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91.
Atsuhisa Mimoto Sojiro Kon Takuya Motomura Minoru Inaba 《Journal of fluorine chemistry》2005,126(7):1101-1110
The Ni-based alloys, such as Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si, prepared by hot isostatic pressing (HIP) at 1000 °C under 2 × 108 Pa for 2 h were employed as the anodes for electrolytic production of NF3. The current efficiencies for NF3 formation were 42-38, 52-40, 52-47, 63-62, 50 and 41% for Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloys, respectively. The current efficiencies only on Ni-Cu alloys with Cu concentrations lower than 10 mol% were almost the same as those on Ni sheet and HIPed Ni anodes, whereas those on the other alloys used in this study were smaller compared with those on both Ni anodes. On the other hand, the current losses caused by anodic dissolution of Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloy electrodes were 7.95-4.42, 6.40-7.02, 5.60-6.30, 3.34-6.33, 5.10 and 0.18%, respectively. The anode consumptions of Ni-5 mol% Cu and Ni-5 mol% Si alloys were almost the same or smaller compared with those of Ni sheet and HIPed Ni electrodes, though those of other alloys used were large compared with those of both Ni anodes. Consequently, addition of Cu to the nickel matrix is available for a cheaper cost of anode with keeping a same current efficiency as that on the Ni anode and addition of Si to the nickel matrix is effective for decreasing anode consumption largely. A Ni sheet electrode containing a trace of impurities, such as Co, Mn, Ag and Al, is also favorable as the anode for electrolytic production of NF3. 相似文献
92.
Herbert Schumann Sebastian Dechert Frank Girgsdies Bernd Heymer Markus Hummert Ji‐Young Hyeon Jens Kaufmann Stefan Schutte Sonja Wernik Birgit C. Wassermann 《无机化学与普通化学杂志》2006,632(2):251-263
Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{μ‐O(CH2)3NMe2}]2 ( 1a ), Me2AlOC6H2(CH2NMe2)3‐2,4,6 ( 2a ), [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]2 ( 3a ) and [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NHCH2Ph}]2 ( 4 ) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH2OH, or (S)‐PhCH2NHCH(i‐Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)2OH, Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH2OH producing the “pick‐a‐back” complexes [Me2AlO(CH2)2NMe2](AlMe3) ( 5 ), [Me2AlO(CH2)3NMe2](AlMe3) ( 1b ), [Me2AlOC6H2(CH2NMe2)3‐2,4,6](AlMe3)2 ( 2b ), and [(S)‐Me2AlOCH2CH(i‐Pr)NH‐i‐Pr](AlMe3) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 6 ) and [{CH2=C(CH3)}(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 8 ) are to obtain from Me2AlCl and Me2N(CH2)2OH and from [Cl2Al{μ‐O(CH2)2NMe2}]2 ( 7 ) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{μ‐O(CH2)3NMe2}]2 ( 9 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]n ( 10 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NHCH2Ph}]n ( 11 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)N(Me)CH2Ph}]n ( 12 ) and [(S)‐Me2Ga{μ‐OCH2(C4H7NHCH2Ph)}]n ( 13 ) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1H‐, 13C‐ and 27Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction. 相似文献
93.
D. W. Davidson Y. P. Handa C. I. Ratcliffe J. A. Ripmeester J. S. Tse J. R. Dahn 《Molecular Crystals and Liquid Crystals》2013,570(1-2):141-149
Low-temperature neutron and X-ray diffraction studies show the gas hydrates of oxygen and nitrogen to be structure II (Fd3m), as recently found also for the hydrates of the small argon and krypton molecules. New lattice parameters of three structure I and 14 structure II hydrates from powder X-ray diffraction at 170 K are reported. The thermal expansion coefficient of tetrahydrofuran hydrate was determined from X-ray diffraction at some 50 temperatures between 18 and 263 K and found to be three times as great as for ice near 100 K and 30% higher near 250 K. Lattice parameters qf 40 type II clathrate hydrates are compared at 0°C and found to lie within 0.10 Å of 17.30 Å. 相似文献
94.
95.
