全文获取类型
收费全文 | 3314篇 |
免费 | 294篇 |
国内免费 | 397篇 |
专业分类
化学 | 2981篇 |
晶体学 | 44篇 |
力学 | 20篇 |
综合类 | 14篇 |
数学 | 16篇 |
物理学 | 930篇 |
出版年
2024年 | 5篇 |
2023年 | 71篇 |
2022年 | 71篇 |
2021年 | 83篇 |
2020年 | 115篇 |
2019年 | 99篇 |
2018年 | 79篇 |
2017年 | 88篇 |
2016年 | 135篇 |
2015年 | 126篇 |
2014年 | 181篇 |
2013年 | 304篇 |
2012年 | 183篇 |
2011年 | 199篇 |
2010年 | 146篇 |
2009年 | 214篇 |
2008年 | 198篇 |
2007年 | 230篇 |
2006年 | 238篇 |
2005年 | 181篇 |
2004年 | 156篇 |
2003年 | 145篇 |
2002年 | 115篇 |
2001年 | 71篇 |
2000年 | 80篇 |
1999年 | 82篇 |
1998年 | 74篇 |
1997年 | 64篇 |
1996年 | 51篇 |
1995年 | 46篇 |
1994年 | 21篇 |
1993年 | 23篇 |
1992年 | 31篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 13篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 2篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有4005条查询结果,搜索用时 203 毫秒
1.
Ajit Kumar Singh Seulgi Ji Baghendra Singh Chittaranjan Das Heechae Choi Prashanth W. Menezes Arindam Indra 《Materials Today Chemistry》2022
Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H+ ion transport. 相似文献
2.
Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed. 相似文献
3.
Yaping Chen Dr. Kun Rui Prof. Jixin Zhu Prof. Shi Xue Dou Dr. Wenping Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):703-713
Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed. 相似文献
4.
Eldad Herceg 《Surface science》2006,600(19):4563-4571
The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N2 TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm−1) peak at 3322 cm−1. The areas of the H2 TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here. 相似文献
5.
A Promising MoO_x-based Catalyst for n-Heptane Isomerization 总被引:1,自引:0,他引:1
Song Hai CHAI Xin Ping WANG* Ying Jun WANG Tian Xi CAI State Key Laboratory of Fine Chemicals Dalian University of Technology Dalian 《中国化学快报》2003,14(7)
The increasing demand for higher-octane gasoline and the regulations limiting the amount of aromatics in the fuel motivate the interest in catalytic isomerization of n-alkanes. In the last ten years, transition metal oxides or oxycarbides based on molybdenum or tungstate have attracted much attention due to their high activity and isomerization selectivity compared to the conventional bifunctional supported platinum catalyst and high resistance to sulphur and nitrogen catalyst poisons1-5. Ma… 相似文献
6.
W. Gao M. Li R. Klie E.I. Altman 《Journal of Electron Spectroscopy and Related Phenomena》2006,150(2-3):136-149
Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH3, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO2. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO3 substrates and their interactions with vanadia were characterized. On LaAlO3 (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V5+ was observed. Continued V2O5 growth led to loss of order, but at high temperatures epitaxial VO2 could be grown; vanadia behaved similarly on anatase films on LaAlO3 (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V5+. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO2 are much more active than bulk V2O5. For WO3, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO3 surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH4 catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C3H6 oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction. 相似文献
7.
N. Moslemzadeh G. Beamson P. Tsakiropoulos J.F. Watts S.R. Haines P. Weightman 《Journal of Electron Spectroscopy and Related Phenomena》2006
High-energy X-ray photoelectron spectroscopy (XPS) is of particular importance for minimizing the effects of surface contamination by increasing photoelectron escape depths. In this study high-resolution high-energy Cu Kα1 and soft Al Kα1 XPS and Auger electron spectroscopy were used to compare the electronic structure of Ti in TiO2 powder and Ti metal. The Ti 1s in TiO2 XPS line is narrower and more symmetric than in Ti metal. A comparison of the relative intensities of the L23M23M45 and L23M23M23 Auger transitions in Ti metal and TiO2 is consistent with the expected transfer of Ti 3d electrons away from the Ti site in the oxide. The satellites accompanying the Ti 1s XPS line excited by Cu Kα1 X-rays occur at the same energies as the satellites accompanying the Ti 2s and 2p XPS lines excited by Al Kα1 X-rays indicating that they do not depend on the core-level, the experimental resolution or inelastic scattering processes. 相似文献
8.
Two distinct humic acids, one extracted from Brazilian peat soil, HAPS, and another one obtained from commercial source, HAFL, were attachment onto silica gel modified with aminopropyltrimethoxysilane, producing two material named SiHAPS and SiHAFL, respectively. The ability of these materials in removing indigo carmine dye from aqueous solution was followed through series of adsorption isotherms adjusted to modified Langmuir equation. The maximum number of moles adsorbed gave 6.82 ± 0.12 × 10−4 and 2.15 ± 0.17 × 10−4 mol g−1 for SiHAPS and SiHAFL, respectively. Same interactions were calorimetrically followed and the thermodynamic data showed endothermic enthalpic values: 12.31 ± 0.55 and 24.69 ± 1.05 kJ mol−1 for SiHAPS and SiHAFL surfaces, respectively. Gibbs free energies for two adsorption processes of indigo carmine dye presented negative values, reflecting dye/surface interactions must be accompanied by an increased in entropy values, which are 65 ± 3 and 98 ± 5 J mol−1 K−1 for SiHAPS and SiHAFL materials, respectively. The adsorption processes for both materials were spontaneous in nature although they presented an endothermic enthalpy for the interaction, resulting in an entropically favored process. 相似文献
9.
In this paper, we report the conducting and electrochemical properties of a homogeneous V2O5-SiO2 xerogel composite obtained from the simultaneous polymerization in both inorganic components (Si-O and V-O based polymers) forming an interpenetrating polymer network, where a mutual “solubility” due to cross-links and entanglements was observed. The presence of V2O5 inside the silica matrix has a strong effect on electrical conductivity; measurements showed room temperature conductivity almost 1000 times higher than what is found in the literature. In addition, the electrochemical behavior is quite similar to that found in V2O5 xerogel. Moreover, the effects of thermal treatment on the conducting and electrochemical properties were investigated. It was found that both properties were improved with no significant effect on V2O5 xerogel layered structure. 相似文献
10.
The physico-chemical properties and reactivity tested by hydrogen reduction have been studied for two series of NiO-ZnO mixed oxides of various composition. The solid nickel oxide or zinc oxide in interaction with the solution of nitrate of the second component were used as the precursors in each series. The differences in some physico-chemical parameters of the samples in both series were correlated with their reduction behaviour, followed both in iso- and non-isothermal regime. Moreower, the influence of various factors modifying the reactivity of mixed oxides was also investigated and the results were compared with those obtained from earlier studied analogous systems of quite different origin.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献