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   9084篇
  免费   1257篇
  国内免费   2113篇
化学   8895篇
晶体学   175篇
力学   646篇
综合类   120篇
数学   291篇
物理学   2327篇
  2024年   30篇
  2023年   192篇
  2022年   450篇
  2021年   618篇
  2020年   516篇
  2019年   423篇
  2018年   358篇
  2017年   456篇
  2016年   554篇
  2015年   464篇
  2014年   601篇
  2013年   898篇
  2012年   716篇
  2011年   669篇
  2010年   466篇
  2009年   624篇
  2008年   598篇
  2007年   571篇
  2006年   489篇
  2005年   435篇
  2004年   390篇
  2003年   304篇
  2002年   276篇
  2001年   169篇
  2000年   159篇
  1999年   159篇
  1998年   137篇
  1997年   124篇
  1996年   68篇
  1995年   74篇
  1994年   68篇
  1993年   79篇
  1992年   68篇
  1991年   35篇
  1990年   26篇
  1989年   32篇
  1988年   39篇
  1987年   23篇
  1986年   21篇
  1985年   17篇
  1984年   8篇
  1983年   7篇
  1982年   10篇
  1981年   8篇
  1980年   4篇
  1979年   7篇
  1978年   3篇
  1973年   3篇
  1971年   2篇
  1957年   2篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Automotive proton exchange membrane fuel cell stacks need to meet manufacturer specified rated beginning-of-life (BOL) performance before being assembled into vehicles and shipped off to customers. The process of “breaking-in” of a freshly assembled stack is often referred to as “conditioning.” It has become an intensely researched area especially in automotive companies, where imminent commercialization of fuel cell electric vehicles (FCEVs) demands a short, energy- and cost-efficient, and practical conditioning protocol. Significant advances in reducing the conditioning time from 1 to 2 days to as low as 4h or less, in some cases without the use of additional inert gases such as nitrogen, and with minimal use of hydrogen, and specialized test stations will be discussed.  相似文献   
2.
A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.  相似文献   
3.
Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device.  相似文献   
4.
This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+, Na+ or K+) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.  相似文献   
5.
占兴  熊巍  梁国熙 《化学进展》2022,34(11):2503-2516
随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。  相似文献   
6.
Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)2] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.  相似文献   
7.
Covalent organic frameworks (COFs) are a new class of crystalline porous polymers comprised mainly of carbon atoms, and are versatile for the integration of heteroatoms such as B, O, and N into the skeletons. The designable structure and abundant composition render COFs useful as precursors for heteroatom-doped porous carbons for energy storage and conversion. Herein, we describe a multifunctional electrochemical catalyst obtained through pyrolysis of a bimetallic COF. The catalyst possesses hierarchical pores and abundant iron and cobalt nanoparticles embedded with standing carbon layers. By integrating these features, the catalyst exhibits excellent electrochemical catalytic activity in the oxygen reduction reaction (ORR), with a 50 mV positive half-wave potential, a higher limited diffusion current density, and a much smaller Tafel slope than a Pt-C catalyst. Moreover, the catalyst displays superior electrochemical performance toward the hydrogen evolution reaction (HER), with overpotentials of −0.26 V and −0.33 V in acidic and alkaline aqueous solution, respectively, at a current density of 10 mA cm−2. The overpotential in the catalysis of the oxygen evolution reaction (OER) was 1.59 V at the same current density.  相似文献   
8.
Copper oxide decorated multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) was prepared for determination of isoniazid (INZ) in various matrices. The electrochemical behavior of INZ was tested with the aid of Cyclic Voltammetry (CV) and quantitative experiments were performed by using Linear Sweep Voltammetry (LSV). Morphological and structural characterization of the modified electrode was performed by utilizing Scanning Electron Microscopy (SEM), X‐Ray Photoelectron Spectroscopy (XPS) while electrochemical characterization was performed by using CV and Electrochemical Impedance spectroscopy (EIS). The proposed sensor exhibited well defined anodic peak at 0.30 V for INZ at pH 6.0 medium. Under the optimum conditions, a linear relation between INZ concentration and peak current was observed in the range of 2.0×10?7 to 5.0×10?5 M. Limit of detection was calculated as 1.0×10?8 M and repeatability and accuracy was found as 5.60 % and 91.0 % for 5.0 10?7 M INZ by using 3 successive measurement, respectively. Then, the analytic performance of the electrode developed was tested by analyzing commercial tablets, artificial human serum and urine samples. The results indicated that satisfactory recoveries was observed for all issue.  相似文献   
9.
Leukotrienes (LTs) and hydroxyeicosatetraenoic acids (HETEs) are important bioactive lipid mediators that participate in various pathophysiological processes. To advance understanding of the mechanisms that regulate these mediators in physiological and pathological processes, an analytical method using liquid chromatography/tandem mass spectrometry for the simultaneous quantification of LTB4, LTC4, LTD4, LTE4, 5‐HETE, 8‐HETE, 12‐HETE and 15‐HETE in cell culture media was developed. A Supel?‐Select HLB solid‐phase extraction cartridge was used for sample preparation. The compounds were separated on a C18 column using gradient elution with acetonitrile–water–formic acid (20:80:0.1, v/v/v) and acetonitrile–formic acid (100:0.1, v/v). The calibration curves of LTB4, LTD4, LTE4 and HETEs were linear in the range of 0.025–10 ng/mL, and the calibration curve of LTC4 was linear in the range of 0.25–10 ng/mL. Validation assessment showed that the method was highly reliable with good accuracy and precision. The stability of LTs and HETEs was also investigated. Using the developed method, we measured LTs and HETEs in the culture supernatant of the human mast cell line HMC‐1. The present method could facilitate investigations of the mechanisms that regulate the production, release and signaling of LTs and HETEs. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
10.
近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.  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