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The adsorption properties of NO molecule on anionic, cationic, and neutral Au(n) clusters (n=1-6) are studied using the density functional theory with the generalized gradient approximation, and with the hybrid functional. For anionic and cationic clusters, the charge transfer between the Au clusters and NO molecule and the corresponding weakening and elongation of the N-O bond are essential factors of the adsorption. The neutral Au clusters have also remarkable adsorption ability to NO molecule. The adsorption energies of NO on the cationic clusters are generally greater than those on the neutral and anionic clusters. 相似文献
33.
Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO2, the primary greenhouse gas. Notably, the concentration of CO2 in the atmosphere is increasing annually at an astounding rate. Electrochemical CO2 reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO2 emissions. Despite the steady progress in the selective generation of C1 products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C2H4) has a higher energy density than do C1 species and is an important industrial feedstock in high demand. However, the conversion of CO2 to C2H4 is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C2H4 by taking advantage of the prominent interaction of Cu with shape-controlled CeO2 nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO2. The overall ECR Faradaic efficiency (FE) over Cu/CeO2(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO2(100) (FE ≈ 51.5%) and Cu/CeO2(111) (FE ≈ 48.4%) in 0.1 mol·L-1 KHCO3 solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO2(100), CeO2(110), and CeO2(111). In particular, the FE toward C2H4 formation and the partial current density increased in the sequence Cu/CeO2(111) < Cu/CeO2(100) < Cu/CeO2(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO2(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO2(100) and Cu/CeO2(111) were FEC2H4 ≈ 31.8% and FEC2H4 ≈ 29.6%, respectively. The C2H4 selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C2H4 remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO2(110) to yield C2H4 was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO2 but also remarkably stabilized Cu+, thereby boosting the ECR to produce C2H4. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering. 相似文献
34.
Wei Sheng Feng Hong Wei Li Xiao Ke Zheng Sui Qing Chen 《中国化学快报》2007,18(12):1518-1520
Two new megastigmane O-glucopyranosides,named (2R,3R,5R,6S,9R)-3-hydroxy-5,6-epoxy-β-ionol-2-O-β-D-glucopyrano- side(1) and (2R,3R,5R,6S,9R)-3-hydroxyl-5,6-epoxy-acety-β-ionol-2-O-β-D-glucopyranoside(2) together with six known mega- stigmanes,were isolated from the leaves of Broussonetia papyrifera (Linn.) Vent.Their structures were established by chemical methods and spectroscopic techniques including 2D NMR. 相似文献
35.
Rapid simultaneous determination of four anthracene derivatives using a single non-linear variable-angle synchronous fluorescence spectrum 总被引:1,自引:0,他引:1
A rapid, simple and inexpensive spectrofluorimetric method has been developed for the simultaneous identification and quantification of anthracene (ANT), 9,10-dimethylanthracene (DIM), 2-aminoanthracene (AMI) and dibenz[ah]anthracene (DIB). A well-resolved spectrum for the mixture of these four compounds is obtained based on a single non-linear variable-angle synchronous scanning. The linear concentration ranges are 10-1,000, 5-500, 50-1,000 and 10-200 ng mL(-1) for ANT, DIM, AMI and DIB, respectively, at lambdaex/lambdaem = 358/380, 399/408, 414/465 and 298/394 nm, respectively. The analyses are performed in cyclohexane. Recoveries of 90.0-111.0% in synthetic mixtures are obtained. The detection limits are 2.0 ng mL(-1) for DIM, 2.7 ng mL(-1) for ANT, 15.8 ng mL(-1) for AMI and 4.2 ng mL(-1) for DIB. The method has also been applied to several real water samples with satisfactory results. 相似文献
36.
Chu YP Gong Y Tan XL Zhang L Zhao S An JY Yu JY 《Journal of colloid and interface science》2004,276(1):182-187
Alkylnaphthalene sulfonates with high purity were selected as model components to research synergism for lowering interfacial tension (IFT) in surfactant/alkali/acidic oil systems. The dynamic IFTs between alkylnaphthalene sulfonates with different alkyl chain length and n-decane, oleic acid model oil, or Shengli crude oil were measured. The results showed that the alkylnaphthalene sulfonates with different alkyl chain lengths had different synergism with different acidic components and their ionized acids under the same conditions. The synergism for lowering dynamic IFT in alkylnaphthalene sulfonate/alkali/acidic oil systems was controlled by alkylnaphthalene sulfonate concentration, alkyl chain length, alkali concentration, alkali type, and oleic acid concentration: optimal physicochemical conditions were necessary to the best synergism. This indicates that the synergism among added surfactant acidic components in crude oil and their ionized acids is controlled by the ratio of their interfacial concentrations. 相似文献
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The readily available alkyl dicyanoacetates 1 reacted with the 1,3-dipolar reagents arenecarbonitrile oxides 2 ′ and arenecarbonitrile imines 5 ′ to afford 1,2,4-oxadiazol and 1,2,4-triazol derivatives. The arenecarbonitrile oxides 2 ′ with electron-donating groups on the arene ring gave products 3a – d resulting from addition on both CN groups of 1 , and those with electron-withdrawing groups provided mono-adducts 4a – e (Scheme 1). Arylnitrile imines 5 ′ reacted with 1 to offer both bis- and mono-addition products (Scheme 2); the bis-adducts 8a , b possess an ester structure, whereas the mono-adducts 6a – d present a ketene-hemiacetal structure. 相似文献
40.
Herein, we demonstrate that silica films with perpendicular macroporous channels and accessible ordered mesopores can be conveniently prepared. The hierarchical macroporous–mesoporous silica films are synthesized by using zinc oxide nanorod array as macroporous template and CTAB surfactant as mesoporous template. In basic surfactant-containing solution, ordered mesoporous silica shells homogeneously grow on the zinc oxide nanorod array. The growth of the mesostructures do not require any chemical modification for the zinc oxide nanorod, which opens a new way for preparing hierarchical silica films with perpendicular mesochannels. The prepared hierarchical macroporous–mesoporous silica films possess a uniform thickness of 2 mm, large perpendicular macropores with a length of 1.8 mm and a width of 80 nm, and accessible ordered mesopores. Separation experiment demonstrates that this macroporous–mesoporous film can effectively separate biomolecules with different sizes. 相似文献