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21.
F. M. Bautista J. M. Campelo A. Garcia D. Luna J. M. Marinas A. A. Romero M. R. Urbano 《Reaction Kinetics and Catalysis Letters》1997,62(1):47-54
The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO4 (Cr/P=1) and CrPO4-AlPO4 (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving
a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol. 相似文献
22.
In this study, we explore the reactions of coordinated arenes, e.g., hydrogenation, nitration, and bromination, to prepare compounds which are not accessible from conventional organic synthesis. The reaction products formed from reactions with the coordinated and the uncoordinated arenes are compared. The polycyclic aromatic hydrocarbons (PAHs) employed for this study include phenanthrene, methyl- and acetyl-phenanthrene, and benz[a]anthracene (BA), The tricarbonylchromium group demonstrated various characteristics which influence the reactions in this work, such as an electronic effect to deactivate hydrogenation, a steric effect to exhibit, highly positional selective nitration, and a free radical mechanism to direct bromine to attack at the ring coordinated to tricarbonylchromium. 相似文献
23.
Halfsandwich Complexes of Chromium with the Trifluoromethyl Isocyanide Ligand The synthesis and properties of the halfsandwich complexes [η6-1,3,5-C6H3(CH3)3]Cr(CO)2(CNCF3), [η6-1,3,5-C6H3(CH3)3]Cr(CO)(CNCH3)(CNCF3) und [η6-1,3,5-C6H3(CH3)3]Cr(CNCF3)3 is reported. The vibrational spectroscopic data proof the strong π accepting character of the trifluoromethyl isocyanide ligand. 相似文献
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26.
CuCrAl和CuCrZr低温液相合成甲醇催化剂的研究 总被引:2,自引:0,他引:2
用络合共沉淀法制备了CuCrAl和CuCrZr复合氧化物液相合成甲醇催化剂,其比表面分别达到119和116m2/g.在5.0~5.5MPa和383K条件下,分别用间歇式和流动式反应釜考察了催化剂的活性和稳定性.结果表明:CuCrAl和CuCrZr的活性均明显高于CuCr;CuCrAl的活性略高于CuCrZr,但甲酸甲酯(MF)的选择性明显低于CuCrZr;两者在12h内未见活性明显下降.甲醇钠在反应过程中部分转化为甲酸钠和NaOH.CuCrAl和CuCrZr有较高的氢解活性可抑制甲醇钠与MF生成甲酸钠,从而有较低的甲酸钠浓度.但是,Al2O3和ZrO2的酸性有利于甲醇脱水,引起甲醇钠水解生成NaOH.溶剂对CuCr基催化剂的活性和选择性有明显影响.对反应机理进行了讨论. 相似文献
27.
Fátima Nunes Serralha José Madeira Lopes Francisco Lemos Duarte Prazeres Maria Aires-Barros Joo Rocha Joaquim Cabral Fernando Ramôa Ribeiro 《Reaction Kinetics and Catalysis Letters》2000,69(2):217-222
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
28.
本文采用脉冲色谱法温室金属铬合中的氢含量,用正交试验法选择了最佳分析条件(含加热时间,加热初级电流,试样重量,浴料及浴比),建立了锡浴法测定铬中氢的方法,方法精度为5.5%。 相似文献
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30.
Alan M Bond Enrico Mocellin Cherrie B Pascual Panit Wedkanjana Grard Jaouen Siden Top 《应用有机金属化学》1990,4(5):557-568
Electrochemical oxidation of α- and β-diastereomers of a range of steroid hormone receptor marker chromium tricarbonyl complexes, (steroid)Cr(CO)3, have been examined at platinum electrodes in dichloromethane. Data confirm the general nature of previously published conclusions on the oxidation of (arene)Cr(CO)3 complexes (arene = benzene or steroid). That is, with 0.1 M Bu4NPF6 as the electrolyte, and in the absence of nucleophiles, a reversible oneelectron process, (steroid)Cr(CO)3 ? [(steroid)Cr(CO)3]+ + e?, is observed, followed by an irreversible one-electron process at considerably more positive potentials. The reversible half-wave potentials (approximately E°-values) calculated for the [(steroid)Cr(CO)3]+/(steroid)Cr(CO)3 redox couple are shown to be dependent on whether the α- or β-diastereomer is oxidized. Similarly the rate of nucleophilic attack on the 17-electron cation [(steroid)Cr(CO)3]+ by nucleophiles such as ClO, PPh3 and bis(diphenylphosphine)methane confirms a previous observation that the stereochemistry of this class of compound is important with respect to redox, kinetic and hormone receptor properties. The nature of the electrochemical data obtained on the (arene)Cr(CO)3 complexes in the presence of nucleophiles suggests that reactions associated with the nucleophilic attack on the 17-electron cations are complex and that a range of reaction pathways occur simultaneously. Electrochemical studies on the oxidation of (benzene)Cr(CO)2PPh3 and (oestradiol)Cr(CO)2PPh3 confirm some aspects of the proposed mechanisms, although it is clear that a great deal still has to be learned concerning mechanistic aspects of nucleophilic attack on these 17-electron complexes. 相似文献