首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1463篇
  免费   49篇
  国内免费   7篇
化学   630篇
晶体学   20篇
力学   68篇
数学   263篇
物理学   538篇
  2023年   11篇
  2022年   12篇
  2021年   31篇
  2020年   35篇
  2019年   41篇
  2018年   43篇
  2017年   30篇
  2016年   54篇
  2015年   42篇
  2014年   59篇
  2013年   90篇
  2012年   95篇
  2011年   112篇
  2010年   92篇
  2009年   73篇
  2008年   70篇
  2007年   84篇
  2006年   45篇
  2005年   61篇
  2004年   31篇
  2003年   33篇
  2002年   23篇
  2001年   13篇
  2000年   21篇
  1999年   18篇
  1998年   9篇
  1997年   13篇
  1996年   26篇
  1995年   21篇
  1994年   12篇
  1993年   19篇
  1992年   11篇
  1991年   11篇
  1990年   5篇
  1989年   9篇
  1988年   11篇
  1987年   9篇
  1986年   10篇
  1985年   14篇
  1984年   10篇
  1983年   5篇
  1982年   7篇
  1981年   14篇
  1980年   13篇
  1979年   10篇
  1978年   6篇
  1977年   11篇
  1976年   7篇
  1974年   6篇
  1973年   6篇
排序方式: 共有1519条查询结果,搜索用时 31 毫秒
1.
We investigate the possibility of phantom crossing in the dark energy sector and the solution for the Hubble tension between early and late universe observations. We use robust combinations of different cosmological observations, namely the Cosmic Microwave Background (CMB), local measurement of Hubble constant (H0), Baryon Acoustic Oscillation (BAO) and SnIa for this purpose. For a combination of CMB+BAO data that is related to early universe physics, phantom crossing in the dark energy sector was confirmed at a 95% confidence level and we obtained the constraint H0=71.03.8+2.9 km/s/Mpc at a 68% confidence level, which is in perfect agreement with the local measurement by Riess et al. We show that constraints from different combinations of data are consistent with each other and all of them are consistent with phantom crossing in the dark energy sector. For the combination of all data considered, we obtained the constraint H0=70.25±0.78 km/s/Mpc at a 68% confidence level and the phantom crossing happening at the scale factor am=0.8510.031+0.048 at a 68% confidence level.  相似文献   
2.

CO2 and steam/CO2 electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnOmix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnOinf –Ag cathode). ZnOmix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO2 and H2/CO2 (4:1 v/v). A maximum overall CO2 conversion of 48% (in H2/CO2) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO2 electroreduction. It was further revealed that for ZnOinf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnOmix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO2 electrolysis. Although ZnOinf –Ag cathode produced trace amount of methane at higher voltages, with ZnOmix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.

  相似文献   
3.
Phenol and its derivatives are extremely useful compounds in organic synthesis, medicinal chemistry and material sciences. The synthesis of phenols involving selective construction of the C?O bond at a C?H bond of arenes using transition‐metal catalysis represents the most appealing strategy. Indeed, active research is currently going on for the synthesis of valuable phenolic compounds using a transition‐metal‐catalyzed C?H functionalization strategy. This short review summarizes recent advances on palladium‐catalyzed C?O bond forming reactions that enable direct access to phenolic compounds. These catalytic reactions proceed either via C?H esterification with trifluoroacetic acid/trifluoroacetic anhydride followed by in situ hydrolysis of the ester or via direct C?H hydroxylation. A brief analysis of substrate scope and limitation, reaction mechanism as well as synthetic utility of these reactions has been included.  相似文献   
4.
Extensive density functional theory calculations are performed to analyze the structure and activity of Cu and Cu Zn/Cu ZnO clusters containing up to 10 Cu/Zn atoms. The minimum-energy structures of Cu Zn and Cu ZnO clusters are found by doping minimum-energy pure Cu clusters with Zn atom(s) and ZnO molecule(s), respectively, followed by energy minimization of the resultant clusters. Odd-even alteration in properties that determine cluster stability/activity is observed with cluster size, which may be attributed to the presence/absence of unpaired electrons. The difference in behavior between Zn/ZnO doping can be interpreted in terms of charge transfer between atoms. Charge transfers from Zn to Cu in the Cu Zn clusters and from Cu and Zn atoms to O atom in Cu-ZnO clusters, which implies that the Cu atom acts as an electron acceptor in the Cu Zn clusters but not in the Cu ZnO clusters. Finally, the adsorption energies of glycerol and hydrogen on Cu Zn/Cu ZnO clusters are computed in the context of the use of Cu Zn/Cu ZnO catalysts in glycerol hydrogenolysis. Glycerol adsorption is generally found to be more energetically favorable than hydrogen adsorption. Dual-site glycerol adsorption is also observed in some of the planar clusters. Fundamental insights obtained in this study can be useful in the design of Cu Zn/Cu ZnO catalysts.  相似文献   
5.
ABSTRACT

