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   1954篇
  免费   272篇
  国内免费   285篇
化学   1590篇
晶体学   26篇
力学   89篇
综合类   23篇
数学   257篇
物理学   526篇
  2024年   5篇
  2023年   31篇
  2022年   59篇
  2021年   52篇
  2020年   63篇
  2019年   69篇
  2018年   67篇
  2017年   55篇
  2016年   75篇
  2015年   95篇
  2014年   100篇
  2013年   136篇
  2012年   174篇
  2011年   175篇
  2010年   123篇
  2009年   111篇
  2008年   128篇
  2007年   119篇
  2006年   108篇
  2005年   101篇
  2004年   95篇
  2003年   75篇
  2002年   93篇
  2001年   69篇
  2000年   50篇
  1999年   51篇
  1998年   36篇
  1997年   24篇
  1996年   28篇
  1995年   16篇
  1994年   21篇
  1993年   20篇
  1992年   13篇
  1991年   12篇
  1990年   11篇
  1989年   7篇
  1988年   5篇
  1987年   5篇
  1986年   6篇
  1985年   8篇
  1984年   3篇
  1983年   3篇
  1982年   5篇
  1981年   3篇
  1980年   3篇
  1979年   2篇
  1977年   1篇
排序方式: 共有2511条查询结果,搜索用时 11 毫秒
101.
Low-flow chromatography has a rich history of innovation but has yet to reach widespread implementation in bioanalytical applications. Improvements in pump technology, microfluidic connections, and nano-electrospray sources for MS have laid the groundwork for broader application, and innovation in this space has accelerated in recent years. This article reviews the instrumentation used for nano-flow LC, the types of columns employed, and strategies for multidimensionality of separations, which are key to the future state of the technique to the high-throughput needs of modern bioanalysis. An update of the current applications where nano-LC is widely used, such as proteomics and metabolomics, is discussed. But the trend toward biopharmaceutical development of increasingly complex, targeted, and potent therapeutics for the safe treatment of disease drives the need for ultimate selectivity and sensitivity of our analytical platforms for targeted quantitation in a regulated space. The selectivity needs are best addressed by mass spectrometric detection, especially at high resolutions, and exquisite sensitivity is provided by nano-electrospray ionization as the technology continues to evolve into an accessible, robust, and easy-to-use platform.  相似文献   
102.
Two-dimensional carbon nitride(2 D-C3 N4)nanosheets are promising materials in photocatalytic water splitting,but still suffer from easy agglomeration and fast photogene rated electron-hole pairs recombination.To tackle this issue,herein,a hierarchical Nb2 O5/2 D-C3 N4 heterostructure is precisely constructed and the built-in electric field between Nb2O5 and 2 D-C3 N4 can provide the driving force to separate/transfer the charge carriers efficiently.Moreover,the strongly Lewis acidic Nb2O5 can adsorb TEOA molecules on its surface at locally high concentrations to facilitate the oxidation reaction kinetics under irradiation,resulting in efficient photogene rated electrons-holes separation and exceptional photocatalytic hydrogen evolution.As expected,the champion Nb2O5/2 D-C3N4 heterostructure achieves an exceptional H2 evolution rate of 31.6 mmol g-1 h-1,which is 213.6 times and 4.3 times higher than that of pristine Nb2O5 and2 D-C3N4,respectively.Moreover,the champion heterostructure possesses a high apparent quantum efficiency(AQE)of 45.08%atλ=405 nm and superior cycling stability.Furthermore,a possible photocatalytic mechanism of the energy band alignment at the hetero-interface is proposed based on the systematical characterizations accompanied by density functional theory(DFT)calculations.This work paves the way for the precise construction of a high-quality heterostructured photocatalyst with efficient charge separation to boost hydrogen production.  相似文献   
103.
The photo-induced ultrafast electron dynamics in both anatase and rutile TiO\begin{document}$_{2}$\end{document} are investigated by using the Boltzmann transport equation with the explicit incorporation of electron-phonon scattering rates. All structural parameters required for dynamic simulations are obtained from ab initio calculations. The results show that although the longitudinal optical modes significantly affect the electron energy relaxation dynamics in both phases due to strong Fr?hlich-type couplings, the detailed relaxation mechanisms have obvious differences. In the case of a single band, the energy relaxation time in anatase is 24.0 fs, twice longer than 11.8 fs in rutile. This discrepancy is explained by the different diffusion distributions over the electronic Bloch states and different scattering contributions from acoustic modes in the two phases. As for the multiple-band situation involving the lowest six conduction bands, the predicted overall relaxation times are about 47 fs and 57 fs in anatase and rutile, respectively, very different from the case of the single band. The slower relaxation in rutile is attributed to the existence of multiple rate-controlled steps during the dynamic process. The present findings may be helpful to control the electron dynamics for designing efficient TiO\begin{document}$_{2}$\end{document}-based devices.  相似文献   
104.
Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10−3 and CPL brightness in the range of 30–40 M−1 cm−1 were observed.  相似文献   
105.
