全文获取类型
收费全文 | 3465篇 |
免费 | 604篇 |
国内免费 | 313篇 |
专业分类
化学 | 917篇 |
晶体学 | 43篇 |
力学 | 1700篇 |
综合类 | 49篇 |
数学 | 252篇 |
物理学 | 1421篇 |
出版年
2024年 | 13篇 |
2023年 | 36篇 |
2022年 | 90篇 |
2021年 | 122篇 |
2020年 | 154篇 |
2019年 | 99篇 |
2018年 | 86篇 |
2017年 | 144篇 |
2016年 | 164篇 |
2015年 | 136篇 |
2014年 | 171篇 |
2013年 | 251篇 |
2012年 | 173篇 |
2011年 | 202篇 |
2010年 | 153篇 |
2009年 | 173篇 |
2008年 | 199篇 |
2007年 | 193篇 |
2006年 | 170篇 |
2005年 | 191篇 |
2004年 | 157篇 |
2003年 | 158篇 |
2002年 | 129篇 |
2001年 | 118篇 |
2000年 | 134篇 |
1999年 | 113篇 |
1998年 | 102篇 |
1997年 | 72篇 |
1996年 | 80篇 |
1995年 | 49篇 |
1994年 | 64篇 |
1993年 | 53篇 |
1992年 | 32篇 |
1991年 | 40篇 |
1990年 | 33篇 |
1989年 | 23篇 |
1988年 | 27篇 |
1987年 | 17篇 |
1986年 | 12篇 |
1985年 | 18篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有4382条查询结果,搜索用时 0 毫秒
81.
R. A. Manzhos B. I. Podlovchenko Yu. M. Maksimov 《Russian Journal of Electrochemistry》2006,42(6):658-664
Transients of the open-circuit potential, which are observed when formic acid is interacting wit adsorbed oxygen (Oads) preliminarily accumulated on polycrystalline “smooth” platinum (pcPt), are measure in an aqueous solution of sulfuric acid. It is shown that, as with platinized platinum (Pt/Pt), at large coverage by adsorbed oxygen (θO = 1?0.8), adsorbed oxygen interacts directly with molecules of formic acid from solution. In the region of medium coverages (θO = 0.8?0.2), on the other hand, a mechanism of “conjugated reactions” is realized. It is established that, in the case of pcPt, the direct interaction of Oads with molecules of HCOOH from solution proceeds slower by nearly three times and the interaction via the mechanism of “conjugated reactions,” faster by about three times, as compared with Pt/Pt. 相似文献
82.
Kalliopi Kousi Dragos Neagu Leonidas Bekris Evangelos I. Papaioannou Ian S. Metcalfe 《Angewandte Chemie (International ed. in English)》2020,59(6):2510-2519
Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies. 相似文献
83.
Dr. Qingwei Zhou Prof. Jialong Duan Prof. Xiya Yang Dr. Yanyan Duan Prof. Qunwei Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22181-22185
Perovskite lattice distortion induced by residual tensile strain from the thermal expansion mismatch between the electron-transporting layer (ETL) and perovskite film causes a sluggish charge extraction and transfer dynamics in all-inorganic CsPbBr3 perovskite solar cells (PSCs) because of their higher crystallization temperatures and thermal expansion coefficients. Herein, the interfacial strain is released by fabricating a WS2/CsPbBr3 van der Waals heterostructure owing to their matched crystal lattice structure and the atomically smooth dangling bond-free surface to act as a lubricant between ETL and CsPbBr3 perovskite. Arising from the strain-released interface and condensed perovskite lattice, the best device achieves an efficiency of 10.65 % with an ultrahigh open-circuit voltage of 1.70 V and significantly improved stability under persistent light irradiation and humidity (80 %) attack over 120 days. 相似文献
84.
This work deals with uncertainty analysis of the thermal conductivity measurement using the transient hot wire method. The characterization is made from a sample of low-density, polyethylene BRALEN SA 200-22. The utilized experimental data are obtained from the test measurements performed on the air at room temperature. The sources of measurement errors are analyzed and the uncertainty of the measured value of the thermal conductivity is evaluated. The analysis shows that in the present case the uncertainty of the thermal conductivity measurement is about ±3.3% for 68% confidence level.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
85.
Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us… 相似文献
86.
Ring strain energies (RSEs) are predicted using homodesmotic reactions at the B3LYP/6-31G* level of theory. Substituents are conserved in the acyclic reference and any difference in energy between the ring and the acyclic reference corresponds exclusively to RSE. Small rings are stabilized by alkyl substituents and this stabilization decreases as the size of the ring increases. There is a destabilization of medium sized rings. Greater stabilization is found upon alkyl substitution at a double bond in an unsaturated ring and this stabilization decreases as ring size increases. The effects of cis-1,2-disubstitution on RSEs have been evaluated and indicate stabilization for both small and medium sized rings. RSEs of saturated and unsaturated polycyclic systems agree well with the RSEs derived from experimental thermochemical data. RSEs are reported for substituted norbornanes, norbornenes, and norbornadienes to complement experimental studies. 相似文献
87.
Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study 下载免费PDF全文
Dr. Benedetta Carlotti Dr. Enrico Benassi Prof. Vincenzo Barone Dr. Giuseppe Consiglio Prof. Fausto Elisei Dr. Alessandra Mazzoli Prof. Anna Spalletti 《Chemphyschem》2015,16(7):1440-1450
Three (donor–π–acceptor)+ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials. 相似文献
88.
Acceleration of Long‐Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs 下载免费PDF全文
Dr. Effi Bätzner Dr. Yu Liang Caroline Schweigert Dr. Andreas‐Neil Unterreiner Prof. Dr. Hans‐Achim Wagenknecht 《Chemphyschem》2015,16(8):1607-1612
The C‐nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq–Hq pairs in double‐stranded DNA. These artificial Hq–Hq pairs may serve as artificial electron carriers for long‐range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time‐resolved transient absorption spectroscopy. For this study, the Hq–Hq pair was combined with a DNA‐based donor–acceptor system consisting of 6‐N,N‐dimethylaminopyrene conjugated to 2′‐deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2′‐position of uridine as electron acceptor. The Hq radical anion was identified in the time‐resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq–Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self‐assembly properties as the most attractive feature of DNA as a supramolecular architecture. 相似文献
89.
Rosario Benavente Ernesto Prez Raúl Quijada 《Journal of Polymer Science.Polymer Physics》2001,39(3):277-285
Stress–strain and microhardness measurements were carried out on a series of copolymers of ethylene and 1‐octadecene with different comonomer contents in the corresponding homopolymer of ethylene, synthesized with a metallocene catalyst. The different mechanical properties, deduced from the stress–strain curves (Young's modulus, yield stress, deformation at break, and energy to break) are interpreted in terms of the crystallinity and molecular weight of the samples because these two characteristics show considerable variations with the comonomer content. The microhardness values are explained in terms of these properties, and they are also correlated with Young's moduli and yield stresses deduced from the stress–strain curves. Linear relations are found between microhardness and yield stress and between the logarithm of the microhardness and the logarithm of the elastic modulus. The properties deduced from these lines are compared with literature values. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 277–285, 2001 相似文献
90.
In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis
of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance
of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously
exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of
white rust θ
2(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting
parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and
to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ
2(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values
of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion
resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with
the polarization resistance of the upper resin coating layer R
p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value
as well with increasing R
p. 相似文献