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991.
Yongseon Kim Jaehyuk Lim Shinhoo Kang 《International journal of quantum chemistry》2013,113(2):148-154
The dissolution phenomenon of Mn ions in LiMn2O4 (LMO) cathode material for lithium ion batteries (LIBs) was investigated by a first principle calculation using the discrete variational Xα molecular orbital method. It was found that the oxidation number of Mn ions easily increases at high temperatures due to the empty levels of Mn 3d orbitals located in the vicinity of the Fermi energy level of LMO crystal. The changes of density of states (DOS) and Mn‐O bonding properties with doping were examined. Analysis of DOS showed that the substitution of elements with a smaller oxidation number than Mn was found effective in keeping Mn ions at higher oxidation states. From the calculation of bonding properties, the dissolution of Mn was found to be strongly correlated with the covalent nature of Mn‐O bond. Based on the results, we concluded that increasing the covalent character of Mn‐O bond is effective to minimize the dissolution of Mn ions, along with suppressing the formation of Jahn‐Teller‐active Mn3+ by inducing Mn ions at high oxidation state with proper selection of doping elements. © 2012 Wiley Periodicals, Inc. 相似文献
992.
Qian‐Lin Tang 《International journal of quantum chemistry》2013,113(16):1992-2001
Practical copper (Cu)‐based catalysts for the water–gas shift (WGS) reaction was long believed to expose a large proportion of Cu(110) planes. In this work, as an important first step toward addressing sulfur poisoning of these catalysts, the detailed mechanism for the splitting of hydrogen sulfide (H2S) on the open Cu(110) facet has been investigated in the framework of periodic, self‐consistent density functional theory (DFT‐GGA). The microkinetic model based on the first‐principles calculations has also been developed to quantitatively evaluate the two considered decomposition routes for yielding surface atomic sulfur (S*): (1) H2S → H2S* → SH* → S* and (2) 2H2S → 2H2S* → 2SH* → S* + H2S* → S* + H2S. The first pathway proceeding through unimolecular SH* dissociation was identified to be feasible, whereas the second pathway involving bimolecular SH* disproportionation made no contribution to S* formation. The molecular adsorption of H2S is the slowest elementary step of its full decomposition, being related with the large entropy term of the gas‐phase reactant under realistic reaction conditions. A comparison of thermodynamic and kinetic reactivity between the substrate and the close‐packed Cu(111) surface further shows that a loosely packed facet can promote the S* formation from H2S on Cu, thus revealing that the reaction process is structure sensitive. The present DFT and microkinetic modeling results provide a reasonably complete picture for the chemistry of H2S on the Cu(110) surface, which is a necessary basis for the design of new sulfur‐tolerant WGS catalysts. © 2013 Wiley Periodicals, Inc. 相似文献
993.
Majid M. Heravi Hamideh Alinejhad Fatemeh Derikvand Hossein A. Oskooie Bita Baghernejad Fatemeh F. Bamoharram 《合成通讯》2013,43(14):2033-2039
We report here two simple methods for the synthesis of benzo[c]acridine derivatives from three-component, one-pot condensation of 1-naphthylamine, dimedone, and a variety of substituted aldehydes in the presence of a catalytic amount of NH2SO3H or H6P2W18O62 · 18H2O under solvent-free conditions at 120 °C or in refluxing ethanol. 相似文献
994.
Qiaoxia Guo Wennian Wang Weiling Teng Liwei Chen Yanqing Wang Baojian Shen 《合成通讯》2013,43(17):2574-2584
A convenient one-pot method for the synthesis of substituted quinolines via the reaction of aniline and aldehyde in the presence of a Lewis acid (AlCl3) and an oxidant (H2O2) has been developed. Hydrogen peroxide was found to promote the reaction by its function as a hydrogen hunter, hindering the formation of by-product N-alkylaniline. The effect of the oxidant on the yield and selectivity was studied. When the molar ratio of aniline, n-butyraldehyde, and H2O2 was 1:3:0.5 at 25 °C, the yield of 3-ethyl-2-propylquinoline was improved from 64% (reaction without H2O2) to 84% (with H2O2), and the quinoline selectivity was improved to almost 100%. Moreover, the reaction time was obviously reduced. The substituent effect was also investigated in this work. 相似文献
995.
An efficient method has been developed for the allylation of aldehydes with allytributylstannane in the presence of a catalytic amount of Mg(NTf2)2·xH2O at room temperature in water to afford the corresponding homoallylic alcohols in good yields. 相似文献
996.
Mohammad Ali Zolfigol Peyman Salehi Arash Ghorbani-Choghamarani Maliheh Safaiee Mozhgan Shahamirian 《合成通讯》2013,43(11):1817-1823
Silica chromate easily converts 1,4‐dihydropyridines to their corresponding pyridines in the presence of NaHSO4 · H2O and wet SiO2 in dichloromethane at room temperature in good to excellent yields. 相似文献
997.
The reaction of primary aromatic amines with aryl aldehydes is found to be catalyzed by cerium chloride heptahydrate under solvent-free conditions to give the corresponding Schiff bases in good yields. 相似文献
998.
Rudhramyna Gnaneshwar 《合成通讯》2013,43(7):885-890
Abstract Conjugate addition of a silyl ketene acetal [Me2C?C (OMe)OSiMe3] to α,β‐unsaturated lactones (namely, 5,6‐dihydro‐2H‐pyran‐2‐one, 2(5H)‐furanone as Michael acceptor) occurs efficiently at room temperature in the presence of a nucleophilic catalyst, tetra‐n‐butyl ammonium bibenzoate (TBABB), in THF as well as Lewis acid catalysts such as Yb(OTf)3 and I2 in CH2Cl2, giving the corresponding 1,4‐adducts in excellent yields. 相似文献
999.
An efficient and rapid method for oxidation of electron‐rich aromatic aldehydes to their corresponding carboxylic acids in excellent yields was developed. It is based on the oxidation of methoxy‐substituted benzaldehydes in methanol with an improved aqueous basic hydrogen peroxide system. Benzaldehydes with electron‐withdrawing substituents are oxidized to the corresponding carboxylic acid in excellent yields under mild reaction conditions. 相似文献
1000.
Daniel R. Zuidema Sarah L. Williams Katherine J. Wert Karin J. Bosma Abigail L. Smith Robert C. Mebane 《合成通讯》2013,43(19):2927-2931
Aryl ketones are readily deoxygenated to their corresponding aryl alkanes upon treatment with Raney nickel catalyst in boiling 2-propanol.