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   7681篇
  免费   1080篇
  国内免费   2036篇
化学   9351篇
晶体学   67篇
力学   66篇
综合类   55篇
数学   7篇
物理学   1251篇
  2024年   3篇
  2023年   124篇
  2022年   180篇
  2021年   285篇
  2020年   431篇
  2019年   328篇
  2018年   301篇
  2017年   288篇
  2016年   389篇
  2015年   389篇
  2014年   492篇
  2013年   829篇
  2012年   554篇
  2011年   523篇
  2010年   461篇
  2009年   453篇
  2008年   527篇
  2007年   567篇
  2006年   495篇
  2005年   427篇
  2004年   398篇
  2003年   447篇
  2002年   258篇
  2001年   227篇
  2000年   219篇
  1999年   199篇
  1998年   131篇
  1997年   155篇
  1996年   136篇
  1995年   129篇
  1994年   90篇
  1993年   77篇
  1992年   70篇
  1991年   44篇
  1990年   40篇
  1989年   27篇
  1988年   26篇
  1987年   12篇
  1986年   17篇
  1985年   13篇
  1984年   8篇
  1983年   4篇
  1982年   5篇
  1981年   9篇
  1980年   2篇
  1979年   3篇
  1977年   1篇
  1973年   1篇
  1969年   1篇
  1959年   1篇
排序方式: 共有10000条查询结果,搜索用时 16 毫秒
1.
2.
Addressing arsenite pollution in groundwater has drawn great attention. It is attractive to pre-oxidize highly mobile As(III) to relatively low-toxic As(V) with a subsequent adsorption separation process. Herein, BiOI anchoring on γ-Fe2O3 is performed to synthesize BiOI/γ-Fe2O3 core–shell nanoparticles for efficient removal of As(III) via a simultaneous photocatalytic oxidization–adsorption process. The physical and chemical structures of BiOI/γ-Fe2O3 are investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction measurements. The photoluminescence and electron spin resonance (ESR) characterization were employed to ascertain the possible reaction mechanism of visible-light-driven photocatalytic oxidation of As(III). Such BiOI/γ-Fe2O3 delivers a superior As(III) removal capability under visible light irradiation with an arsenic removal efficiency of 99.8% within 180 min, higher than those of BiOCl/γ-Fe2O3 (81.7%) and BiOBr/γ-Fe2O3 (98.9%). The optimal BiOI/γ-Fe2O3 (molar ratio of 2:1) is obtained by rationally adjusting the molar ratio of BiOI to γ-Fe2O3. The as-synthesized BiOI/γ-Fe2O3 performs well in a wide pH range of 2–8. Only coexisting PO43? anions have a significant effect on the As(III) removal. The free radical trapping experiment and ESR results demonstrate that the ?O2? and h+ are the main active substances for the photocatalytic oxidation of As(III) on BiOI/γ-Fe2O3. This work not only gives a novel magnetic core–shell nanoparticle photocatalyst for efficient photocatalytic oxidation and adsorption of As(III) but also offers a new strategy to rationally design BiOX for its related practical applications.  相似文献   
3.
Due to the water-insoluble nature of Hg0, its oxidization to Hg2+, which is water-soluble, is a viable approach for its effective removal at coal-fired plants using existing flue gas desulfurization (FGD) unit. In this study, the adsorption and oxidation of elemental mercury on an Mn-doped g-C3N4 material were investigated. The spin-polarized density functional theory method was adapted to optimize the geometry structures and then to determine the corresponding electronic structures, while the CI-NEB method was adopted to search for the stable intermediates during the reaction(s). The analysis of energy and project density of states shows that the Mn-g-C3N4 exhibits an excellent affinity to Hg atoms. It is found that it is feasible for Hg atoms to oxidize on the Mn-g-C3N4 surface via two possible E-R paths, but with relatively high energy barriers. This research provides insights into a viable way for mercury removal using O2 as the oxidizing agent.  相似文献   
4.
Volatile organic compounds(VOCs) have become one of the most serious threats to human health and eco-environment due to their volatility, toxicity and diffusivity, etc. Catalytic completely oxidation had been regarded as a highly efficient strategy for the VOCs abatement. Metal or metal oxides supported on zeolite have been considered as superior catalysts for the treatment of VOCs. Among them, Beta zeolites have attracted many attentions due to their unique structure and consequently catalytic properties in the oxidation of VOCs. The progresses and developments made in the understanding and design of Beta zeolites-based catalysts in the completely oxidation of VOCs in the past two decades have been systematically summarized in this review.  相似文献   
5.
Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.  相似文献   
6.
Conjugated polymers feature promising structure and properties for photocatalytic water splitting. Herein, a hydrolysis strategy was demonstrated to rationally modulate the surface hydrophilicity and band structures of conjugated poly-benzothiadiazoles. High hydrophilicity not only enhances the dispersions of polymeric solids in an aqueous solution but also reduces the absorption energy of water molecules. Besides, both theoretical and experimental results reveal that a more positive valence band potential is generated, which contributes to enhancing the photocatalytic water oxidation performance. Accordingly, the surface-modified conjugated polymers show largely promoted photocatalytic water oxidation activities by deposition of cobalt oxides as cocatalysts.  相似文献   
7.
