全文获取类型
收费全文 | 70368篇 |
免费 | 9875篇 |
国内免费 | 6644篇 |
专业分类
化学 | 46982篇 |
晶体学 | 659篇 |
力学 | 4661篇 |
综合类 | 515篇 |
数学 | 8454篇 |
物理学 | 25616篇 |
出版年
2024年 | 228篇 |
2023年 | 1399篇 |
2022年 | 2280篇 |
2021年 | 2466篇 |
2020年 | 2522篇 |
2019年 | 2422篇 |
2018年 | 2188篇 |
2017年 | 1939篇 |
2016年 | 2965篇 |
2015年 | 3078篇 |
2014年 | 3652篇 |
2013年 | 4844篇 |
2012年 | 5891篇 |
2011年 | 6014篇 |
2010年 | 4079篇 |
2009年 | 4018篇 |
2008年 | 4188篇 |
2007年 | 3789篇 |
2006年 | 3567篇 |
2005年 | 3092篇 |
2004年 | 2478篇 |
2003年 | 1895篇 |
2002年 | 1682篇 |
2001年 | 1520篇 |
2000年 | 1418篇 |
1999年 | 1563篇 |
1998年 | 1330篇 |
1997年 | 1169篇 |
1996年 | 1227篇 |
1995年 | 1071篇 |
1994年 | 1007篇 |
1993年 | 866篇 |
1992年 | 768篇 |
1991年 | 664篇 |
1990年 | 555篇 |
1989年 | 482篇 |
1988年 | 366篇 |
1987年 | 350篇 |
1986年 | 298篇 |
1985年 | 300篇 |
1984年 | 202篇 |
1983年 | 176篇 |
1982年 | 145篇 |
1981年 | 112篇 |
1980年 | 82篇 |
1978年 | 56篇 |
1977年 | 52篇 |
1976年 | 50篇 |
1975年 | 57篇 |
1973年 | 57篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Hongyang Su Lanlan Chen Yizhen Chen Prof. Rui Si Yuting Wu Xiaonan Wu Dr. Zhigang Geng Prof. Wenhua Zhang Prof. Jie Zeng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20591-20596
Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH3). Reported herein is a novel Fe-MoS2 catalyst with Fe atomically dispersed onto MoS2 nanosheets, imitating natural nitrogenase, to boost N2 electroreduction into NH3 at room temperature. The Fe-MoS2 nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mgcat.−1 h−1 for NH3 at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N2 was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS2 with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N2 into NH3. This work provides new ideas for the design of catalysts for N2 electroreduction and strengthens the understanding about N2 activation over Mo-based catalysts. 相似文献
992.
The pretreatment technique of microwave-assisted extraction on-line headspace solid-phase microextraction (MAE-HS-SPME) was designed and studied for one-step in-situ sample preparation prior to the chromatographic analysis of a pesticide on vegetables. The pesticide on chopped vegetables was extracted into an aqueous solution with the aid of microwave irradiation and then directly onto the SPME fiber in headspace. After being collected on to the SPME fiber and desorbed in the GC injection port, the pesticide (dichlorvos) was analyzed with a GC-electron-capture detection system. The optimum conditions for obtaining extraction efficiency, such as the pH, the polarity modifier, and the salt added in sample solution, the microwave irradiation, as well as the desorption parameters were investigated. Experimental results indicated that the proposed MAE-HS-SPME technique attained the best extraction efficiency of 106% recovery under the optimized conditions, i.e. irradiation of extraction solution (10% aqueous ethylene glycol) at pH 5.0 with medium microwave power for 10 min. Desorption at 220 degrees C for 3 min offered the best detection result. The detection was linear at 5-75 microg/l with correlation coefficient of 0.9985. Detection limit was obtained at approximately 1.0 microg/l level based on S/N=3. The proposed method provided a very simple, fast, and solvent-less procedure to collect pesticides directly from vegetables for GC determination. Its application was illustrated by the analysis of trace dichlorvos in vegetables. 相似文献
993.
