全文获取类型
收费全文 | 2266篇 |
免费 | 151篇 |
国内免费 | 152篇 |
专业分类
化学 | 966篇 |
晶体学 | 129篇 |
力学 | 45篇 |
综合类 | 9篇 |
数学 | 248篇 |
物理学 | 474篇 |
无线电 | 698篇 |
出版年
2024年 | 4篇 |
2023年 | 18篇 |
2022年 | 36篇 |
2021年 | 42篇 |
2020年 | 63篇 |
2019年 | 54篇 |
2018年 | 42篇 |
2017年 | 66篇 |
2016年 | 84篇 |
2015年 | 91篇 |
2014年 | 107篇 |
2013年 | 129篇 |
2012年 | 162篇 |
2011年 | 115篇 |
2010年 | 110篇 |
2009年 | 156篇 |
2008年 | 140篇 |
2007年 | 101篇 |
2006年 | 117篇 |
2005年 | 100篇 |
2004年 | 100篇 |
2003年 | 83篇 |
2002年 | 102篇 |
2001年 | 75篇 |
2000年 | 59篇 |
1999年 | 57篇 |
1998年 | 51篇 |
1997年 | 43篇 |
1996年 | 32篇 |
1995年 | 43篇 |
1994年 | 27篇 |
1993年 | 19篇 |
1992年 | 31篇 |
1991年 | 15篇 |
1990年 | 17篇 |
1989年 | 13篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有2569条查询结果,搜索用时 15 毫秒
51.
A novel and simple flow-based method was developed for the simultaneous determination of As(III) and As(V) in freshwater samples. Two miniature columns with a solid phase anion exchange resin, placed on two 6-way valves were utilized for the solid-phase collection/concentration of arsenic(III) and arsenic(V), respectively. As(III) could be retained on the column after its oxidation to As(V) species with an oxidizing agent. The collected analytes were then sequentially eluted by 2 M nitric acid and introduced into ICP-AES. Potassium permanganate was examined as potential oxidizing agent for conversion of As(III) to As(V). The standard deviation of the analytical signals (peak height) for the replicate analysis (n = 5) of 0.5 μg l−1 solution were 3 and 5% for As(III) and As(V), respectively. The limit of detection (3σ) for both As(III) and As(V) were 0.1 μg l−1. The proposed system produced satisfactory results on the application to the direct analysis of inorganic arsenic species in freshwater samples. 相似文献
52.
J.W. Guthrie M.S.A. Salam C.A. Murimboh C.L. Chakrabarti D.C. Grégoire 《Analytica chimica acta》2005,528(2):205-218
Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V. 相似文献
53.
G. Tav?ar 《Journal of fluorine chemistry》2004,125(11):1579-1584
A new class of coordination compounds of the type [Mn+(L)p](AF6−)n and [Mn+(L)r](BF4−)n, where M is Mg, Ca, Sr, Ba, Cd, Pb, lanthanides, A is P, As, Sb, Bi and L is XeF2, XeF4, XeF6, KrF2, was studied. A review of all known coordination compounds with L is XeF2 is given: (a) synthetic routes for the preparation of these compounds; (b) analysis of their crystal structures (molecular, dimer, chain, double chain, layer, strongly interconnected double layers and three-dimensional network); (c) the influence of the ligand XeF2 (small formula volume, linear, semi-ionic, charge of −0.5e on each F ligand); (d) the influence of the central metal ion; (e) the influence of the anions: AF6− and BF4− (the formula volume, Lewis basicity). On the basis of all properties of the metal ions, ligand and anions the obtained variety of the structures is analyzed. 相似文献
54.
Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献
55.
Fe3+/V5+/TiO2复合纳米微粒光催化性能的研究 总被引:29,自引:1,他引:29
采用溶胶凝胶法制备了Fe^3 /V^5 /TiO2复合纳米微粒作为光催化剂。光降解反应结果表明,其掺杂催化剂Fe^3 /V^5 /TiO2的光催化活性明显提高。光电化学研究显示,铁离子可以成为电荷陷阱,促进空穴的界面传递反应。适量钒离子掺杂使TiO2电极的光电流升高,导带中电子浓度的增大,加快了界面的电子传递反应。共掺杂催化剂中,Fe^3 、V^5 分别提供了空穴与电子的陷阱,同时加快了电子与空穴的界面传递反应,从 更有效地提高光催化活性。双组份共掺杂为提高TiO2光催化活性提供新的途径。 相似文献
56.
