全文获取类型
收费全文 | 1444篇 |
免费 | 207篇 |
国内免费 | 270篇 |
专业分类
化学 | 1142篇 |
晶体学 | 72篇 |
力学 | 7篇 |
综合类 | 6篇 |
物理学 | 324篇 |
无线电 | 370篇 |
出版年
2024年 | 7篇 |
2023年 | 21篇 |
2022年 | 34篇 |
2021年 | 54篇 |
2020年 | 63篇 |
2019年 | 47篇 |
2018年 | 53篇 |
2017年 | 43篇 |
2016年 | 72篇 |
2015年 | 50篇 |
2014年 | 77篇 |
2013年 | 145篇 |
2012年 | 91篇 |
2011年 | 87篇 |
2010年 | 67篇 |
2009年 | 114篇 |
2008年 | 111篇 |
2007年 | 92篇 |
2006年 | 85篇 |
2005年 | 77篇 |
2004年 | 83篇 |
2003年 | 73篇 |
2002年 | 69篇 |
2001年 | 39篇 |
2000年 | 36篇 |
1999年 | 30篇 |
1998年 | 33篇 |
1997年 | 32篇 |
1996年 | 33篇 |
1995年 | 20篇 |
1994年 | 31篇 |
1993年 | 15篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 5篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 3篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1921条查询结果,搜索用时 8 毫秒
61.
Dr. Mark Feyand Milan Köppen Prof. Dr. Gernot Friedrichs Prof. Dr. Norbert Stock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12537-12546
A systematic investigation of the systems Bi3+/carboxylic acid/HNO3 for the tri‐ and tetracarboxylic acids pyromellitic acid (H4Pyr), trimellitic acid (H3Tri) and trimesic acid (H3BTC) acid led to the discovery of five new bismuth carboxylates. Structural characterisation allowed the influence of the linker geometry and the Bi3+:linker molar ratio in the starting solution on the crystal structure to be determined. The crystallisation of three selected compounds was investigated by in situ energy‐dispersive X‐ray diffraction. Three new crystalline intermediates were observed within minutes, and two of them could be isolated by quenching of the reaction mixture. Their crystal structures were determined from laboratory and synchrotron X‐ray powder diffraction data and allowed a possible reaction pathway to be established. In depth characterisation of the luminescence properties of the three bismuth pyromellate compounds was carried out. Fluorescence and phosphorescence could be assigned to (mainly) ligand‐ and metal‐based transitions. The polymorphs of Bi(HPyr) exhibit different luminescence properties, although their structures are very similar. Surprisingly, doping of the three host structures with Eu3+ and Tb3+ ions was only successful for one of the polymorphs. 相似文献
62.
Georgina M. S. Alves Júlia M. C. S. Magalhães Helena M. V. M. Soares 《Electroanalysis》2013,25(5):1247-1255
A simple, fast, sensitive and greener voltammetric procedure for simultaneous analysis of nickel (Ni) and cobalt (Co) by square wave adsorptive cathodic stripping voltammetry (SW‐AdCSV) using a solid bismuth vibrating electrode is presented for the first time. The procedure enables to determine Ni together with Co, in ammonia buffer 0.1 M (pH 9.2) and in the presence of oxygen, and involves an adsorptive accumulation of metal‐dimethylglyoxime (Ni‐DMG and Co‐DMG) complexes on the electrode surface. For Ni and Co, the detection limits, obtained with 30 s of accumulation time, were 0.6 and 1.0 µg L?1, respectively. The method was free of metals (Cd2+, Cr3+, Cr6+, Cu2+, Fe3+ and Pb2+ up to 50 µg L?1, Al3+ and Mn2+ up to 500 µg L?1; Zn2+ up to 300 µg L?1) interferences up to the concentrations mentioned in brackets. The proposed method was validated for simultaneous determination of Ni and Co in a certified reference surface and river waters with good results. 相似文献
63.
螯合型二甘醇钛酸酯的合成及其催化性能研究 总被引:3,自引:0,他引:3
报导了两种新的螯合型二甘醇钛酸酯的合成方法,进行了IR和UV鉴定,并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系,探讨了催化剂结构与催化性能的关系。 相似文献
65.
