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   282篇
  免费   40篇
  国内免费   252篇
化学   529篇
物理学   45篇
  2023年   4篇
  2022年   8篇
  2021年   3篇
  2020年   20篇
  2019年   13篇
  2018年   11篇
  2017年   2篇
  2016年   16篇
  2015年   14篇
  2014年   27篇
  2013年   22篇
  2012年   37篇
  2011年   41篇
  2010年   44篇
  2009年   19篇
  2008年   42篇
  2007年   44篇
  2006年   43篇
  2005年   30篇
  2004年   27篇
  2003年   21篇
  2002年   13篇
  2001年   13篇
  2000年   4篇
  1999年   6篇
  1998年   3篇
  1997年   6篇
  1996年   4篇
  1995年   4篇
  1994年   5篇
  1993年   4篇
  1992年   3篇
  1991年   3篇
  1990年   3篇
  1989年   3篇
  1988年   3篇
  1987年   3篇
  1986年   3篇
  1985年   3篇
排序方式: 共有574条查询结果,搜索用时 31 毫秒
1.
We have prepared well-resolved Nbn+(n=1-10) clusters and report here an in-depth study on the essentially different reactivity with N2 and O2,by utilizing a multiple-ion laminar flow tube reactor in tandem with a customized triple quadrupole mass spectrometer(MIFT-TQMS).As results,the Nbn+ clusters are found to readily react with N2 and form adsorption products NbnN2 m+;in contrast,the r...  相似文献   
2.
《中国化学快报》2020,31(10):2712-2716
The heterogeneous reaction of SO2 on mineral dust surfaces is generally considered as an important chemical pathway for secondary sulfate formation in the troposphere. To this day, there are no reported studies that assess the impact of atmospheric CO2 in sulfate production on mineral dust surfaces. In this work, we investigate the impact of CO2 on SO2 uptake on dust proxy aluminum oxide particles using a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). CO2 is demonstrated to suppress the heterogeneous oxidation of SO2 on alpha-Al2O3. Compared to that measured in the CO2-free case, the uptake coefficient is decreased by nearly 57% when Al2O3 particles are exposed to the gas flow with atmospheric CO2 at a relative humidity (RH) of 25%. It is also found that there is a balance between the yield of active moiety −OH provided by Al(OH)3(CO)(OH)2 clusters and the loss of basic hydroxyl group on aluminum oxide surfaces blocked by CO2-derived (bi)carbonate species. This work, for the first time, reveals a negative effect of atmospheric CO2 on the sulfate formation, which potentially decreases solar-radiation scattering and further exacerbates global warming.  相似文献   
3.
Dissociation of molecular hydrogen (H2) is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H2 dissociation by Au1-doped closed-shell titanium oxide cluster anions AuTi3O7- and AuTi3O8- has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and massselected to react with H2 in an ion trap reactor. In the reaction of AuTi3O8- with H2, the ion pair Au+-O22- rather than Au+-O2- is the active site to promote H2 dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H2 dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H2 activation and dissociation.  相似文献   
4.
Fully utilizing solar energy for catalysis requires the integration of conversion mechanisms and therefore delicate design of catalyst structures and active species. Herein, a MOF crystal engineering method was developed to controllably synthesize a copper–ceria catalyst with well-dispersed photoactive Cu-[O]-Ce species. Using the preferential oxidation of CO as a model reaction, the catalyst showed remarkably efficient and stable photoactivated catalysis, which found practical application in feed gas treatment for fuel cell gas supply. The coexistence of photochemistry and thermochemistry effects contributes to the high efficiency. Our results demonstrate a catalyst design approach with atomic or molecular precision and a combinatorial photoactivation strategy for solar energy conversion.  相似文献   
5.
Organic semiconductor (OSC) crystals have great potential to be applied in many fields, as they can be flexibly designed according to the demands and show an outstanding device performance. However, OSCs with the capacity of solid-state crystallization (SSC) are developing too slowly to meet demands in productions and applications, due to their difficulties in molecular design and synthesis, unclear mechanism and high dependence on experimental conditions. In this work, in order to solve the problems, we synthesized an organic semiconductor capable of SSC at room temperature by adjusting the relationship between conjugated groups and functional groups. The thermodynamic and kinetic properties have been studied to discover the model of film SSC. Moreover, it can be purposefully controlled to prepare the high-quality crystals, and their corresponding organic electronic devices were further fabricated and discussed.  相似文献   
6.
The design of DNA-based logic circuits has become an active research field in DNA nanotechnology and holds great potential in intelligent bioanalysis. To date, although many DNA-based logic systems have been realized, the implementation of advanced logic functions is still challenging, especially with simple and homogeneous compositions. Herein, by integrating two DNA tetraplex structures (G-quadruplex and i-motif), a completely label-free logic platform with high scalability was established, with which a series of advanced functions were realized, including arithmetic (adders and subtractors) and nonarithmetic ones (majority and dual-transfer gates). Furthermore, the platform was also applied as an intelligent biosensor to coanalyze two cancer-related micro-RNAs with high sensitivities and specificities. Considering the excellent versatility, expandability, and biocompatibility, the platform may promote the development of DNA computing and hold great potential in multiparameter sensing and medical diagnosis.  相似文献   
7.
