全文获取类型
收费全文 | 2707篇 |
免费 | 333篇 |
国内免费 | 585篇 |
专业分类
化学 | 2194篇 |
晶体学 | 28篇 |
力学 | 62篇 |
综合类 | 16篇 |
数学 | 2篇 |
物理学 | 275篇 |
综合类 | 1048篇 |
出版年
2024年 | 3篇 |
2023年 | 24篇 |
2022年 | 55篇 |
2021年 | 67篇 |
2020年 | 83篇 |
2019年 | 81篇 |
2018年 | 53篇 |
2017年 | 79篇 |
2016年 | 130篇 |
2015年 | 129篇 |
2014年 | 152篇 |
2013年 | 272篇 |
2012年 | 220篇 |
2011年 | 180篇 |
2010年 | 154篇 |
2009年 | 129篇 |
2008年 | 154篇 |
2007年 | 166篇 |
2006年 | 187篇 |
2005年 | 173篇 |
2004年 | 159篇 |
2003年 | 171篇 |
2002年 | 110篇 |
2001年 | 90篇 |
2000年 | 80篇 |
1999年 | 74篇 |
1998年 | 49篇 |
1997年 | 62篇 |
1996年 | 52篇 |
1995年 | 60篇 |
1994年 | 47篇 |
1993年 | 30篇 |
1992年 | 29篇 |
1991年 | 24篇 |
1990年 | 27篇 |
1989年 | 18篇 |
1988年 | 16篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
1955年 | 3篇 |
排序方式: 共有3625条查询结果,搜索用时 328 毫秒
191.
Synthesis and Isolation of the Titanium–Scandium Endohedral Fullerenes—Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80 and Sc2TiC2@Ih‐C80: Metal Size Tuning of the TiIV/TiIII Redox Potentials 下载免费PDF全文
Katrin Junghans Dr. Kamran B. Ghiassi Nataliya A. Samoylova Qingming Deng Marco Rosenkranz Prof. Marilyn M. Olmstead Prof. Alan L. Balch Dr. Alexey A. Popov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13098-13107
The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed‐metal Sc–Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4C2@C80 (the most abundant EMF from this synthesis), Sc3C2@C80, isomers of Sc2C2@C82, and the family Sc2C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3CH@C80. The Sc–Ti/CH4 system produces the mixed‐metal Sc2TiC@C2 n (2 n=68, 78, 80) and Sc2TiC2@C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition‐metal‐containing endohedral fullerenes, Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80, and Sc2TiC2@Ih‐C80, were characterized by NMR spectroscopy. The structure of Sc2TiC@Ih‐C80 was also determined by single‐crystal X‐ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2TiC‐ and Sc2TiC2‐containing clusterfullerenes have Ti‐localized LUMOs. Encapsulation of the redox‐active Ti ion inside the fullerene cage enables analysis of the cluster–cage strain in the endohedral fullerenes through electrochemical measurements. 相似文献
192.
系统地研究了TS-1分子筛催化双氧水氧化环己烷的反应。制备了三种TS-1分子筛,它们具有窄的粒径分布,在60℃表现出高的活性和选择性。考察了溶剂、催化剂、反应温度、反应时间、TS-1中Ti含量及H2O7用量对氧化反应的影响。对具有完好晶型的TS-1分子筛役有必要进行预处理。最佳反应温度为80~110℃,丙酮为最佳溶剂。环己酮的选择性与TS-1粒子大小有关,而H2O2选择性与TS-1用量无关。实验结果显示.溶剂在反应中间体的形成中起重要作用,Ti与丙酮配体的过氧配合物具有活化环己烷的活性。关键词 TS-1 环己烷 催化氧化 H2O2 相似文献
193.
G. R. Kosmambetova V. I. Gritsenko P. E. Strizhak A. M. Korduban 《Theoretical and Experimental Chemistry》2006,42(2):133-138
We have studied the catalytic properties of copper-cerium oxide catalysts, supported on zirconium, aluminum, titanium, and
manganese oxides, in the reaction of selective oxidation of CO in hydrogen-rich mixtures. We have shown that the high activity
and selectivity of catalysts supported on zirconium and aluminum oxides is connected with the presence of (in addition to
divalent copper) higher amounts of copper in the (+1) oxidation state in the catalysts.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 119–124, March–April, 2006. 相似文献
194.
In the literature it was found that titanium oxide clusters of a few metal atoms encapsulated inside the micropores of zeolite Y exhibit large blue shifts in the Ti-O ligand-to-metal charge-transfer band as compared to non-encapsulated bulk titanium dioxide particles. This blue shift of the Ti-O absorption band is believed to have a negative effect on the photocatalytic activity of zeolite-encapsulated TiO2. We report here on circumventing this problem and increasing visible-light absorption by means of a red shift of the absorption band caused by addition of some organic molecular modifiers containing acidic OH groups that can strongly bind with titanol groups TiOH. In the studied series of zeolite-encapsulated TiO2 samples, the red shift of the optical spectrum follows the order: catechol > 4-aminobenzoic acid > benzoic acid. Also N-doping of zeolite-encapsulated TiO2 clusters by thermal treatment with urea leads to a red shift of the TiO2 absorption band that depends on the annealing and hydration conditions. By comparison to the degradation of phenol in aqueous solution, we have demonstrated that these changes in the absorption spectrum on addition of the organic modifier are also reflected in the photocatalytic activity of the samples; a greater increase in photocatalytic activity (about 30%) was observed for the additive catechol. 相似文献
195.