Surface oxygen functionalities (particularly C−O configuration) in carbon materials have negative influence on their electrical conductivity and Na+ storage performance. Herein, we propose a concept from surface chemistry to regulate the oxygen configuration in hierarchically porous carbon nanosheets (HPCNS). It is demonstrated that the C−O/C=O ratio in HPCNS reduces from 1.49 to 0.43 and its graphitization degree increases by increasing the carbonization temperature under a reduction atmosphere. Remarkably, such high graphitization degree and low C−O content of the HPCNS-800 are favorable for promoting its electron/ion transfer kinetics, thus endowing it with high-rate (323.6 mAh g−1 at 0.05 A g−1 and 138.5 mAh g−1 at 20.0 A g−1) and durable (96 % capacity retention over 5700 cycles at 10.0 A g−1) Na+ storage performance. This work permits the optimization of heteroatom configurations in carbon for superior Na+ storage.  相似文献   
106.
采用水热法合成了尖晶石型NiFe2O4,并利用X射线粉末衍射仪对其物相进行了表征,利用紫外-可见分光光度计对其光催化降解刚果红的性能进行了研究。以刚果红为光催化降解底物,探究了刚果红初始浓度、催化剂用量、溶液pH、不同光源等因素对NiFe2O4光催化降解刚果红活性的影响。结果表明,当刚果红溶液浓度为20 mg/L、催化剂NiFe2O4的用量为0.065 g、pH 2~10、在太阳光下照射480 min时,刚果红的降解率高达99%以上,催化剂性能稳定,适合处理刚果红类有机污染物。  相似文献   
107.
吲哚乙酸与磷钼黄反应及其极谱分析的研究   总被引:1,自引:0,他引:1  
在NH3-NH4Cl缓冲溶液中(pH=9.5),吲哚乙酸与磷钼黄的还原产物在滴汞电极上于-1.10V(vs.SCE)处产生一灵敏的极谱波,该波波高与吲哚乙酸的浓度在1.0×10-7-5.0×10-6mol/L范围内成线性关系,检测下限为5.0×10-8mol/L。如在上述还原产物中加入偶氮胭脂红B、孔雀绿、甲基紫等染料及聚乙烯醇,可使极谱波的灵敏度提高,使吲哚乙酸的浓度在5.0×10-8-1.0×10-6mol/L范围内与波高成线性关系,检测下限降低至1.0×10-8mol/L。  相似文献   
108.
阻抑-褪色光度法测定痕量间苯二酚   总被引:8,自引:0,他引:8  
在NH3 NH4Cl介质中 ,间苯二酚能阻抑Fe(Ⅲ )为催化剂 ,邻菲罗啉为活化剂的过氧化氢氧化甲酚红的褪色反应。研究了该反应的最佳条件和动力学参数。建立了一种测定痕量间苯二酚的新方法。方法检出限为 3 5× 1 0 - 4 g·L- 1 ,测定范围为 0 .30mg/L~ 7.0mg/L ,方法可用于废水中间苯二酚的测定  相似文献   
109.
The dynamics of metal-to-ligand charge transfer (MLCT) in a cis-bis(4,4'-dicarboxy-2,2'-bipyridine)-bis(isothiocyanato)ruthenium(II) dye (N3) are compared for the free dye in solution and the dye adsorbed on the surface of the TiO(2) nanoparticles from resonance Raman spectroscopy. The 544-nm MLCT absorption band of N3 adsorbed on TiO(2) is slightly blue-shifted from that of the free N3, indicating a weak electronic coupling between N3 and TiO(2). The resonance Raman spectra of N3 and the N3|TiO(2) complex obtained upon excitation within the lowest-lying MLCT singlet state of the dye are similar except for slight shifts in band positions. Resonance Raman cross sections have been obtained for the vibrational modes of both N3 and N3|TiO(2) with excitation frequencies spanning the 544-nm MLCT band. Self-consistent analysis of the resulting resonance Raman excitation profiles and absorption spectrum using a time-dependent wave packet formalism over two electronic states yields mode-specific vibrational and solvent reorganization energies. Despite the weak electronic coupling between N3 and TiO(2) in N3|TiO(2), adsorption strongly affects the reorganization energies of N3 in the intramolecular MLCT state. Adsorption of N3 onto TiO(2) increases the absolute Raman cross section of each mode by a factor of ca. 1.6 and decreases the vibrational and solvent reorganization energies by factors of 2 and 6, respectively. The excited-state dynamics of N3 adsorbed on the surface of TiO(2) nanoparticles were observed to be independent of the number of N3 molecules adsorbed per TiO(2) nanoparticle. The effect of TiO(2) on the dynamics of the adsorbed N3 is primarily due to both mode-specific vibrational and electronic pure dephasing, with the dominant contribution from the latter process.  相似文献   
110.
纳米尺寸团簇NinZrn(n=3~5)的几何结构与成键规律研究   总被引:3,自引:0,他引:3  
根据化学键理论与拓扑原理,设计了团簇NinZrn(n=3-5)的可能几何构型,并用从头算方法进行构型优化,结果表明,由NiZr组成的团簇原子间的Zr-Zr和Zr-Ni键明显较强,而Ni-Ni的成键较弱,并发与NinZrn(n=3-5)团簇电子性质与有机烯烃分子等瓣相似,原子之间的成键按照强弱相间的规则分布。  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