The detection of free radicals and related species has attracted considerable attention in recent years due to their critical roles in physiological and pathological processes. Among the various methods for the detection of free radicals, electron spin resonance coupled with spin-trapping technique has been an effective approach for the characterization and quantification of free radicals due to its high specificity. In this study, we designed and synthesized a novel amphiphilic spin trap, 2-(diethoxyphosphoryl)-2-heptadecanyl-3,4-dihydro-2H-pyrrole-1-oxide (DEPHdPO), from 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide with a long hydrocarbon chain at the C-5 position of the pyrroline ring, providing the amphiphilic character. The free-radical-trapping ability of DEPHdPO was evaluated by capturing hydroxyl radicals (·OH), superoxide anions (\( {\text{O}}_{2}^{ \cdot - } \)), and carbon-centered free radicals in a model membrane prepared from sodium dodecyl sulfate (SDS). The results indicate that the hydrophobic hydrocarbon chain of DEPHdPO can be inserted into the inner core of SDS micelles, and the hydrophilic nitronyl functional moiety is located on the surface layer. Thus, various free radicals, including ·OH radicals, \( {\text{O}}_{2}^{ \cdot - } \) anions, and carbon-centered radicals could be site-specifically detected near the membrane surface. Moreover, DEPHdPO could be successfully located on the surface of thylakoid membranes, and the nearby photo-initiated \( {\text{O}}_{2}^{ \cdot - } \) anions could be trapped site-specifically.  相似文献   
8.
Methane activation by transition metal species has been extensively investigated over the past few decades. It is observed that ground-state monocations of bare 3d transition metals are inert toward CH4 at room temperature because of unfavorable thermodynamics. In contrast, many mono-ligated 3d transition metal cations, such as MO+ (M = Mn, Fe, Co, Cu, Zn), MH+ (M = Fe, Co), and NiX+ (X = H, CH3, F), as well as several bis-ligated 3d transition metal cations including OCrO+, Ni(H)(OH)+, and Fe(O)(OH)+ activate the C―H bond of methane under thermal collision conditions because of the pronounced ligand effects. In most of the above-mentioned examples, the 3d metal atoms are observed to cooperate with the attached ligands to activate the C―H bond. Compared to the extensive studies on active species comprising of middle and late 3d transition metals, the knowledge about the reactivity of early 3d transition metal species toward methane and the related C―H activation mechanisms are still very limited. Only two early 3d transition metal species HMO+ (M = Ti and V) are discovered so far to activate the C―H bond of methane via participation of their metal atoms. In this study, by performing mass spectrometric experiments and density functional theory calculations, we have identified that the diatomic vanadium boride cation (VB+) can activate methane to produce a dihydrogen molecule and carbon-boron species under thermal collision conditions. The strong electrostatic interaction makes the reaction preferentially proceed the V side. To generate experimentally observed product ions, a two-state reactivity scenario involving spin conversion from high-spin sextet to low-spin quartet is necessary at the entrance of the reaction. This result is consistent with the reported reactions of 3d transition metal species with CH4, in which the C―H bond cleavage generally occurs in the low-spin states, even if the ground states of the related active species are in the high-spin states. For VB+ + CH4, the insertion of the synergetic V―B unit (rather than a single V or B atom) into the H3C―H bond causes the initial C―H bond activation driven by the strong bond strengths of V―CH3 and B―H. The mechanisms of methane activation by VB+ discussed in this study may provide useful guidance to the future studies on methane activation by early transition metal systems.  相似文献   
9.
The side-on-end-on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V5N5]) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV).  相似文献   
10.
Metal carbide species have been proposed as a new type of chemical entity to activate methane in both gas‐phase and condensed‐phase studies. Herein, methane activation by the diatomic cation MoC+ is presented. MoC+ ions have been prepared and mass‐selected by a quadrupole mass filter and then allowed to interact with methane in a hexapole reaction cell. The reactant and product ions have been detected by a reflectron time‐of‐flight mass spectrometer. Bare metal Mo+ and MoC2H2+ ions have been observed as products, suggesting the occurrence of ethylene elimination and dehydrogenation reactions. The branching ratio of the C2H4 elimination channel is much larger than that of the dehydrogenation channel. Density functional theory calculations have been performed to explore in detail the mechanism of the reaction of MoC+ with CH4. The computed results indicate that the ethylene elimination process involves the occurrence of spin conversions in the C?C coupling (doublet→quartet) and hydrogen atom transfer (quartet→sextet) steps. The carbon atom in MoC+ plays a key role in methane activation because it becomes sp3 hybridized in the initial stages of the ethylene elimination reaction, which leads to much lower energy barriers and more stable intermediates. This study provides insights into the C?H bond activation and C?C coupling involved in methane transformation over molybdenum carbide‐based catalysts.  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