全文获取类型
收费全文 | 502篇 |
免费 | 52篇 |
国内免费 | 299篇 |
专业分类
化学 | 716篇 |
晶体学 | 21篇 |
力学 | 10篇 |
综合类 | 3篇 |
数学 | 2篇 |
物理学 | 101篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 13篇 |
2021年 | 18篇 |
2020年 | 16篇 |
2019年 | 15篇 |
2018年 | 15篇 |
2017年 | 22篇 |
2016年 | 17篇 |
2015年 | 24篇 |
2014年 | 22篇 |
2013年 | 38篇 |
2012年 | 33篇 |
2011年 | 51篇 |
2010年 | 34篇 |
2009年 | 32篇 |
2008年 | 40篇 |
2007年 | 52篇 |
2006年 | 70篇 |
2005年 | 54篇 |
2004年 | 48篇 |
2003年 | 63篇 |
2002年 | 29篇 |
2001年 | 34篇 |
2000年 | 30篇 |
1999年 | 30篇 |
1998年 | 10篇 |
1997年 | 13篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 3篇 |
排序方式: 共有853条查询结果,搜索用时 15 毫秒
61.
Yuhong Wang Yunting Gan Roger Whiting Guanzhong Lu 《Journal of solid state chemistry》2009,182(9):2530-2534
A new method has been developed for the preparation of sulfated titania (S-TiO2) supported on mesoporous silica. The use of direct exchange of metal containing precursors for the surfactants in the as-synthesized MCM-41 substrate produced a product with high sulfur content without serious blockage of the pore structure of MCM-41. The pore sizes and volumes of the resultant S-TiO2/MCM-41 composites were found to vary markedly with the loading of TiO2. The strong acidic character of the composites obtained was examined by using them as catalysts for the esterification of acetic acid and n-butanol. 相似文献
62.
Benaskar F Engels V Rebrov EV Patil NG Meuldijk J Thüne PC Magusin PC Mezari B Hessel V Hulshof LA Hensen EJ Wheatley AE Schouten JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(6):1800-1810
New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)). 相似文献
63.
韩晓 《中国无机分析化学》2015,5(2):34-38
采用电感耦合等离子体发射光谱法测定了铜渣精矿中砷、锑、铋、铅、锌、镁的量。其测定范围:ω(As):0.05%~0.45%,ω(Sb):0.07%~0.30%,ω(Bi):0.01%~0.20%,ω(Pb):1.00%~4.50%,ω(Zn):1.00%~4.50%,ω(Mg):0.10%~1.00%。经加标回收实验,各元素的加标回收率为92%~104%(n=3),相对标准偏差(RSD)小于5%(n=11)。方法准确快速可靠,适用于铜渣精矿中砷、锑、铋、铅、锌、镁量的同时测定. 相似文献
64.
高效TiO2基光催化材料的开发一直是催化领域的研究热点,主要的策略是如何有效地分离光生载流子.制备多晶相的TiO2材料可引入异质/相结结构使电子与空穴朝不同方向移动,从而避免电子与空穴复合;另外,在TiO2中掺杂其他金属或非金属也可以有效地降低电子与空穴的复合率,掺杂的元素作为电子捕获阱俘获光生电子,以实现电子空穴的有效分离.近些年,作为一种全新的掺杂剂,氧空穴可以有效改善TiO2的光催化活性,所制TiO2具有可见光的全光谱吸收能力,因此该类TiO2呈现出黑色.通过上述方法均可以制备出高活性TiO2基光催化材料,如果能够将这些方法耦合一起,则可能制备出活性更高的光催化剂.因此,本文将异相结结构和空穴掺杂耦合起来,用多孔钛酸盐衍生物在H2中高温焙烧制得一种全新的黑色TiO2(B)/锐钛矿双晶TiO2–x纳米纤维.不同于其他TiO2基光催化材料,该样品仅由Ti和O元素组成,通过Ti和O元素的组合,形成了双晶结构和空穴掺杂两种特殊的结构,借助场发射(FESEM)、拉曼光谱(Raman)、氮气物理吸脱附、X射线光电子能谱(XPS)、热重(TG)、紫外可见漫反射光谱(UV-Vis)和荧光光谱(PL)等表征分析了样品的结构及其光催化性能间构效关系. FESEM结果显示,黑色TiO2(B)/锐钛矿双晶TiO2–x为长1–5mm、宽0.2mm的纤维结构, Raman结果表明,锐钛矿相在特征波段(140 cm–1左右)和TiO2(B)的特征波段(220–260 cm–1)均发生蓝移,说明该两相中均存在氧空穴;该样表面未检测到Ti3+,因此氧空穴可能分散在TiO2(B)和锐钛矿相的体相中.根据黑色TiO2(B)/锐钛矿双晶TiO2–x和白色TiO2(B)/锐钛矿双晶TiO2的失重差,估算出前者的O/Ti原子比为1.97.光催化降解甲基橙实验结果显示,黑色TiO2(B)/锐钛矿双晶TiO2–x的光催化活性是白色双晶TiO2的4.2倍,锐钛矿TiO2的10.5倍,且连续反应10次后未出现失活现象,显示出了良好的光催化稳定性.前期,我们已经证明了白色TiO2(B)/锐钛矿双晶TiO2由于具有TiO2(B)和锐钛矿的异相结结构,致使其电子空穴有效地分离,从而表现出优异的光催化活性;本文的PL结果显示,由于氧空穴的引入,异相结与氧空穴两者共同作用,进一步促进了黑色TiO2(B)/锐钛矿双晶TiO2–x电子与空穴的有效分离,因此黑色TiO2(B)/锐钛矿双晶TiO2–x表现出高的光催化活性.由于其特殊的结构,黑色TiO2(B)/锐钛矿双晶TiO2–x纳米纤维将在环境与能源领域表现出良好的应用前景. 相似文献
65.