The article deals with the study of plane wave propagation in the thermoelastic medium in the presence of voids. The problem is considered in the context of three-phase-lag model of generalized thermoelasticity. There exists three longitudinal waves, namely elastic (E-mode), thermal (T-mode) and volume fraction (V-mode) in addition to transverse waves which get decoupled from the rest of motion and not affected by thermal and volume fraction fields. The fundamental solution of the system of differential equations in case of steady oscillations in terms of the elementary functions has been constructed. The phase velocity and attenuation coefficient of these waves are computed numerically and presented graphically.  相似文献   
6.
7.
8.
9.
A new HfIV‐based metal‐organic framework with UiO‐66 topology was synthesized via a one‐step solvothermal method by using 3‐methyl‐4‐phenylthieno[2,3‐b]thiophene‐2,5‐dicarboxylic acid (H2MPTDC) as a ligand. The MOF material showed a high stability in a broad pH range (from pH 2 to pH 12) in an aqueous medium. The presence of hydrophobic methyl and phenyl substituents in the carboxylic acid ligand and strong Hf?O bond play crucial roles in its stability. The new MOF material was systematically characterized by various techniques such as XRPD, N2 sorption, thermogravimetric analyses and FT‐IR spectroscopy. The photophysical properties of the MOF material were also examined by steady‐state and time‐resolved fluorescence studies. It was observed that the blue fluorescence of the MOF material was selectively quenched in the presence of Fe3+ ion in pure aqueous medium. A mechanistic study disclosed that quenching occurs via a strong inner filter effect (IFE) arising from Fe3+ ion in aqueous medium. Interestingly, the fluorescence of the MOF material can be recovered by elimination of the IFE of Fe3+ ion via reduction of Fe3+ ion by ascorbic acid (AA). Based on the fluorescence recovery by AA, a MOF based on‐off‐on probe was developed for the sensing of Fe3+ ion and AA in aqueous medium. Inspired by this reversible sensing event, we demonstrate basic (NOT, OR, YES, INHIBIT and IMP) and higher integrated logic operations utilizing this fluorescent MOF. This MOF‐based logic systems could be potentially used for next‐generation logic‐gate based analytical applications as well as for the detection and discrimination of targeted molecules in various complex domains.  相似文献   
10.
Three isostructural lanthanide‐based two‐ dimensional coordination polymers (CPs) {[Ln2(L)3(H2O)2]n ? 2n CH3OH) ? 2n H2O} (Ln=Gd3+ ( 1 ), Tb3+ ( 2 ), Dy3+ ( 3 ); H2L=cyclobutane‐1,1‐dicarboxylic acid) were synthesized by using a low molecular weight dicarboxylate ligand and characterized. Single‐crystal structure analysis showed that in complexes 1 – 3 lanthanide centers are connected by μ3‐bridging cyclobutanedicarboxylate ligands along the c axis to form a rod‐shaped infinite 1D coordination chain, which is further linked with nearby chains by μ4‐connected cyclobutanedicarboxylate ligands to form 2D CPs in the bc plane. Viewing the packing of the complexes down the b axis reveals that the lattice methanol molecules are located in the interlayer space between the adjacent 2D layers and form H‐bonds with lattice and coordinated water molecules to form 1D chains. Magnetic properties of complexes 1 – 3 were thoroughly investigated. Complex 1 exhibits dominant ferromagnetic interaction between two nearby gadolinium centers and also acts as a cryogenic magnetic refrigerant having a significant magnetic entropy change of ?ΔSm=32.8 J kg?1 K?1 for ΔH=7 T at 4 K (calculated from isothermal magnetization data). Complex 3 shows slow relaxation of magnetization below 10 K. Impedance analysis revealed that the complexes show humidity‐dependent proton conductivity (σ=1.5×10?5 S cm?1 for 1 , σ=2.07×10?4 S cm?1 for 2 , and σ=1.1×10?3 S cm?1 for 3 ) at elevated temperature (>75 °C). They retain the conductivity for up to 10 h at high temperature and high humidity. Furthermore, the proton conductivity results were correlated with the number of water molecules from the water‐vapor adsorption measurements. Water‐vapor adsorption studies showed hysteretic and two‐step water vapor adsorption (182000 μL g?1 for 1 , 184000 μL g?1 for 2 , and 1874000 μL g?1 for 3 ) in the experimental pressure range. Simulation of water‐vapor adsorption by the Monte Carlo method (for 1 ) confirmed the high density of adsorbed water molecules, preferentially in the interlayer space between the 2D layers.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号