Sh. Yu X. Li A. Ren D. Shao Ch. Chen X. Wang 《Journal of Radioanalytical and Nuclear Chemistry》2006,268(2):387-392
Summary The
removal of heavy metal ion Co(II) from aqueous solution was studied usingg-Al2O3
by batch technique. The experiments were performed at T=20±2 °C, in 0.01M
NaNO3 solutions and under aerobic conditions. The effect of pH,
ionic strength, fulvic acid (FA) and alumina amount on the sorption of Co(II)
on alumina were also investigated. The pH affected the sorption of Co(II)
significantly as compared with the effect of FA and ionic strength. The results
indicated that strong chemical bonds are formed between Co(II) and functional
groups of the bare or FA coated alumina, and a precipitation of Co(II) takes
place on the alumina surface, induced by a transition from the adsorption to
surface. The addition sequences of Co/FA on Co(II) sorption were also studied:
the sorption of Co(II) in the ternary system was found independent of addition
sequences.</p>
</p> 相似文献
994.
Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries 总被引:6,自引:0,他引:6
Luo X Lu Z Xi J Wu Z Zhu W Chen L Qiu X 《The journal of physical chemistry. B》2005,109(43):20310-20314
The preparation and physical characterization of a poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane prepared by a solution-grafting method were described. These membranes exhibited high conductivity with a value 3.22 x 10(-2) S/cm at 30 degrees C. ICP studies revealed that the PVDF-g-PSSA membrane showed dramatically lower vanadium ion permeability compared to Nafion 117. Trivalent vanadium ions had the highest permeability through all these membranes in contrast to pentavalent vanadium ions with the lowest. The VRB with the low-cost PVDF-g-PSSA membrane exhibited a higher performance than that with Nafion 117 under the same operating conditions, and its energy efficiency reached 75.8% at 30 mA/cm(2). The performance of VRB with the PVDF-g-PSSA membrane can be maintained after more than 200 cycles at a current density of 60 mA/cm(2). 相似文献
995.
Yanbing Zhao Wanyu Chen Yajiang Yang Xiangliang Yang Huibi Xu 《Colloid and polymer science》2007,285(12):1395-1400
Ionically cross-linked polyampholytic hydrogels were synthesized by redox copolymerization of acrylamide and an ionic complex
of (N,N-diethylamino)ethyl methacrylate and acrylic acid (designated as PADA hydrogel). The swelling behavior of the hydrogels in
water indicated that a minimal equilibrium swelling ratio is found when the molar ratio of anionic/cationic monomers was 1.55.
In NaCl solution, the hydrogels exhibited the typical swelling behavior of conventional polyampholytic gels. Their equilibrium
swelling ratios increased with an increase in the NaCl concentration. In solutions of multivalent ions (CaCl2 and trisodium citrate solutions), the equilibrium swelling ratios of the hydrogels increased first and were then followed
by a decrease with an increase in salt concentration. Interestingly, an unexpected abrupt swelling phenomenon was observed
when the fully swollen hydrogels in salt solution were transmitted to pure water. The unique swelling behavior of PADA hydrogels
depends not only on the molar ratio of the anionic/cationic monomers but also on the valency of the ions. 相似文献
996.
Jun-Ming Chen Shean-Ell Chiou Chin-Wang Huang 《Journal of Radioanalytical and Nuclear Chemistry》1994,181(2):335-342
Environmental characters have been established by tritium contents in well water, coastal seawater and reservoir water collected from various places around Taiwan island. Tritium concentrations of samples were detected by a liquid scintillation analyzer TRI-CARB-LSC 2550 TR mode, with a low level standard quench curve. After samples were concentrated by electrolysis, tritium concentration was detected in optimum conditions of LLLSA. An electrolytic enrichment technique was also developed with a eurrent density of 100 mA/cm2 and 0.4–0.6% (Na2O2) electrolyte in concentrated samples. Data observed show a lower tritium concentration for coastal seawater than for wells in the same area. The tritium concentration ratio of well and coastal seawater on the western side of Taiwan is 4.000 and on the eastern side 5.801. Tritium content of reservoir water is related to the logarithm of effective volume capacity. 相似文献
997.