Sol-gel-derived titania films were analyzed by temperature programmed desorption (TPD) and X-ray diffraction (XRD) techniques.
The relationship between the TPD curves measured for two types of titania gel films and their crystal structures was investigated.
On the basis of the analyses, a preparation process for a titania sol solution containing anatase nanocrystals was designed
and developed. Using this process, a colloidal anatase titania sol solution was prepared by heating aqueous titanium hydroxide
containing HCl at 60°C for 2 h. The nanocrystal structure of the titania films obtained by coating the sol on glass substrates
was confirmed by TPD and XRD measurements. 相似文献
66.
67.
以磷铁废渣(Fe1.5P)和温室效应气体CO2为原料,以磷酸为补充磷源合成磷酸铁锂(LiFePO4)的前驱体Fe2P2O7,并研究了其合成过程对LiFePO4正极材料储能性能的影响。采用SEM观察了LiFePO4的表面形貌,采用XRD分析了LiFePO4和Fe2P2O7的晶体结构。进一步对该方法进行优化,发现Fe1.5P与磷酸混合物(nFe1.5P:nH3PO4=1:1)在800℃热处理6 h合成的Fe2P2O7对应的LiFePO4/C电化学性能最好,在0.1C,0.2C,0.5C和1C倍率下的容量分别可达130,126,117和108 mAh·g-1。该方法具有成本低廉,减少碳排放和环境友好等特点,为LiFePO4正极材料的生产提出了一种新的工艺。 相似文献
68.
水热沉淀法制备掺铁二氧化钛中空球及其光催化性能 总被引:1,自引:0,他引:1
以碳球为模板剂, 采用水热沉淀法制备了不同配比掺 Fe 的 TiO2 (Fe-TiO2) 中空球, 并运用 X 射线粉末衍射、扫描电子显微镜、元素分析能谱、红外光谱和热重等方法对其进行了表征. 结果表明, 中空球为锐钛矿相, 大小为 0.5~3.20 ?m, 壳层厚度为 30~60 nm, 比表面积为 150~300 m2/g. 随着 Fe 掺杂量的增加, 中空球在可见光区的吸收强度逐渐增加. 光催化降解实验表明, 掺 Fe 后, TiO2 中空球的可见光催化活性升高, 其中 0.5% Fe-TiO2 在 80 min 内降解亚甲基蓝超过 75%. 同时还讨论了光催化机制. 相似文献
69.
Carbon‐doped titania (C‐TiO2) nanoparticles were synthesized by the sol–gel method at different calcination temperatures (300–600°C) employing titanium tetraisopropoxide (TTIP) as the titanium source and polyoxyethylene sorbitan monooleate (Tween 80) as the carbon source. The physical properties of C‐TiO2 samples were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activities were checked through the photodegradation of phenolphthalein (PHP) under ultraviolet irradiation. The UV spectrum showed that the carbon doping extends the absorption range of TiO2 to the visible region. However, the photocatalytic activity is affected by the electron–hole recombination phenomenon, as revealed by the photoluminescence (PL) study. According to the PL spectra, carbon doping reduces the edge‐to‐edge electron–hole recombination. Nevertheless, the number of defect sites is greatly influenced by the calcination temperature of C‐TiO2. C‐TiO2 that was calcined at 400°C showed the highest photodegradation percentage of PHP, which was mainly attributed to the synergic effect of the low direct edge‐to‐edge electron–hole recombination, high content of defect sites, and retention of active electrons on the surface hydroxyl group. 相似文献
70.
TiO~2修饰的介孔分子筛MCM-41的合成、表征及光 催化性研究 总被引:12,自引:2,他引:12
首次以三种不同的含钛有机物为氧化钛的前驱体,合成了三种TiO~2呈单层分散状态的TiO~2修饰的介孔分子筛MCM-41,并以XRD,FT-IR,液氮温度下N~2吸附-脱附曲线,固体UV-vis漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究。TiO~2在介孔分子筛MCM-41孔道中分散,MCM-41仍能保持骨架结构,没有晶相TiO~2生成;TiO~2与MCM-41孔道表面的≡Si-OH以化学键连接,生成Si-O-Ti键;TiO~2在MCM-41内孔壁呈均匀单层分散状态;TiO~2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。并以苯酚降解反应为模型检验合成的具有光催化性的TiO~2修饰的MCM-41的光催化活性。 相似文献