全文获取类型
收费全文 | 12515篇 |
免费 | 2255篇 |
国内免费 | 2344篇 |
专业分类
化学 | 10176篇 |
晶体学 | 248篇 |
力学 | 677篇 |
综合类 | 186篇 |
数学 | 1454篇 |
物理学 | 4373篇 |
出版年
2024年 | 49篇 |
2023年 | 286篇 |
2022年 | 506篇 |
2021年 | 477篇 |
2020年 | 568篇 |
2019年 | 632篇 |
2018年 | 482篇 |
2017年 | 442篇 |
2016年 | 603篇 |
2015年 | 679篇 |
2014年 | 716篇 |
2013年 | 927篇 |
2012年 | 1078篇 |
2011年 | 1005篇 |
2010年 | 819篇 |
2009年 | 736篇 |
2008年 | 887篇 |
2007年 | 784篇 |
2006年 | 701篇 |
2005年 | 648篇 |
2004年 | 509篇 |
2003年 | 536篇 |
2002年 | 672篇 |
2001年 | 604篇 |
2000年 | 423篇 |
1999年 | 297篇 |
1998年 | 188篇 |
1997年 | 128篇 |
1996年 | 142篇 |
1995年 | 99篇 |
1994年 | 79篇 |
1993年 | 62篇 |
1992年 | 61篇 |
1991年 | 61篇 |
1990年 | 49篇 |
1989年 | 28篇 |
1988年 | 29篇 |
1987年 | 18篇 |
1986年 | 18篇 |
1985年 | 18篇 |
1984年 | 17篇 |
1983年 | 19篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1973年 | 3篇 |
1968年 | 1篇 |
1957年 | 2篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
用电化学沉积法将三聚氰胺修饰在玻碳电极上,应用此三聚氰胺修饰玻碳电极测定银时,试液在pH 4.6的乙酸-乙酸钠缓冲溶液中,在—0.45V处还原60 s,然后在0~+0.6V范围内扫描,使银离子从修饰电极上溶出,实现了水样中银离子的溶出伏安法测定,在+0.27V处可得银离子的氧化峰电位,银的浓度在6.0×10~(-9)~5.0×10~(-7)mol·L~(-1)范围内与其峰电流呈线性关系,检出限(3S/N)为1.0×10~(-9)mol·L~(-1)。方法用于实际水样中痕量银的测定,加标回收率在90.0%~96.0%之间。 相似文献
992.
Fang J Kelarakis A Lin YW Kang CY Yang MH Cheng CL Wang Y Giannelis EP Tsai LD 《Physical chemistry chemical physics : PCCP》2011,13(32):14457-14461
We report a simple, scalable approach to improve the interfacial characteristics and, thereby, the performance of commonly used polyolefin based battery separators. The nanoparticle-coated separators are synthesized by first plasma treating the membrane in oxygen to create surface anchoring groups followed by immersion into a dispersion of positively charged SiO(2) nanoparticles. The process leads to nanoparticles electrostatically adsorbed not only onto the exterior of the surface but also inside the pores of the membrane. The thickness and depth of the coatings can be fine-tuned by controlling the ζ-potential of the nanoparticles. The membranes show improved wetting to common battery electrolytes such as propylene carbonate. Cells based on the nanoparticle-coated membranes are operable even in a simple mixture of EC/PC. In contrast, an identical cell based on the pristine, untreated membrane fails to be charged even after addition of a surfactant to improve electrolyte wetting. When evaluated in a Li-ion cell using an EC/PC/DEC/VC electrolyte mixture, the nanoparticle-coated separator retains 92% of its charge capacity after 100 cycles compared to 80 and 77% for the plasma only treated and pristine membrane, respectively. 相似文献
993.
以氯甲基杂环聚醚酮(CMPPEK)为原料,加入三乙胺进行铵化,并分别加入二乙烯三胺(DETA)和二乙胺(DEA),生成的仲胺基(或叔胺基)与邻近分子链氯甲基团进行自交联.经过制膜和离子交换反应,制备了DETA自交联杂萘联苯聚芳醚阴离子交换膜(DETA-QPPEK-OH)和DEA自交联杂萘联苯聚芳醚阴离子交换膜(DEA-QPPEK-OH).采用傅里叶变换红外(FTIR)光谱对制备自交联膜的化学结构进行表征.研究了DETA-QPPEK-OH和DEA-QPPEK-OH膜的理化性质,结果表明前者具有较低吸水率和更低溶胀度.通过研究DETAQPPEK-OH和DEA-QPPEK-OH膜的离子传导率随温度的变化规律,结果表明在80°C时其离子传导率分别达到0.060和0.028 S cm-1,表明本文制备的自交联膜具有较高离子传导率.此外还通过热重分析(TGA)对两类自交联膜的热稳定性进行了研究. 相似文献
994.