Auf der Grundlage des Zirkulations-Diffusions-Prinzips wurden zwei Trennrohre für die Hochanreicherung von Gasen enytwickelt. Als Modellgasmischungen dienten H2-N2 Kr-CH4 und Luft. Neben Wasserdampf wurden Methanol- und Äthaanoldämpfe als Treibmittel benutzt. Gute Trennungen wurden in einem nur 20 cm langen Rohr erzielt, dessen Trennspalt horizontal durch Lamellen in kleine Sektionen und durch ein Drahtdiaphragma vertikal in zwei Ringkammern geteilt wird. Drei Rohre dieses Typs wurden in einer rechteckigen Kaskadenanordnung getestet. Die Theorie des Transportes im Trennrohr sowie die Behandlung des hydrodynamischen Problems werden angegeben. Eine Anwendung des beschriebenen Trennrohres zur Isotopentrennung und zur Gashochanreicherung erscheint aussichtsreich. 相似文献
96.
97.
Tianyong Liu Qian Dang Xunhui Zhou Jin Li Zhen Ge Hang Che Prof. Shaobin Tang Prof. Yi Luo Prof. Jun Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(23):6945-6953
Developing the low-cost and efficient single-atom catalysts (SACs) for nitrogen reduction reaction (NRR) is of great importance while remains as a great challenge. The catalytic activity, selectivity and durability are all fundamentally related to the elaborate coordination environment of SACs. Using first-principles calculations, we investigated the SACs with single transition metal (TM) atom supported on defective boron carbide nitride nanotubes (BCNTs) as NRR electrocatalysts. Our results suggest that boron-vacancy defects on BCNTs can strongly immobilize TM atoms with large enough binding energy and high thermal/structural stability. Importantly, the synergistic effect of boron nitride (BN) and carbon domains comes up with the modifications of the charge polarization of single-TM-atom active site and the electronic properties of material, which has been proven to be the essential key to promote N2 adsorption, activation, and reduction. Specifically, six SACs (namely V, Mn, Fe, Mo, Ru, and W atoms embedded into defective BCNTs) can be used as promising candidates for NRR electrocatalysts as their NRR activity is higher than the state-of-the art Ru(0001) catalyst. In particular, single Mo atom supported on defective BCNTs with large tube diameter possesses the highest NRR activity while suppressing the competitive hydrogen evolution reaction, with a low limiting potential of −0.62 V via associative distal path. This work suggests new opportunities for driving NH3 production by carbon-based single-atom electrocatalysts under ambient conditions. 相似文献
98.
Prof. Dr. Axel Schulz Dr. Alexander Villinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2032-2038
Pure, solvent‐free Zn(N3)2 was prepared by reaction of diethyl zinc and hydrazoic acid in aprotic solvents. The single‐crystal structure determination, along with the comprehensive characterization of α‐Zn(N3)2 and two metastable polymorphs, could be achieved for the first time. Since these data disagree in large parts with the known, previously reported values, all previous syntheses of Zn(N3)2, and for comparison Zn(N3)2?2.5 H2O and Zn(OH)N3 were reinvestigated, indicating that some of the earlier work has to be revised. 相似文献
99.
Structure of Amido Pyridinium Betaines: Persistent Intermolecular C−H⋅⋅⋅N Hydrogen Bonding in Solution
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Dr. Robert J. Thatcher Dr. David G. Johnson Dr. John M. Slattery Dr. Richard E. Douthwaite 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3414-3421
A hydrogen bond of the type C?H???X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C?H???O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C?H???N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C?H???N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C?H???N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol?1 per hydrogen bond, which is similar to chemically and biologically relevant C?H???O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts. 相似文献
100.
Bomin Feng Xiuju Wu Ling Li Wei Gao Dr. Weihua Hu Prof. Chang Ming Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(49):11560-11565
It remains challenging to rationally synthesize iron/nitrogen-doped carbon (Fe/N-C) catalysts with rich Fe−Nx atomic active sites for improved oxygen reduction reaction (ORR) electrocatalysis. A highly efficient Fe/N-C catalyst, which has been synthesized through a spatial isolation strategy, is reported. Derived from bioinspired polydopamine (PDA)-based hybrid microsphere precursors, it is a multifunctional carrier that loads atomically dispersed Fe3+/Zn2+ ions through coordination interactions and N-rich melamine through electrostatic attraction and covalent bonding. The Zn2+ ions and melamine in the precursor efficiently isolate Fe3+ atoms upon pyrolysis to form rich Fe−Nx atomic active sites, and generate abundant micropores during high-temperature treatment; as a consequence, the resultant Fe-N/C catalyst contains rich catalytically active Fe−Nx sites and a hierarchical porous structure. The catalyst exhibits improved ORR activity that is superior to and close to that of Pt/C in alkaline and acidic solutions, respectively. 相似文献