全文获取类型
收费全文 | 447篇 |
免费 | 14篇 |
国内免费 | 1篇 |
专业分类
化学 | 339篇 |
晶体学 | 5篇 |
力学 | 5篇 |
数学 | 8篇 |
物理学 | 105篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 6篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 8篇 |
2015年 | 8篇 |
2014年 | 14篇 |
2013年 | 23篇 |
2012年 | 24篇 |
2011年 | 32篇 |
2010年 | 15篇 |
2009年 | 11篇 |
2008年 | 30篇 |
2007年 | 14篇 |
2006年 | 26篇 |
2005年 | 23篇 |
2004年 | 11篇 |
2003年 | 20篇 |
2002年 | 21篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 11篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 5篇 |
1971年 | 2篇 |
1967年 | 1篇 |
排序方式: 共有462条查询结果,搜索用时 578 毫秒
11.
Commercially available powdered photocatalysts such as P-25 are known to show high photocatalytic performance. However, in practical use, their anchoring onto a substrate without any binders is still very difficult. The purpose of this study is to design and develop high-performance photocatalysts that can be anchored onto a substrate, and to this end we have prepared a titanium oxide photocatalyst using a wet process. The results of this study led to the successful development of rectangular column structured titanium oxide crystals which could be anchored onto silica sheets. The rectangular columnar crystal was 100- 500 nm wide and 1000- 5000 nm long. Moreover, investigations on the complete oxidation reaction of acetaldehyde into CO2 and H2O showed a high performance equivalent to that of the most efficient marketed powdered photocatalysts. 相似文献
12.
Hara K Wang ZS Sato T Furube A Katoh R Sugihara H Dan-Oh Y Kasada C Shinpo A Suga S 《The journal of physical chemistry. B》2005,109(32):15476-15482
We have developed oligothiophene-containing coumarin dyes fully functionalized for dye-sensitized nanocrystalline TiO(2) solar cells (DSSCs). DSSCs based on the dyes gave good performance in terms of incident photon-to-current conversion efficiency (IPCE) in the range of 400-800 nm. A solar energy-to-electricity conversion efficiency (eta) of 7.4% was obtained with a DSSC based on 2-cyano-3-[5'-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-[2,2']bithiophenyl-5-yl]acrylic acid (NKX-2677) under simulated AM 1.5G irradiation (100 mW cm(-2)) with a mask: short-circuit current density (J(sc)) = 13.5 mA cm(-2); open-circuit voltage (V(oc)) = 0.71 V; fill factor (FF) = 0.77. Transient absorption spectroscopy measurements indicated that electron injection from NKX-2677 to the conduction band of TiO(2) is very rapid (<100 fs), which is much faster than the emission lifetime of the dye (1.0 ns), giving a highly efficient electron injection yield of near unity. 相似文献
13.
14.
Sotoyama W Satoh T Sato H Matsuura A Sawatari N 《The journal of physical chemistry. A》2005,109(43):9760-9766
The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results. 相似文献
15.
Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation. 相似文献
16.
Properties of Sr2Cu(PO4)2 and Ba2Cu(PO4)2 having [Cu(PO4)2]∞ linear chains in their structures with Cu-O-P-O-Cu linkages were studied by magnetic susceptibility (T=2-400 K, H=100 Oe) and specific heat measurements (T=0.45-21 K). Magnetic susceptibility versus temperature curves, χ(T), showed broad maxima at TM=92 K for Sr2Cu(PO4)2 and TM=82 K for Ba2Cu(PO4)2 characteristic of quasi-one-dimensional systems. The χ(T) data were excellently fitted by the spin susceptibility curve for the uniform S=1/2 chain (plus temperature-independent and Curie-Weiss terms) with g=2.153(4) and J/kB=143.6(2) K for Sr2Cu(PO4)2 and g=2.073(4) and J/kB=132.16(9) K for Ba2Cu(PO4)2 (Hamiltonian H=JΣSiSi+1). The similar J/kB values were obtained from the specific heat data. No anomaly was observed on the specific heat from 0.45 to 21 K for both compounds indicating that the temperatures of long-range magnetic ordering, TN, were below 0.45 K. Sr2Cu(PO4)2 and Ba2Cu(PO4)2 are an excellent physical realization of the S=1/2 linear chain Heisenberg antiferromagnet with kBTN/J<0.34% together with Sr2CuO3 (kBTN/J≈0.25%) and γ-LiV2O5 (kBTN/J<0.16%). Sr2Cu(PO4)2 and Ba2Cu(PO4)2 were stable in air up to 1280 and 1150 K, respectively. 相似文献
17.
Masao Matsuoka Tsuyoshi Matsuda June Tamaki Yoshifumi Yamamoto Chiaki Iwakura 《Research on Chemical Intermediates》2006,32(5):389-402
Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based
material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification
of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty
was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM
observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy
with a composition of Zr0.9Ti0.1Ni1.1Co0.1Mn0.5V0.2Cr0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing
mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic
stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and
diffusion path length of hydrogen. 相似文献
18.
Wang ZS Hara K Dan-oh Y Kasada C Shinpo A Suga S Arakawa H Sugihara H 《The journal of physical chemistry. B》2005,109(9):3907-3914
A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface. 相似文献
19.
Carbamoylimidazolium salts act as efficient N,N-disubstituted carbamoylating reagents. These salts are readily prepared by the sequential treatment of secondary amines with N,N′-carbonyldiimidazole (CDI) and iodomethane. The carbamoylimidazolium salts are more efficient carbamoyl transfer reagents than the intermediate carbamoylimidazoles, as a result of the ‘imidazolium’ effect. Kinetic studies on the base promoted hydrolysis of both carbamoylimidazoles and carbamoylimidazolium salts reveal over a hundred-fold rate acceleration. The salts react with amines, thiols, phenols/alcohols, and carboxylic acids in high yields, without the need for subsequent chromatographic purification of the products, producing ureas, thiocarbamates, carbamates, and amides, respectively. Analogous thiocarbamoylimidazolium salts were also synthesized from secondary amines and N,N′-thiocarbonyldiimidazole (TCDI), followed by methylation with iodomethane. 相似文献
20.
Hiroatsu Matsuura Yoshiyuki Kawashima Chiaki Hirose 《Journal of Molecular Structure》1974,20(2):205-212
The rotational constant B and the l-type doubling constant q were determined for the v5, v3+v6 and v2, states of CH2I from the microwave transition frequencies, in combination with the infrared data previously reported. Since these vibrational states were coupled through the Fermi resonance and the xy-type E-E and A1-E Coriolis resonances, the analysis was made by setting up and solving the complete form of the secular determinants of the energy matrices. The rotational and l-type doubling constants were determined as B5, = 0.250 173 cm?1, B36 = 0.247 600 cm?1, B2 = 0.249 369 cm?1, q5 = ?0.000 027 cm?1 and q36 = ?0.000 179 cm?1, which are unperturbed by Fermi and Coriolis interactions. Other band constants for v5 and v3+v6 were also refined in accordance with the new values of B5 and B36. The present study indicated that the combined analysis of microwave and infrared spectral data was useful for the precise determination of vibration-rotation, levels in the perturbed system. 相似文献