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   2409篇
  免费   257篇
  国内免费   745篇
化学   3129篇
晶体学   38篇
力学   21篇
综合类   30篇
物理学   193篇
  2024年   1篇
  2023年   88篇
  2022年   103篇
  2021年   165篇
  2020年   176篇
  2019年   127篇
  2018年   99篇
  2017年   120篇
  2016年   135篇
  2015年   95篇
  2014年   119篇
  2013年   210篇
  2012年   225篇
  2011年   140篇
  2010年   111篇
  2009年   177篇
  2008年   150篇
  2007年   188篇
  2006年   166篇
  2005年   146篇
  2004年   111篇
  2003年   100篇
  2002年   87篇
  2001年   48篇
  2000年   45篇
  1999年   53篇
  1998年   40篇
  1997年   35篇
  1996年   15篇
  1995年   30篇
  1994年   27篇
  1993年   21篇
  1992年   19篇
  1991年   5篇
  1990年   7篇
  1989年   5篇
  1988年   6篇
  1987年   5篇
  1986年   7篇
  1985年   1篇
  1982年   2篇
  1979年   1篇
排序方式: 共有3411条查询结果,搜索用时 15 毫秒
1.
The detection of cancer biomarkers is of great significance for the early screening of cancer. Detecting the content of sarcosine in blood or urine has been considered to provide a basis for the diagnosis of prostate cancer. However, it still lacks simple, high-precision and wide-ranging sarcosine detection methods. In this work, a Ti3C2TX/Pt–Pd nanocomposite with high stability and excellent electrochemical performance has been synthesized by a facile one-step alcohol reduction and then used on a glassy carbon electrode (GCE) with sarcosine oxidase (SOx) to form a sarcosine biosensor (GCE/Ti3C2TX/Pt–Pd/SOx). The prominent electrocatalytic activity and biocompatibility of Ti3C2TX/Pt–Pd enable the SOx to be highly active and sensitive to sarcosine. Under the optimized conditions, the prepared biosensor has a wide linear detection range to sarcosine from 1 to 1000 µM with a low limit of detection of 0.16 µM (S/N = 3) and a sensitivity of 84.1 µA/mM cm2. Besides, the reliable response in serum samples shows its potential in the early diagnosis of prostate cancer. More importantly, the successful construction and application of the amperometric biosensor based on Ti3C2TX/Pt–Pd will provide a meaningful reference for detecting other cancer biomarkers.  相似文献   
2.
双金属有机骨架及其衍生物一方面具有单金属有机骨架孔道丰富、比表面积大、结构可调、活性位点丰富等特点,另一方面具有双组分与多孔结构之间的协同效应,因而受到了研究人员的密切关注,在储能、催化、分离、传感器、医药、气体存储等领域广泛应用。和单金属MOFs类似,双金属MOFs的导电性不佳、结构易坍塌,这极大地限制了其在电化学储能中的应用。通过对双金属MOFs进行热处理,易得到分布均匀的多孔碳@双金属氧化物/硫化物/磷化物/硒化物等衍生物,不仅保持了独特的多孔结构,而且提高了材料的导电性和结构稳定性,有利于在电化学储能中的应用。因此,本文从双金属MOFs中的主要金属离子入手,综述了双金属MOFs及其衍生物用于超级电容器、锂离子电池、钠离子电池、金属空气电池等电化学储能器件的最新应用进展。在此基础上,总结了双金属MOFs在电化学储能应用中的优势,并对其制备、作用机理和后处理研究提出了建议。  相似文献   
3.
Several p H-dependent processes and reactions take place in the human body;hence,the p H of body fluids is the best indicator of disturbed health conditions.However,accurate and real-time diagnosis of the p H of body fluids is complicated because of limited commercially available p H sensors.Hence,we aimed to prepare a flexible,transparent,disposable,userfriendly,and economic strip-based solid-state p H sensor using palladium nanoparticles(Pd NPs)/N-doped carbon(NC)composite material.The Pd NPs/NC composite material was synthesized using wool keratin(WK)as a precursor.The insitu prepared Pd NPs played a key role in the controlled switching of protein structure to the N-doped carbon skeleton withπ–πarrangement at the mesoscale level,which mimics the A–B type polymeric structure,and hence,is highly susceptible to H+ions.The optimized carbonization condition in the presence of Pd NPs showed that the material obtained using a modified Ag/Ag Cl reference electrode had the highest p H sensitivity with excellent stability and durability.The optimized p H sensor showed high specificity and selectivity with a sensitivity of 55 m V/p H unit and a relative standard deviation of 0.79%.This study is the first to synthesize Pd NPs using WK as a stabilizing and reducing agent.The applicability of the sensor was investigated for biological samples,namely,saliva and gastric juices.The proposed protocol and material have implications in solid-state chemistry,where biological material will be the best choice for the synthesis of materials with anticipated performance.  相似文献   
4.