通过有机物分解碳化处理TiO2 纳米管制得了TiO2C, 并以其为载体制备了Pd/TiO2C电催化剂,考察了该催化剂对碱性介质中乙醇电催化氧化的活性. 结果表明,碳化导电处理的TiO2C纳米管载体能有效改善催化剂中贵金属的分散度和电极结构,从而提高催化剂的电催化活性. 对催化剂活性组分的优化实验表明, Pd/TiO2C质量比为1/1时催化剂的活性最高. 在1 mol/L KOH溶液中Pd载量均为0.3 mg/cm2的条件下, Pd/TiO2C催化剂对乙醇氧化的催化活性是Pd/C催化剂的3.8倍. 相似文献
196.
采用表面涂覆硅烷偶联剂KH550、两步光接枝、阳极氧化等方法,在钛表面成功制备出一种pH型敏感膜覆盖的载银二氧化钛(TiO2)纳米管阵列。利用扫描电镜(SEM)、透射电镜(TEM)、能谱分析(EDS)、原子吸收光谱(AAS)对该pH敏感膜覆盖的载银TiO2纳米管阵列理化性能进行了表征,采用抑菌环实验定性考察了样品的抗菌特性,并计算其抑菌率。结果表明,含银离子溶液在毛细管力作用下大量进入TiO2纳米管中,并在pH型敏感膜的调控下,使银离子在不同pH环境下具备不同的释放行为,从而达到良好的控释效果;载银TiO2纳米管的抑菌率与银离子负载量成正比,且抗菌性能持久。 相似文献
197.
Hierarchical graphene oxide (GO)‐TiO2 composite microspheres with different GO/TiO2 mass ratios were successfully prepared by mixing GO and TiO2 microspheres under ultrasonic conditions. Ultrasonication helped the GO and TiO2 microsphere to uniformly mix on the microscale. The results showed that the GO‐TiO2 composites that were prepared by ultrasonic mixing exhibited significantly higher hydrogen‐evolution rates than those that were synthesized by simple mechanical grinding, owing to synergetic effects, including enhanced light absorption and scattering, as well as improved interfacial charge transfer because of the excellent contact between the GO sheets and TiO2 microspheres. In addition, GO‐TiO2‐3 (3 wt. % GO) showed the highest hydrogen‐generation rate (305.6 μmol h?), which was about 13 and 3.3‐times higher than those of TiO2 microsphere and GO‐P25 (with 3 wt. % GO), respectively. Finally, a tentative mechanism for hydrogen production is proposed and supported by photoluminescence and transient photocurrent measurements. This work highlights the potential applications of GO‐TiO2 composite microspheres in the field of clean‐energy production. 相似文献
198.
本文首次通过pH值控制沉淀法制备前驱物丁二酸钛肼复盐, 并进一步热分解制备大比表面积钛黑颜料-黑色钛氧化物。通过比表面积(BET)、电子能谱(EDS)、X射线光电子能谱分析(XPS)、X射线粉末衍射(XRD)、场发射扫描电子显微镜(HRSEM)、物理吸附仪、激光粒度仪和Color i5型台式分光测色仪对黑色钛氧化物进行了表征, 确定了黑色钛氧化物的组成为2TiO2·Ti2O3, 其表面积为53.854 4 m2·g-1。并考察了酸源、水合肼用量、酸钛比、反应时间、pH、NaOH浓度和煅烧温度等各种反应参数对黑色钛氧化物的颗粒尺寸、分布均匀性和黑色度的影响。用元素分析仪和等离子体光谱仪测定了前驱物组成, 确定其组成为[Ti(C4H4O4)2]0.85·2Ti2O3·6N2H4·3H2O, 并探讨了黑色钛氧化物形成机理, 为新型混合价材料黑色钛氧化物的制备提供重要参考依据。 相似文献
199.
电感耦合等离子体发射光谱法测定钒钛铁矿中二氧化钛 总被引:1,自引:0,他引:1
传统的分光光度法或滴定法测定矿石中二氧化钛,操作繁琐,周期长,且分析效率低,不适合大批量样品的快速分析. 采用氢氟酸、盐酸、硝酸、高氯酸混合酸和1 mL 1+1硫酸溶解试样,用10%的盐酸进行提取,再以电感耦合等离子发射光谱直接测定二氧化钛含量. 试验结果表明,在波长336.1 nm处,钒钛磁铁矿国家标准物质的测定值与标准值基本一致. 方法确定在波长336.1 nm处进行实验,二氧化钛的检出限为30 μg/g,精密度(RSD,n=12)小于0.8%. 方法操作简单,数据准确可靠,适合批量钒钛 相似文献
200.
Hiroshi Onishi 《Catalysis Surveys from Japan》2002,6(1-2):1-8
The present account describes first time examples of scanning tunneling microscope (STM) visualization of reaction intermediates on a metal oxide surface. The topographic response of reactant-adsorbed TiO2(110) surfaces to a temperature increment or to a pressure increment was monitored as a sequence of STM images. Acetates thermally decomposing to ketene were resolved in a temperature-jump STM observation. The kinetics of the acetate consumption was determined on the number of acetates resolved in the microscope images and agreed with the macroscopic rate law of ketene production. A pressure-jump study revealed how a chemisorbed carboxylate (RCOO-) is exchanged by another carboxylate (R'COO-) supplied from the ambient vapor phase. An impinging R'COOH was immobilized on the top of a RCOO- and then squeezed itself into the monolayer of the RCOO-. One of the carboxylates in the squeezed state returned to the vapor phase via the immobilized state. 相似文献