341个衍射点,其中3148个独立衍射点,2754(F0>6σ(F0))为可观察反射点。在晶胞内,客体分子和结晶水形成氢键:,客体分子与主体分子形成氢键晶胞之间形成氢键晶胞之内和晶胞之间主体分子和客体分子以及结晶水以氢键和范德华力相联系形成稳定的晶格。 相似文献
57.
58.
One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported. 相似文献
59.
meso-四(邻烷氧基苯基)卟啉合钴的合成、表征和性能研究 总被引:3,自引:0,他引:3
合成了meso-四(邻烷氧基苯基)卟啉合钴配合物10个,其中未见文献报道的新化合物8个,研究了其合成、分离、纯化方法,首次得到了该系列化合物的晶体或固体。用1H NMR、MS、IR、UV、元素分析等表征确证了其结构,报道和解析了该类卟啉钴配合物的1H NMR特殊波谱现象。用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性。研究了烷氧基链长、金属离子和分子空间结构对卟啉液晶性能的影响,烷氧基链长的增加、金属配合物的形成有利于液晶性能的改善。 相似文献
60.
The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1a) with 3-methylbutanal (2) in heterogeneous MOH (solid)-benzene systems in the presence of 5–10 mol.% of benzyltriethylammonium chloride (BTEAC) gives the reaction product (3) with a higher, for M=K, or lower, for M=Li, ratio of 2E,4E and 2Z,4E-stereoisomers than that observed in the absence of BTEAC. Tetrabutylammonium bromide (TBAB) as a catalyst of the reaction1a + 2 3 in the system KOH (solid)-wet benzene leads to a higher [2E,4E-3][2Z,4E-3] ratio than BTEAC; this ratio grows from 4456 without TBAB to 8020 at 100 mol.% of TBAB. In the latter case the stereochemical outcome of the reaction is similar to that obtained when tetrabutylammonium hydroxide in dry benzene is used as the deprotonating agent. The corresponding diisopropyl phosphonate (1b) and 3,7-dimethyloctanal (4a) interact in the system KOH (solid)-wet benzene-TBAB to give hydroprene (5) containing 88 % of the 2E,4E-isomer (5a) while in the case of 1 equiv. of [(n-Bu4)N]OH in dry benzene the content of5a is 92 %. Diisopropyl 3-isopropoxycarbonyl-2-methyl-2-propenylphosphonate (1c) and 7-methoxy-3,7-dimethyloctanal (4b) under either of these conditions afford methoprene (6) containing 93 % of the 2E,4E-isomer.Part 6, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1094–1098, June, 1993. 相似文献