薛世翔  吴攀  赵亮  南艳丽  雷琬莹 《化学进展》2022,34(12):2686-2699
析氧反应(OER)是电催化裂解水、二次金属-空气电池和可再生燃料电池等绿色可持续能源储存和转化技术中的关键步骤,但其较高的势垒和迟滞的动力学过程限制了反应的效率。因此,设计开发高效、稳定的非贵金属催化剂是新能源领域面临的挑战之一。钴铁水滑石(CoFe LDH)材料具有独特的二维层状结构、丰富多变的化学组成、高分散的金属阳离子、优异的稳定性和成本低廉等优点,在OER反应中有广泛的应用前景。但不良的导电性和有限的活性位点阻碍了CoFe LDH的工业化应用。本文首先介绍了CoFe LDH的结构并阐述了其OER反应机理,接着总结了CoFe LDH的制备工艺,并详细综述了近年来提升其 OER性能的改性策略:插层剥离、空位制造、材料复合、离子取代和衍生物等。最后讨论了水滑石材料现阶段存在的问题和未来在能源转化和利用领域的发展方向。  相似文献   
5.
Electrochemical glucose sensors have garnered considerable attention because of their attractive prospect in point-of-care testing (POCT). In this review, we firstly introduce the principles and challenges of electrochemical glucose sensors. Subsequently, we present an overview of the application of electrochemical glucose sensors and discuss their advantages and drawbacks. Wearable and implantable devices based on diverse target biofluid and platforms provide a considerable prospect of accurate and continuous monitoring. Thus, we believe that the future development direction of electrochemical glucose sensors is non-invasive, wearable devices and implantable devices with minimally invasive for continuous glucose monitoring in real time.  相似文献   
6.
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   
7.
采用一步电化学法在金属Bi板上成功制备了BiOCl0.5Br0.5/BiPO4双层异质结薄膜,并通过多种表征手段对薄膜的晶型结构、元素组成及化合价、形貌和尺寸特征、吸光性能和荧光强度进行了表征。结果表明,制备得到的复合薄膜呈现出上层为梭子状的BiPO4颗粒层分散在下层为BiOCl0.5Br0.5固溶体层的双层结构。这样的双层膜排列顺序使得光生电子和空穴在不同组分之间的界面电场作用下分别向薄膜两侧流动,促进光致载流子的分离,提高了BiOCl0.5Br0.5/BiPO4复合薄膜的光催化活性。活性测试结果表明,在模拟太阳光照射120 min后,BiOCl0.5Br0.5/BiPO4复合薄膜对苯酚的降解率达到了99.97%,是相同条件下制备的BiOCl/BiPO4和BiOBr/BiPO4复合薄膜对苯酚降解率的1.69倍和1.20倍。在苯酚的降解过程中,主要参与的活性物种是空穴(h+)和羟基自由基(·OH)。其光催化活性增强的原因归功于BiOCl0.5Br0.5/BiPO4复合薄膜拓宽的光谱吸收范围和增强的载流子分离率。  相似文献   
8.
Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, CaxV2O5-H2O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.  相似文献   
9.
以清洁可再生电能为驱动力,常温常压下将二氧化碳(CO2)选择性还原转化生成高附加值化学品或燃料,是解决目前能源和环境问题、实现CO2资源化利用、促进碳循环回归平衡的有效手段之一。由于生成不同产物的还原电位和反应历程不同,单位产物的生产成本各有差异。最近研究表明,HCOOH是所有电化学CO2还原产物中最具有经济效益和实用价值的产物之一。本文从电催化还原CO2制HCOOH生成机理出发,综述了p区金属(如Sn、Bi、In)基催化剂在电催化还原CO2制HCOOH领域取得的重要研究进展,其中以典型催化剂为例分析了CO2还原生成HCOOH活性提高策略如氧化物还原转化、形貌调控、掺杂和合金化等,重点探讨了活性位点种类、数量以及催化剂电子结构在关键中间体*CO2.-、*OCHO的形成和吸附中的作用,最后总结了目前该领域面临的挑战以及未来发展方向。  相似文献   
10.
Understanding the biocatalytic or the interfacial electron transfer processes of redox enzymes is decisive to develop high-performance biofuel cells, mimetic catalysts, bioelectrosynthesis reactors, biosensors, and bioelectronic devices. The state-of-art of redox enzyme electrochemistry lies in using in situ and operando instrumentation, in which protein electrochemistry is resourcefully coupled to or hyphenated with numerous analytical techniques. Nevertheless, there is still a lot to research about the manipulation of redox proteins in the unusual sample holding environments, and bioelectrodes engineering emerges as a key. Here, we discuss these challenges in detail, focusing on contemporary instrumentation setups.  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