Macrocycles consisting of two tris(phenylene ethynylene) (or tri-PE) units connected via two flexible linkers adopt an ‘unfolded’ conformation that is converted into a folded conformation upon introducing intramolecular hydrogen bonding interaction. These foldable macrocycles are capable of forming inclusion charge transfer (CT) complex with electron-deficient small aromatics. 相似文献
995.
在稳流条件下,考察了KNO3体系中离子液体辅助煤浆电解脱硫效果.研究了煤浆电解过程中离子液体结构、浓度、温度和时间对脱硫率的影响.当咪唑类离子液体有机结构相同时,不同阴离子脱硫率由高到低顺序为:Br- >BF4- >Cl-;当阴离子同为Br-时,咪唑脱硫效果优于吡啶.随着吡啶类离子液体([BPy]Br)浓度增加,脱硫率先增加,在0.3 mol/L处达到最大值,而后下降.此外,脱硫率随温度和时间增加而增大.最后,通过X射线光电子能谱(XPS)分析技术对实验前后煤中有机硫形态进行了分析.结果表明,噻吩主要通过萃取-氧化反应脱除,而其他形式有机硫(如硫醚、亚砜)则主要通过促进氧化及水解反应脱除. 相似文献
996.
A simple electrochemical method was developed to determine metronidazole based on β‐cyclodextrin‐functionalized gold nanoparticles/poly(L ‐cysteine) modified glassy carbon electrode (β‐CD‐GNPs/poly(L ‐cys)/GCE). The electropolymerized film of poly(L ‐cys) provides a stable matrix for the fabrication of a sensing interface. β‐CD‐GNPs can form inclusion complexes with metronidazole and act as a modifier with catalytic function. The modified electrode exhibited excellent electrocatalytic activity towards metronidazole. The reaction of metronidazole at the modified electrode was an irreversible process controlled by diffusion. Under optimum experimental conditions, the logarithm of catalytic currents shows a good linear relationship with that of the metronidazole concentration in the range of 0.1–600 µmol/L with a low detection limit of 14 nmol/L. In addition, the modified electrode exhibited satisfactory stability, sensitivity and reproducibility, and could be applied to the determination of metronidazole in an injection solution. 相似文献
997.
Dr. Guo‐Qiang Kong Zhi‐Da Han Dr. Yabing He Sha Ou Dr. Wei Zhou Prof. Dr. Taner Yildirim Prof. Dr. Rajamani Krishna Dr. Chao Zou Prof. Dr. Banglin Chen Prof. Dr. Chuan‐De Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14886-14894
Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m2 g?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future. 相似文献
998.
Dispersion of copper(Ⅱ) phthalocyanine (CuPc), copper(Ⅱ) phthalocyaninesulfonate (CuPcS) and cobalt(Ⅱ)phthalocyaninetetrasulfonate (CoPcTS) on the surface of titanium dioxide was investigated by XRD, XPS, FT-IR and UV-Vis techniques. Results show that interaction between CuPc and TiO2 was very weak and CuPc was difficult to disperse on the surface of the support. While partly sulfurized CuPcS could be dispersed on the surface of support through sulfo-groups and its dispersion capacity was determined to be 0.085 g CuPcS/g TiO2. Completely sulfurlzed CoPcTS could also be dispersed on the surface of TiO2 as a monolayer and its dispersion capacity was 0.12 g CoPcTS/g TiO2. Interactions of the sulfo-groups as well as the electrons of CoPcTS with the surface of TiO2 could be evidenced by FT-IR characterization. Therefore, it was suggested that CoPcTS molecules be adsorbed on the surface of TiO2 in a flat-lying mode while CuPcS in a slanting one. UV-Vis spectra show that the dispersed CuPcS and CoPcTS molecules exist in both forms of monomers and dimers. 相似文献
999.
1000.
The influence of both light and heat on the stability of nitrofurazone aqueous solution was studied. Results show that in either heating experiments or the exposure to light at high temperatures, the degradation rate obeyed zero-order kinetics. The total rate constant ktotal caused by both light and heat can be divided into two parts: ktotal =kdark klight, where kdark and klight are the degradation rate constants caused by heat and light, respectively. The klight can be expressed as klight=Alight*exp(-Ea,light/RT)*E, where E is the illuminance of light, and Alight and Ea,light both are experimental constants. The values of these kinetic parameters were determined based on the experiments in the dark and upon exposure to three different light sources. Results show that the values of Alight and Ea, light varied with the light source. To save time, labor, and drugs, exponential heating experiments were employed and compared with the isothermal experiments. Results indicated that kinetic parameters obtained by exponential heating experiments are comparable to those obtained by isothermal experiments either in the dark or upon exposure to light. 相似文献