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   3300篇
  免费   384篇
  国内免费   636篇
化学   2053篇
晶体学   131篇
力学   188篇
综合类   71篇
数学   766篇
物理学   1111篇
  2024年   7篇
  2023年   28篇
  2022年   83篇
  2021年   92篇
  2020年   125篇
  2019年   113篇
  2018年   161篇
  2017年   175篇
  2016年   170篇
  2015年   166篇
  2014年   199篇
  2013年   395篇
  2012年   219篇
  2011年   253篇
  2010年   249篇
  2009年   248篇
  2008年   268篇
  2007年   263篇
  2006年   197篇
  2005年   146篇
  2004年   99篇
  2003年   79篇
  2002年   86篇
  2001年   83篇
  2000年   77篇
  1999年   55篇
  1998年   46篇
  1997年   40篇
  1996年   20篇
  1995年   16篇
  1994年   9篇
  1993年   18篇
  1992年   19篇
  1991年   17篇
  1990年   9篇
  1989年   9篇
  1988年   10篇
  1987年   18篇
  1986年   5篇
  1985年   6篇
  1984年   8篇
  1983年   7篇
  1982年   4篇
  1981年   6篇
  1980年   6篇
  1979年   4篇
  1971年   1篇
  1957年   1篇
  1938年   1篇
  1936年   2篇
排序方式: 共有4320条查询结果,搜索用时 15 毫秒
31.
树脂吸附法处理水杨酸甲酯生产废水的研究   总被引:7,自引:0,他引:7  
采用吸附树脂NDA—99处理水杨酸甲酯生产废水,结果表明该树脂时废水中的5磺基水杨酸及水杨酸均具有良好的吸附—脱附性能.废水经预处理和吸附处理后,CODCr由57000-59000mg/L降至6300mg/L左右,去除率接近89%.用IBV8%NaOH 3BVH2O作脱附剂,在温度为60℃、流量为IBV/h的条件下,脱附率接近100%,树脂可重复使用.高浓度脱附液经酸化、浓缩、冷却结晶,可回收5—磺基水杨酸,回收率为95%左右。纯度为78%。  相似文献   
32.
用TEACO2激光9P(24),9P(22),9P(20),9P(18)四支线组成的多频强红外场“超激发”氟里昂113分子,使其达到很高激发态。由分解曲线可以看出CF2Cl·CFCl2与CF3·CCl3之间的V-V能量转移有明显的“虹吸”作用。从所得主要产物C2P6,C2Cl6,C关键词:  相似文献   
33.
Enhancing Isolated Ti( Ⅳ ) Framework Sites in HMS   总被引:1,自引:0,他引:1  
IntroductionTitanium modified mesoporous molecular sieves,such as Ti-MCM-41[1—4], Ti-HMS[5], Ti-SBA15[6, 7], and their catalytic performances havebeen investigated. Framework substitution and graftingtechniques have been employed for the preparation ofti…  相似文献   
34.
Surface Characterization of Sepiolite by Inverse Gas Chromatography   总被引:1,自引:0,他引:1  
Inverse gas chromatography (IGC) was applied to characterize the surface of sepiolite. The adsorption thermodynamic parameters (the standard enthalpy (ΔH 0), entropy (ΔS 0) and free energy of adsorption (ΔG 0)), the dispersive component of the surface energy (γ S d ), and the acid/base character of sepiolite surface were estimated by using the retention time of different non-polar and polar probes at infinite dilution region. The specific free energy of adsorption (ΔG sp ), the specific enthalpy of adsorption (ΔH sp ), and the specific entropy of adsorption (ΔS sp ) of polar probes on sepiolite were determined. ΔH sp were correlated with the donor and modified acceptor numbers of the probes to quantify the acidic K A and the basic K D parameters of the sepiolite surface. The values obtained for the parameters K A and K D indicated an acidic character for sepiolite surface.  相似文献   
35.
