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   10918篇
  免费   622篇
  国内免费   2083篇
化学   10077篇
晶体学   185篇
力学   150篇
综合类   90篇
数学   1350篇
物理学   1771篇
  2024年   11篇
  2023年   122篇
  2022年   308篇
  2021年   245篇
  2020年   245篇
  2019年   254篇
  2018年   226篇
  2017年   283篇
  2016年   301篇
  2015年   249篇
  2014年   320篇
  2013年   819篇
  2012年   575篇
  2011年   721篇
  2010年   615篇
  2009年   818篇
  2008年   795篇
  2007年   761篇
  2006年   708篇
  2005年   644篇
  2004年   654篇
  2003年   490篇
  2002年   451篇
  2001年   333篇
  2000年   350篇
  1999年   260篇
  1998年   220篇
  1997年   242篇
  1996年   208篇
  1995年   229篇
  1994年   207篇
  1993年   173篇
  1992年   157篇
  1991年   115篇
  1990年   87篇
  1989年   88篇
  1988年   56篇
  1987年   30篇
  1986年   45篇
  1985年   23篇
  1984年   27篇
  1983年   11篇
  1982年   20篇
  1981年   29篇
  1980年   19篇
  1979年   20篇
  1978年   18篇
  1977年   7篇
  1976年   12篇
  1974年   7篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
771.
Reactive black 5 (RB-5) dye was removed from a water stream using two cationic surfactants, cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC), via micellar enhanced ultrafiltration. Three membranes with different pore size were used for the determination of rejection coefficient and permeate flux of the solution at 1.5 bar trans-membrane pressure (TMP). The two surfactants (CPC and CTAB) played an almost negligible role in rejection efficiency with 5000 and 10,000 molecular weight cut-off membrane (MWCO), respectively. In this case, high rejection and low permeate flux was the result of a larger molecular size of RB-5 DYE being retained by comparatively smaller sized pores of membrane via ultrafiltration. However, CPC and CTAB surfactants showed 83% and 98% rejection coefficient, respectively, at a concentration greater than their CMC values against 30,000 MWCO. Permeate flux remained low and constant in presence of 5000 and 10,000 MWCO with a small variation against 30,000 MWCO for the two surfactants, thereby no appreciable effect on both surfactant concentrations on concentration polarization was estimated. Thus, RB-5 dye alone was determined to be responsible for membrane plugging or concentration polarization and ultimately for low permeate flux. The effect of trans-membrane pressure was also investigated during this study.  相似文献   
772.
采用扫描电子显微镜、X射线衍射和粉末微电极分别考察了TiO2粉末的形貌、结构以及氧化I-的光电化学行为.结果表明,TiO2粉末晶型为锐钛矿,粒径在100~200 nm范围内.在光照条件下,在TiO2半导体电极上电化学氧化I-生成I2的超电势数值降低约1 V.以TiO2/ITO和Li4Ti5O12分别作为正负极,电解液为碳酸丙烯酯(PC)+LiClO4+LiI,并以聚偏氟乙烯(PVDF)作为隔膜构成分隔式电解池,进行整体电解并结合紫外-可见光谱进行分析.结果表明,该装置在光照条件下电池充电电压比非光照条件下的充电电压降低约0.9 V,且充电效率接近100%.该光电化学装置是一种可以利用光能充电的二次锂离子电池.  相似文献   
773.
生物油模型化合物催化裂化制备芳香烃的实验研究   总被引:1,自引:0,他引:1  
通过HZSM-5分子筛催化剂对生物油典型模型化合物(乙酸、愈创木酚、正庚烷和环己烷等)在550℃进行了催化裂化反应,研究模型化合物催化裂化特性和反应机理以及催化剂性质。结果表明,正庚烷和环己烷裂化产物主要是芳香烃(53%和91%,均为积分面积分数),对于此类不含氧的模型化合物,催化裂化反应过程更容易进行;随着催化剂用量的增加,可以有效增加乙酸裂化产物中芳香烃含量(12%到90%,均为积分面积分数);愈创木酚结构比较复杂,HZSM-5催化剂主要脱除了甲氧基,催化剂用量的增加可以使芳香烃类稳定物质更容易形成。  相似文献   
774.
Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).  相似文献   
775.
A new coordination polymer, {[CdL(en)]'DMF}n (1, H2L = 4-[(8-hydroxy-5- quinolinyl)azo]-benzenesulfonic acid, en = ethylenediamine, DMF = N,N-dimethylformamide), has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffrac- tion, infrared (IR) spectra, elemental analysis, powder X-ray diffractions (PXRD) and thermo- gravimetric analysis (TGA). Compound 1 crystallizes in monoclinic, space group P2Jc with a = 14.6525(9), b = 13.3917(9), c = 11.8838(8) A, β = 101.2290(10)°, V = 2287.2(3) A3, Z = 4, C20H24CdN6OsS, Mr = 572.91, Dc. = 1.664 mg-mm-3, F(000) = 1160, p = 1.091 mm-1, R = 0.0232 and wR = 0.0587 for 3597 observed reflections (I 〉 2σ(I)). Compound 1 exhibits a one-dimensional (1D) double-chain structure which is further connected through hydrogen bonding and π-π interactions into a three-dimensional (3D) supramolecular network. In addition, it exhibits blue fluorescence at room temperature in the solid state.  相似文献   
776.