We present a new set of V–V rate coefficients for vibrational levels 0–5 in H2 at 300 K, measured using a stimulated Raman–spontaneous Raman pump/probe apparatus. The measured rate of the non-resonant process, H2(v = 1) + H2(v = 1) → H2(v = 0) + H2(v = 2), is consistent with the previously reported experimental value of Kreutz et al. However, semi-classical predictions of such non-resonant processes, using the identical inter-molecular potential and methodology to that given by Cacciatore and Billing, results in rates which are too slow, by a factor of approximately 3. For the “resonant” V–V process, H2(v = 1) + H2(v = 0) → H2(v = 0) + H2(v = 1), the semi-classical rate is found to be too slow by an even larger factor, of approximately 30, compared to the experimental rate, but consistent with the previously reported experimental result of Farrow and Chandler. Further, unlike the semi-classical model prediction in which the (1, 1 → 2, 0) process rate is predicted to exceed that of the (1, 0 → 0, 1) process, the experimental data shows it to be a factor of approximately 2.5 less, suggesting that semi-classical methods that treat the rotational motion classically are unsuitable for the highly anharmonic H2 molecule. The ratio of pure rotation and rotation–vibration Raman cross sections for scattering from levels 0 and 1 is also determined, with results which agree with calculations of Schwartz and LeRoy, but are somewhat larger than previous experimental results of Cureton. 相似文献
57.
FlorianC. Stintzing Florian Kugler Reinhold Carle Jürgen Conrad 《Helvetica chimica acta》2006,89(5):1008-1016
Due to their inherent liability towards highly acidic conditions previously considered to be a prerequisite for data acquisition, betaxanthin structure dereplication by NMR spectroscopy has been scarcely reported and was, hitherto, exclusively based on 1H‐NMR data interpretation. Applying only slightly acidic conditions, we herein report the first 13C‐NMR data of two betaxanthins, i.e., indicaxanthin ( 1 ), isolated from yellow‐orange cactus pear fruits (Opuntia ficus‐indica [L.] Mill . cv. ‘Gialla’), and of miraxanthin V ( 2 ) from yellow Swiss chard petioles (Beta vulgaris L. ssp. cicla [L.] Alef . cv. ‘Bright Lights’), as derived by gHSQC‐ and gHMQC‐NMR experiments and inverse detection. 相似文献
58.
铜掺杂五氧化二钒的制备及电化学性质 总被引:1,自引:0,他引:1
采用沉淀法于300 和600 ℃制备了结晶状的Cu0.04V2O5材料. 扫描电镜显示, 300 ℃时制备的样品具有多孔特征, 而600 ℃时制备的样品具有很高的结晶度. X射线研究表明, 少量铜掺杂不会改变V2O5的正交晶体结构. 红外光谱研究表明, 300 ℃时制备的Cu0.04V2O5样品含有少量水. 热失重分析确定了样品中所含水分是以吸附水的形式存在, 1 mol材料分子吸附水的摩尔数约为0.18 mol. 铜掺杂显著改善了V2O5的结构稳定性, 进而提高了材料的充放电循环性能. 于600 ℃制备的样品在C/5.6倍率下具有160 mAh·g-1的可逆比容量, 但提高放电倍率明显降低了材料的循环性能. 于300 ℃制备的样品在C/5.6倍率时的循环性能不如600 ℃样品, 但该材料在C/1.9倍率时仍具有100 mAh·g-1左右的可逆比容量. 两种材料在电化学性能上的差异与材料的微结构有关. 低温样品在较高放电倍率时良好的循环性能得益于其多孔的微结构, 而高温样品由于其较高的结晶度而表现出优异的低倍率充放电性能. 相似文献
59.
The kinetics of polymerization of acrylonitrile (AN) initiated by quinquevalent vanadium (V~(5+))-thiourea (TU) redox system has been investigated in aqueous nitric acid in the temperature range from 30 to 50℃. The polymerization rate (R_p) can be expressed as follows: In the copolymerization of acryionitrile with methyl acrylate (MA), the reactivity ratios were found to be 1.0 and 1.1, respectively. The experimental observations suggest that the initiating species is probably a complex consisting of a central ion of Lewis acid-VO_2~+ and the ligands of Lewis bases-acrylonitrile, thiourea, and nitrate anions, while the initiating system in lower concentration, the polymerization of acrylonitrile does not occur if the thiourea is acidified prior to its reaction with quinquevalent vanadium. This indicates that the primary radicals (or the monomeric radicals in the present article) are produced by associated thiourea rather than isothlourea. 相似文献
60.
S. J. Pearton U. K. Chakrabarti A. Katz A. P. Perley W. S. Hobson M. Geva 《Plasma Chemistry and Plasma Processing》1991,11(4):405-422
A systematic study has been performed of the dry etching characteristics of GaAs, Al0.3Ga0.7As, and GaSb in chlorine-based electron cyclotron resonance (ECR) discharges. The gas mixtures investigated were CCl2F2/O2, CHCl2F/O2, and PCl3. The etching rates of all three materials increase rapidly with applied RF power, while the addition of the microwave power at moderate levels (150 W) increases the etch rates by 20–80%. In the microwave discharges, the etch rates decrease with increasing pressure, but at 1 m Torr it is possible to obtain usable rates for self-bias voltages 100 V. Of the Freon-based mixtures, CHCl2F provides the least degradation of optical (photoluminescence) and electrical (diode ideality factors and Schottky barrier heights) properties of GaAs as a result of dry etching. Smooth surface morphologies are obtained on all three materials provided the microwave power is limited to 200 W. Above this power, there is surface roughening evident with all of the gas mixtures investigated. 相似文献