Alkali Blue 6B-attached poly(2-hydroxyethyl methacrylate) (poly(HEMA)) microporous films were investigated as chelate forming sorbents for heavy metal removal. Poly(HEMA) microporous films were prepared by UV-initiated photo-polymerization of HEMA in the presence of an initiator (azobisisobutyronitrile (AIBN)). Alkali Blue 6B was attached covalently. These films with a swelling ratio of 58%, and carrying 14.8 mmol Alkali Blue 6B m(-2) which were then used in the removal of Cd(II), Zn(II) and Pb(II) from aqueous media. Adsorption rates were very high, equilibrium was achieved in about 30 min. The maximum adsorption of heavy metal ions onto the Alkali Blue 6B-attached films were 41.4 mmol m(-2) for Cd(II), 52.4 mmol m(-2) for Zn(II), and 64.5 mmol m(-2) for Pb(II). When the heavy metal ions competed during the adsorption from a mixture the adsorption values for Cd(II), Zn(II) and Pb(II) were quite close. Heavy metal ions were desorbed by using 0.1 M HNO(3). A significant amount of the adsorbed heavy metal ions (up to 95%) could be desorbed in 30 min. Repeated adsorption/desorption cycles showed the feasibility of these novel dye-attached microporous films for heavy metal removal.  相似文献   
36.
The title compound [Mn(phendione)(PDC)(H2O)2]·2H2O (H2PDC=pyridine-2,6-dicarboxylic acid) has been prepared in aqueous solution and characterized by single X-ray diffraction structure determination, elemental analysis, IR spectroscopy, and thermal analyses. The compound crystallizes in Monoclinic system, space group C2/ca=1.017 51(11) nm, b=1.483 25(11) nm, c=1.461 21(13) nm, β=109.86(10)°, V=2.074 1(3) nm3Z=4, F(000)=1 028, μ=0.701 mm-1Dc=1.609 g·cm-3R1=0.028 9, wR2=0.078 8 [I>2σ(I)]. Crystal structure reveals that complex consists of one-dimensional chain framework bridged by hydrogen bonds that formed by uncoordinated water and oxygen atom of carboxyl group in PDC2-. Furthermore, the complexes form a three-dimensional super-molecular structure through hydrogen bonds. CCDC: 648570.  相似文献   
37.
The composites with nano-particles of Ni-Fe alloys dispersed on the nano-layers of expanded graphite (EG) were prepared by the impregnation of EG with ethanol solutions of nickel and iron acetates, followed by drying and reduction in H2. The square nano-particles of Ni-Fe alloys with particle sizes of mainly 20~40 nm were found to be well spread on the layers of EG. The alloy nano-particles exhibited high shielding effectiveness (SE) for electromagnetic radiations at low frequencies due to their high magnetic conductivity. Since EG is electronically conductive and displayed high SE at high frequencies, the composites exhibited good SE at wide range of frequencies. The electric and magnetic conductivities of the composites could be monitored through regulating the loadings of alloy nano-particles on EG, and it was found that the composites with 20%~40% of the alloys exhibited good SE. Specifically, the composite 27%Ni-3%Fe-EG showed the excellent SE from 66 to 110 dB at the frequencies from 300 kHz to 1.5 GHz.  相似文献   
38.
Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H2L) were prepared with the formula [MoO2(L)D] (D = H2O, methyl, n-butyl, and n-undecyl alcohol, DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental analysis, IR and 1H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air, and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex was studied by X-ray diffractometry. The text was submitted by the authors in English.  相似文献   
39.
设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.  相似文献   
40.
利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学. 实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度, 使得实验在准一级条件下进行. 加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响. 在(298±1) K和1.01×105 Pa条件下, 测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10-17和(8.20±1.01)×10-17 cm3·molecule-1·s-1. 与文献中已有的其它胺类的臭氧反应数据比较后发现, 臭氧与胺的反应可以用亲电反应机制来解释. 另外, 通过对比发现, 臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率. 这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实. 利用测得的速率常数和大气中臭氧浓度, 还估算了二乙胺和三乙胺与臭氧反应的大气寿命. 结果显示, 与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径, 尤其是在污染严重地区.  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