Xiao‐Yuan Wu Quan‐Guo Zhai Li‐Juan Chen Can‐Zhong Lu 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m261-m263
The title complex, poly[di‐μ3‐oxo‐hepta‐μ2‐oxo‐tetraoxobis(1,10‐phenanthroline)‐μ4‐terephthalato‐dicopper(II)tetramolybdate(VI)], [Cu2Mo4(C8H4O4)O13(C12H8N2)2], represents a novel two‐dimensional copper–molybdate compound with mixed ligands. Tetranuclear molybdenum oxide clusters are joined through corner‐sharing into a ribbon‐like chain, with [Cu(phen)]2+ (phen is 1,10‐phenanthroline) complexes grafted onto either side. The terephthalate ligand lies about an inversion centre and links these chains to form a layer via Cu—O and Mo—O bonds. Face‐to‐face π–π stacking interactions between adjacent phen ligands stabilize the structure. 相似文献
998.
Chen CH Liu KY Sudhakar S Lim TS Fann W Hsu CP Luh TY 《The journal of physical chemistry. B》2005,109(38):17887-17891
Thin films of silica hybrid materials consisting of two to three covalently bound organic chromophores at different ratios were conveniently synthesized and fabricated. The photophysical properties of these materials have been studied. The fluorescence spectra reveal complete fluorescence resonance energy transfer (FRET) from donor to acceptor, and the light-harvesting ability of these hybrid materials increases with increasing the molar fraction of donor chromophore. In a three-chromophore system, the energy is transferred from 300 to 530 nm successfully. Time-resolved fluorescence experiments are employed to elucidate the average rates and efficiencies (84-97%) of energy transfer in these organic/inorganic hybrid systems. The hybrid materials have been shown to provide antenna effect to facilitate energy transfer and light harvesting. 相似文献
999.
Hui Chen Yujiao Fan Nian Zhang Sylvain Trpout Bergam Ptissam Annie Brûlet Ben Zhong Tang Min-Hui Li 《Chemical science》2021,12(15):5495
Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio fPEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with fPEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.Fluorescent Imm cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation. 相似文献
1000.
Synthesis of Spherical Titanium Dioxide Particles by Homogeneous Precipitation in Acetone Solution 总被引:1,自引:0,他引:1
Titania powders were synthesized by thermal hydrolysis of titanium tetrachloride in a mixed solvent was studied. The dielectric constant was tuned by regulating the acetone/water volume ratio (R/H ratio) and temperature of the solvent. Hydroxypropyl cellulose (HPC) was used as a steric dispersant. The synthesis were carried out at R/H ratios of 0–4, temperatures of 70–90°C, TiCl4 concentrations of 0.05–0.2 M, HPC concentrations of 0–5 × 10–3 g/cm3, and synthesis times of 15–60 min. The TiO2 particles obtained at an R/H ratio of 0, i.e., pure water system, were fine and agglomerated. In contrast, the TiO2 particles prepared at an R/H ratio of 3 were uniform and spherical. The TiO2 particle size increased with increasing TiCl4 concentration. The synthesis temperature did not influence the particle size, but greatly influenced the morphologyof the TiO2. Adding HPC to the solution yielded more uniform and spherical particles. In addition, the synthesis time should be longer than 30 min to obtain the most uniform and spherical particles. The dielectric constant of the acetone-water mixed solvent at 28 gave the most uniform and spherical TiO2 particles. The powders prepared at the condition of 0.1 M TiCl4, R/H ratio of 3, HPC concentration of 0.001 g/cm3, temperature of 70°C, and synthesis time of 1 h exhibited the most uniform and spherical morphology. The as-synthesized powder was anatase and retained the phase below 400°C. It transformed to the rutile phase after calcination at 700°C. 相似文献