Kamisaki H Nanjo T Tsukano C Takemoto Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):626-633
The formal synthesis of hemiterpene spirooxindole alkaloids elacomine (1) and isoelacomine (2) is described. Heck reaction of protected iodoanilines with 5,6-dihydro-2H-pyran-2-one or six-membered unsaturated lactams was investigated. The coupling product was readily converted to a carbamoyl chloride with an incorporated diene unit. The spiro(pyrrolidine-3,3'-oxindole) skeleton, which corresponds to the carbon skeleton of 1 and 2, was efficiently constructed from this intermediate by using a domino palladium-catalyzed Heck reaction and bismuth-catalyzed hydroamination. An isolated byproduct of the reaction could also be converted to the spirooxindole skeleton. 相似文献
66.
WANG Yong-Jinga b ZHANG Han-Huia b② HUANG Chang-Canga b YU Xiao-Honga SUN Qiao-Zhena SUN Rui-Qinga a 《结构化学》2004,(8)
1 INTRODUCTION As a rich remarkable class of inorganic cluster systems, polyoxometalates continue to be the focus of significant attention in the 21th century because of their various and alluring topologies as well as their unusual physicochemical prope… 相似文献
67.
Seto Y. Umemoto K. Arii T. Masuda Y. 《Journal of Thermal Analysis and Calorimetry》2004,76(1):165-177
New solid complex of nitrilotriacetic acid and bismuth trichloride was synthesized by a solid phase reaction of nitrilotriacetic
acid and bismuth trichloride at room temperature. The composition of the sample is BiCl3[N(CH2COOH)3]2.5. The crystal structure of the complex belongs to triclinic system with the lattice parameters: α=0.7849 nm, β=0.9821 nm,
χ=2.0021 nm, α=96.50°, β=98.76° and γ=90.49°. The far-infrared spectra show the bonding between the Bi ion and N atom of nitrilotriacetic
acid. The thermal analysis also demonstrates the complex formation between the bismuth ion and nitrilotriacetic acid. The
gaseous pyrolysis product and the final residue in the thermal decomposition process are determined to check the thermal decomposition
reaction.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
68.
Jennifer S. Forrester Jennifer S. Zobec Erich H. Kisi 《Journal of solid state chemistry》2004,177(10):3553-3559
The pressure-less sintering behavior of PbTiO3 powders synthesized by mechanical alloying TiO2 and PbO was investigated using dilatometry and Rietveld refinements of X-ray diffraction patterns. As-synthesized, the powders are nanocrystalline with a mean particle size of 20 nm. Pressure-less sintering in the range 500-1050°C gives single phase ceramics with densities of 85-90% and crystallite sizes in the range 80-400 nm. Cracking due to the paraelectric-ferroelectric phase transition was not observed in samples sintered below 700°C due to the small crystallite size whereas macroscopic cracks formed in samples sintered above 700°C. Rietveld analysis indicates the formation of Pb vacancies in samples sintered and held for 24 h at intermediate temperatures (600-1000°C) which gives some insight into the mechanism of Pb loss and second phase formation in this system. 相似文献
69.
通过可控水热法,制备出层状、花形和棒状钛酸铋(Bi4Ti3O12,BIT)纳米结构。通过X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)观测其结构和形貌特征。XRD图显示,所制备的样品为层状钙钛矿结构。FESEM结果表明,通过控制水热过程的反应参数可以得到不同形貌的纳米粉体。紫外-可见漫反射光谱(UV-Vis DRS)表明BIT样品的带隙能约为2.63~2.95 eV。利用可见光(λ>420 nm)照射下的甲基橙降解实验评价了BIT样品的光催化性能。结果表明,BIT的光催化活性比掺氮TiO2(N-TiO2)高得多。所制备的层状BIT纳米结构光催化效率最高,经可见光照射360 min,甲基橙溶液的降解率可达95.0%。同时还研究了结构和形貌对不同条件下制备的BIT样品光催化活性的影响。 相似文献
70.
固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物 总被引:2,自引:0,他引:2
合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。 相似文献