Three isomeric metal-organic frameworks,[Cd2(X)(btc)(DMA)3]n(X = Cl(1),Br(2),I(3),H3btc =1,3,5-benzenetricarboxylic acid and DMA = N,Nˊ-dimethylacetamide),have been synthesized and characterized by elemental analysis,infrared spectra(IR),thermogravimetric(TG) analyses and single-crystal X-ray diffraction.Single-crystal X-ray analysis reveals that compounds 1–3 crystallize in the orthorhombic P212121 space group,and feature a three-dimensional(3D) extended framework containing dinuclear [Cd2(COO)3] units as the secondary building units(SBUs).Topological analysis reveals that compounds 1–3 can be simplified into a 3-connected srs topological network.  相似文献   
777.
Photoluminescence (PL) of a heterocomposite, consisting of the nematic liquid crystal (LC) 4-pentyl-4´-cyanobiphenyl (5CB) and anisometric nanoparticles of montmorillonite (MMT) clay, modified by cetyltrimethylammonium bromide (CTAB) has been investigated at 4.2 and 300 K. The incorporation of this organoclay (B4) to 5CB decreases the emission intensity by 7–8 times due to efficient resonant quenching of the exciting energy by the organoclay. The spectrum shifts to a long-wave region, with this effect being considerably larger at low temperatures. Graphical separation of complex bands, corresponding to the bulk 5CB and 5СВ?+?В4 heterosystem at both temperatures revealed that the presence of the organoclay resulted in a significant growth of LC dimer quantity, shifting spectra towards longer wavelengths. Changes in the 5CB luminescence under organoclay influence can be explained by quite strong interphase interactions specified earlier by infrared spectroscopy between the MMT surface and LC, and by a realisation of more flat conformations of 5CB molecules. Confinement effects prevent full crystallisation of 5CB in the 5CB?+?B4 composite, and LC dimer structures located in the organoclay near-surface layers on the outer surface of the nanoparticles and inside its galleries remain in a larger amount, at low temperature, when compared to bulk 5CB. The remaining LC crystallises and photoluminescence from the 5CB monomers becomes intense.  相似文献   
778.
ABSTRACT

The polluting effects of Iponri-Alaka Canal in Surulere area of Lagos State on the environment have been studied using six sampling points. The study aimed at assessing the effects of exposure to pollutants on humans and other life forms. The quality of air, wastewater and sediments was assessed between March and August 2017. The concentrations of SO2 and H2S were measured using MSA Altair 5X. Temperature, pH and DO were measured in-situ using Thermometer, pH meter and Winkler method, respectively. TSS, TDS, TS, TA, TH, BOD, chloride Cl?, PO43-, SO42- and NO3? were determined using appropriate standard methods in the laboratory. EC and some heavy metals (Cr, Pb, Mn, Cd and Ni) concentrations were determined using conductivity meter and Atomic Absorption Spectroscopy, respectively. The results showed that pH, TS, DO and TH were well within the WHO and FEPA maximum limits. EC, SO42- and TDS were observed to be higher than guideline values only at one sampling point. The TSS, BOD, TA, NO3? and PO43- were higher than WHO and FEPA guideline limits at all sampling points. Cr was seen to be within, while Pb and Mn were higher than WHO and FEPA guideline values. Cd was higher than guideline values only at two sampling points. Ni was below detection concentration at all the sampling points.

The concentration of SO2 was seen to be higher than WHO and NESREA guideline values at two sampling points, while H2S concentration was higher than WHO limit at all the six sampling points.  相似文献   
779.
The self‐inclusion behavior of monoester copillar[5]arenes depends on the position of the ester group, which causes different guest selectivities. Monoester copillar[5]arenes bearing an acetate chain can form stable self‐inclusion complexes in low‐ and high‐concentration solution and exhibit high guest selectivity. However, a monoester copillar[5]arene bearing a butyrate chain can not form a self‐inclusion complex and exhibits low guest selectivity. Thus, a new class of stable self‐inclusion complexes of copillar[5]arenes was explored to improve the selectivity of molecular recognition.  相似文献   
780.
以自制不对称双子季铵盐表面活性剂为模板, 在水热合成体系中控制合成系列硅铝比纳米薄层ZSM-5分子筛.采用X射线衍射(XRD)、N2吸附-脱附、X射线荧光光谱(XRF)、扫描电镜(SEM)和27Al魔角旋转核磁共振(27Al MAS-NMR)对合成的样品进行了表征. 详细研究了晶化温度、晶化时间、结构导向剂(SDA)用量、碱度等对合成的影响和纳米薄层ZSM-5分子筛的形成过程. 结果表明: 分子筛硅铝比越高, 结构导向剂用量越大, 所需的晶化时间越短; 晶化温度越高, 晶化时间越短; 且不同硅铝比纳米薄层ZSM-5分子筛的形貌规整度、比表面积和介孔/微孔孔容比例随着硅铝比而变化.  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