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991.
Mingxing Qian 《Tetrahedron letters》2005,46(16):2927-2930
The reaction of alkynylzinc bromides with benzyl bromides or chlorides in the presence of a catalytic amount of Pd(DPEphos)Cl2 in THF at 23 °C cleanly produces the corresponding benzylated alkynes in 73-97% yields. With 10−3 mol % of Pd(DPEphos)Cl2, the maximum turnover number of 7.1 × 104 has been observed for the formation of PhCCCH2Ph. 相似文献
992.
993.
trans-2,3-Divinyl epoxides have been found to be good substrates for the generation of carbonyl ylides in CCl4 and 145 °C. These ylides, to a limited extent, undergo isomerization to cis-2,3-divinyl epoxides, leading to the isolation of 4,5-dihydrooxepins. Of greater potential usefulness is the finding that these ylides can be efficiently trapped in an intermolecular sense by a dipolarophile, leading to dihydrofurans. 相似文献
994.
研究了一些氧化物的H2-TPR及CO-TPR行为,结果发现,Co3O4/Al2O3,NiO/SiO2,NiO和Pd/NiO的H2-TPR温度要低于它们的CO-TPR温度,特别是Pd/NiO样品,它的H2-TPR温度为598K,而其CO-TPR温度高达949K,差别为351K,因此有可能利用Pd/NiO在一定温度下选择性地与CO中的H2反应而将其除去. 实验结果表明,Pd/NiO可在603K及4000h-1的条件下从H2(0.34%),CO(50%)和N2(余)的混合气中选择性地除去90%以上的H2,吸氢容量为每克样品55mL标准态H2. 相似文献
995.
Yu. V. Tomilov I. V. Kostyuchenko E. V. Shulishov O. M. Nefedov 《Russian Chemical Bulletin》1997,46(3):511-518
The reaction of diazocyclopropane generatedin situ with acrylonitrile or methyl acrylate to give 1∶1, 1∶2, and 2∶1 cycloadducts was carried out. The products resulting from
1,3-dipolar cycloaddition and subsequent isomeriation,viz., 3-cyano- and 3-methoxycarbonylspiro(2-pyrazoline-5,1′-cyclopropanes), isolated in the first step in ∼70% yield, react in
an alkaline solution with the above acrylates or diazocyclopropane as C(3)-nucleophiles to give the corresponding 3-(2′-cyanoethyl)-,
3-(2′-methoxycarbonylethyl)-, or 3-(cyclopropylazo)-1-pyrazolines. The thermal deazotization of these pyrazolines to spiropentane
derivatives was investigated.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 532–539, March, 1997. 相似文献
996.
The efficient utilization of carbon dioxide (CO2) as a C1 feedstock is of great significance for green and sustainable development. Therefore, the efficient chemical conversion of CO2 into value-added products has recently attracted a lot of research attention in recent years. The transformation of CO2 generally requires high-energy substrates, specific catalysts, and harsh reaction conditions due to its high thermodynamic stability and kinetic inertness. Consequently, several efforts have been dedicated toward the development of high-performance catalysts and new reaction routes for CO2 conversion over the last few decades. To date, many routes of convert CO2 into value-added chemicals have been proposed, together with the development of heterogeneous and homogeneous catalysts. Among the advanced catalysts reported to date, ionic liquids (ILs) have been widely investigated and show great potential for the efficient, selective, and economical conversion of CO2 into highly valuable products under mild conditions, even under ambient conditions. Some task-specific ILs have been designed with unique functional groups (e.g., —OH, —SO3H, —NH2, —COOH, and —C≡N), which can act as the solvent, absorbent, activating agent, catalyst, or cocatalyst to realize the transformation of CO2 under metal-free and mild conditions. In addition, a variety of catalytic systems composed of ILs and metal catalysts have also been reported for the transformation of CO2, in which the combination of the IL and metal catalyst is responsible for CO2 conversion with high efficiency. In this review article, we summarize the recent advances in IL-mediated CO2 transformation into chemicals prepared via C—O, C—N, C—S, C—H, and C—C bond forming processes. ILs that can chemically capture CO2 with high capacity are first introduced, which can activate CO2 via the formation of IL-based carbonates or carbamates, thus realizing the transformation of CO2 under metal-free and mild conditions. Recent progress in IL-mediated CO2 transformations to form carbonates and various kinds of N- and S-containing compounds (e.g., oxazolidinones, ureas, benzimidazolones, formamides, methylamines, benzothiazoles, and other chemicals) as well as CO2 hydrogenation to give formic acid, methane, acetic acid, low-carbon alcohols, and hydrocarbons has been summarized in this review with a focus on the reaction routes, catalytic systems, and reaction mechanism. In these reactions, ILs can simultaneously activate the substrate via strong H-bonding in addition to activating CO2, and the cooperative effects among the ionic and molecular species and metal catalysts accomplish the reactions of CO2 with various kinds of substrates to afford a wide range of value-added chemicals. Finally, the shortcomings and perspectives of ILs are discussed. In short, IL-mediated CO2 transformations provide green and effective routes for the synthesis of high-value chemicals, which may have great potential for a wide range of applications. 相似文献
997.
The products of high-vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane were studied by matrix IR spectroscopy. The
decomposition of 1,1,1-trifluoro-2-bromo-2-chloroethane was shown to occur predominantlyvia two directions: to form the 1,1,1-trifluoro-2-chloroethyl radical and trifluoromethylcarbene isomerizing to trifluoroethylene.
The CF3CHCl radical has been detected in the matrix for the first time. The bands observed in the IR spectrum were calculated by
the quantum-chemical B3LYP/6-311 G(d,p) method and assigned to normal vibrations of the radical.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2085–2088, October, 1998. 相似文献
998.
The kinetics of the reaction between organocobaloximes, RCo(DH)2H2O, and iodine have been investigated. They reveal the participation of an RCo(DH)2H2O · I2 intermediate which undergoes intramolecular transalkylation and acts as an electrophile towards a second organocobaloxime molecule. The trend in reactivity as the R group is varied is discussed. 相似文献
999.
trans-RhCl(CO)(TPPTS)2 (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS)2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS)2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins. 相似文献
1000.
ZrO2在Cu-ZnO-ZrO2甲醇水蒸汽重整制氢催化剂中的作用 总被引:2,自引:0,他引:2
通过对一系列Cu-ZnO-ZrO2甲醇水蒸汽重整(SRM)催化剂的XRD、TEM和BET表征及催化性能测定,研究催化剂中ZrO2对催化剂粒径、比表面以及对SRM反应性能的影响.结果表明,ZrO2的加入,使催化剂的粒径从15 nm降至10 nm(其中CuO和ZnO的平均粒径分别从7.7和10.4 nm降至3.9和8.7 nm),BET比表面从60 m2•g-1增至78 m2•g-1.随着催化剂含ZrO2量不同,甲醇的转化率和H2、CO2的选择性均产生变化,当催化剂中Zr含量为24.0%(w),反应温度为220 ℃,水、醇摩尔比为1.3时,甲醇的转化率达到51.6%, H2和CO2的选择性达到100%(CO和CH4在产物气体中的体积分数小于10-4),这一结果对甲醇燃料电池甲醇重整器的应用具有重要的意义. 相似文献