Dehydrogenation of an organic compound is the first and the most fundamental elementary reaction in many organic reactions. In ethanol oxidation reaction (EOR) to form CO2, there are a total of 46 pathways in C2HxO (x=1–6) species leading to the removal of all six hydrogen atoms in five C−H bonds and one O−H bond. To investigate the degree of dehydrogenation in EOR under operando conditions, we performed density function theory (DFT) calculations to study 28 dehydrogenation steps of C2HxO on Ir(100). An activation energy surface was then constructed and compared with that of the C−C bond cleavages to understand the importance of the degree of dehydrogenation in EOR. The results show that there are likely 28 dehydrogenations in EOR under fuel cell temperatures and the last two hydrogens in C2H2O are less likely cleaved. On the other hand, deep dehydrogenation including 45 dehydrogenations can occur under ethanol steam reforming conditions.  相似文献   
8.
Pressure oxidation leaching behavior of chalcopyrite in sulfuric acid solution from 110 °C to 150 °C were investigated by in-situ electrochemical methods. Leaching experiments under saturated vapor pressure conditions were used to simulate the anoxic environment that may be encountered in industrial applications. Scanning electron microscope and X-ray photoelectron spectroscopy were used to characterize the morphology and the chemical status of chalcopyrite surface. Results show that the copper extraction was increased with the increase of leaching temperature. Under the optimal leaching conditions under saturated vapor pressure, the copper and iron extraction are 8.3% and 29.8%, respectively. When the temperature increased from 110 °C to 150 °C, the self-corrosion potential and electrochemical reaction resistance firstly increased and then decreased. In contrast, the resistance of the passive film was always increased with the increase of temperature. The electrochemical study results indicated that the increase in temperature affected the oxidation of chalcopyrite by altering the kinetics of the cathodic reaction and the anodic passivation. Both the self-corrosion current density (icorr) and rate constant were affected by the reduction of Fe(III). The XPS results show that elemental sulfur and H3O(Fe3(SO4)2(OH)6) were the main leaching solid products. The formation of H3O(Fe3(SO4)2(OH)6) not only caused a decrease in cathodic reaction kinetics, but also increased the resistance of mass transfer process. Due to the faster release of iron, copper-rich sulphides were formed, which mixed with the elemental sulfur and/or H3O(Fe3(SO4)2(OH)6) led to coverage of the chalcopyrite surface.  相似文献   
9.
近年来,半导体光催化在环境净化和有机合成领域的研究引起了广泛的重视.其中,在有机合成领域中,光催化技术已经应用在醇类、环己烷以及芳香族化合物的选择性氧化研究.而另一类具有特殊结构的有机物——N-杂环芳烃,在药物化学和材料科学中具有重要意义.而传统用于合成N-杂化芳烃的脱氢催化氧化反应通常需要高温高压的苛刻环境,传统方法通常还需要使用贵金属催化剂,这也增加了N-杂化芳烃的合成成本;另外,如果合成是均相催化过程,则催化剂难以实现回收利用.因此,开发室温常压条件下的非贵金属多相光催化技术具有巨大的应用前景.本文以能够被可见光驱动的钼酸铋半导体为催化剂,利用氧缺陷策略来提升钼酸铋的光催化氧化性能.不同于传统氧缺陷制备方法(氢气还原热处理、离子掺杂等),本文采用一种低成本的乙二醛辅助溶剂热的方法合成具有可调控的含氧空位Bi2MoO6催化剂(OVBMO).通过X射线粉末衍射(XRD)、扫描电镜、透射电镜、紫外可见漫反射吸收光谱、氮气物理吸附脱附、X射线光电子能谱(XPS)、电子自旋共振光谱、光致发光光谱及电化学测试等技术对制备的OVBMO材料进行了物理化学性质及能带研究.XPS,XRD,Raman和FT-IR结果表明,氧空位存在于[Bi2O2]2+和MoO6八面体的层间.紫外可见漫反射结果表明,随着氧空位的引入,Bi2MoO6的光吸收范围扩大,带隙变窄.结合莫特肖特基和VBXPS分析获得OVBMO的能带位置,发现氧空位的存在不仅会导致禁带中出现缺陷带能级,还会导致价带顶位置上移,促进光生空穴的迁移.PL和电化学结果表明,氧空位的存在使得载流子浓度、载流子的分离能力与界面电荷迁移能力都有较大提升,这是因为氧空位引入的缺陷能级可以浅势捕获电子,抑制光催化剂中的电子与空穴的复合,改变化学反应的速率.同时,氧空位有助于捕获分子氧,分子氧与捕获的光生电子发生反应,产生更多的超氧自由基(·O2)和空穴(h+),从而极大地提升光催化剂的氧化性能.因此,OVBMO在1,2,3,4-四氢喹啉脱氢氧化产生喹啉及系列抗生素(环丙沙星、四环素、盐酸土霉素)的降解反应中,表现出较好的光催化氧化性能.结合多种表征分析,本文还进一步阐明了OVBMO催化剂将1,2,3,4-四氢喹啉脱氢氧化为喹啉的自由基参与的多相催化反应机理.  相似文献   
10.
1,3-二羟基丙酮(DHA)是一种重要的化工原料,广泛应用于医药、化妆品及食品等领域.通过催化选择性氧化甘油制备DHA是一条高效、经济的工艺路线,而催化剂的种类及反应方式被证明对DHA的产率有较大影响.因此,结合近些年来相关文献,系统阐述了热、光和电这3种催化反应方式在甘油氧化制取DHA上的研究进展,并重点介绍了热催化路径中所选用的催化剂、相关研究实例及反应机理.最后,对甘油制备DHA的多路径选择性氧化的研究前景进行了展望.  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