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1.
The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected CuI, AgI and AuI species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)4]BF4, compound 1 [Cu2(bqmpp)2](BF4)2 is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). CuI complex 2 [Cu4Cl3(bqmpp)2]BF4 contains a rarely observed Cu4Cl3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF6] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by 31P{1H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline-2-ylmethyl)bisphenyl-phosphine ( tqmbp ) compound [Ag2(tqmbp)2](SbF6)2 4 is formed by elimination of quinaldine. The Au(I) compound [Au2(bqmpp)2]PF6 ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around AuI.  相似文献   
2.
Thiacalixarene-supported Co32nanoclusters encapsulated in polyacrylonitrile nanofibers(Co32@PAN-NFs) by electrospinning have been utilized as precursors to fabricate N-doped CoO@Co9S8 carbon nanofibers(CoO@Co9S8@CNFs) for superior Li-ion storage. The S-rich Co32 clusters capped by organic sheets afforded the well dispersed cobalt oxide/sulfide nanoparticles embedded in carbon nanofiber composites by direct calcination. The N-doped CoO@Co9S8@CNFs nanocomposites have been utilized as anode materials for lithium ion battery with the reversible capabilities being of 1051.8, 967.6, 894.7, 782.7, 669.5 and 525.4 mA·h/g at 0.1, 0.2, 0.5, 1, 2 and 3 A/g, respectively. The CoO@Co9S8@CNFs also showed a relatively high stable capacity of 551.7 mA·h/g at the current density of 1 A/g after 200 cycles of rate experiments. The as-obtained N-doped CoO@Co9S8@CNFs nanocomposites exhibited superior reversible capacity, rate performance, Coulomb efficiency(74.5% vs. 63.9%) and cyclic stability comparing with the CoO@Co9S8@C derived from simple annealing of Co32 templates.  相似文献   
3.
黑色直液笔是一种新型书写工具,目前对该种笔墨迹的相关研究较少。为给文件检验工作中墨迹的分析提供新的参考依据,本实验使用显微共聚焦拉曼光谱技术,采集了30支不同品牌、型号的黑色直液笔墨迹光谱数据,进行Savitzky-Golay卷积平滑处理后,依据光谱图的拉曼位移及拉曼谱峰差异对墨迹进行初步分析。设置聚类方法为组间联接,区间距离测量方式为平方欧式距离,对采集的光谱数据进行群分析,将30支黑色直液笔墨迹样本分成了3类,并与品牌建立了相关联系;同时通过主成分分析验证了群分析的可靠性和准确性。研究表明,显微共聚焦拉曼光谱技术结合群分析方法可实现对黑色直液笔墨迹的无损分析及有效鉴别,该方法操作简便、结果准确,适用于法庭科学文件检验。  相似文献   
4.
析氢反应是电解水产制氢的关键反应之一.在碱性条件下,由于催化剂表面与反应过程中产生的氧物种、氢物种与催化剂的吸附未处于最佳状态,析氢反应动力学往往比较缓慢,比在酸性条件下慢2-3个数量级.目前,铂基纳米催化剂被认为是最优的析氢催化剂,但因价格昂贵、稳定性较差,限制了其在电解水器件上的大规模应用.因此,设计一种价格较为低廉、活性高和稳定性好的碱性析氢催化剂尤为必要.钌作为铂族金属之一,其价格约为铂的三分之一,但其与氢的结合能却与铂类似.因此,钌基催化剂被认为是有望替代铂作为析氢催化剂.本文结合模板法、静电纺丝和碳化热解策略构筑了一种负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼催化剂,有效提升了碱性条件下析氢反应性能.该催化剂具有较高的比表面积,丰富的缺陷结构,原子级分散的金属Co掺杂以及无定型钌纳米簇结构,并在碱性条件下催化析氢反应时,表现出了低起始过电位,低Tafel斜率(62 mV dec-1)和高稳定性.X射线衍射(XRD)结果表明,该催化剂中钌和钴以无定型形式存在.选区电子衍射结果表明了无定型结构的存在,并且钌以纳米簇形式存在,其平均粒径为1.48 nm.X射线光电子能谱结果表明该催化剂含有较高的氮掺杂,拉曼光谱证明了其存在碳缺陷结构.进一步通过X射线近边吸收谱和扩展边精细结构谱研究了钌和钴的配位环境,结果发现,钌带轻微正电荷,并且存在Ru-Ru键;钴带正电荷,价态介于0与+2价之间,其主要与N配位.在1 mol/L氢氧化钾电解液中,该杂化催化剂的电催化活性明显高于没有钴掺杂的催化剂以及商业化铂/碳催化剂.在电流密度为10 mA cm-2时,过电位仅为40 mV,在过电位为100 mV时,该催化剂的质量催化活性达到了3.77 mAμgRu-1,远超商业化铂/碳(2.01 mAμgRu-1)和钌/碳(1.66 mAμgRu-1).该催化剂也表现出了优异的析氢催化稳定性,5000圈循环后,10 mA cm-2下的过电位仅增加了2 mV,在恒电流测试中,10 h后电位仅下降了95 mV.  相似文献   
5.
Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al2O3 and SiO2. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al2O3 and SiO2. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al2O3 and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO2 as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al2O3 than those in Pd supported on SiO2, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O2 titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm−1) reacted first with oxygen in the case of CO-saturated Pd on Al2O3 and SiO2, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.  相似文献   
6.
自1981年创刊以来,《光学学报》以发表国内优秀光学科研成果为己任,为我国光学科技人员提供了高水平、活跃的学术交流平台。《光学学报》经历了近40年的洗礼,见证了国内一代代优秀光学科研人员的成长。本文首先回顾了《光学学报》从创刊到转企、集群化发展,再到数字化出版的变革之路;其次,统计了《光学学报》历年来的出版数据、数据库收录、引证指标、荣誉等信息;最后,阐述了《光学学报》未来办刊策略和发展方向。  相似文献   
7.
Zhihang Xu 《中国物理 B》2022,31(4):40304-040304
We propose a novel scheme for remote state preparation of an arbitrary three-qubit state with unit success probability, utilizing a nine-qubit cluster-GHZ state without introducing auxiliary qubits. Furthermore, we proceed to investigate the effects of different quantum noises (e.g., amplitude-damping, phase-damping, bit-flip and phase-flip noises) on the systems. The fidelity results of three-qubit target state are presented, which are usually used to illustrate how close the output state is to the target state. To compare the different effects between the four common types of quantum noises, the fidelities under one specific identical target state are also calculated and discussed. It is found that the fidelity of the phase-flip noisy channel drops the fastest through the four types of noisy channels, while the fidelity is found to always maintain at 1 in bit-flip noisy channel.  相似文献   
8.
Many small biological objects, such as viruses, survive in a water environment and cannot remain active in dry air without condensation of water vapor. From a physical point of view, these objects belong to the mesoscale, where small thermal fluctuations with the characteristic kinetic energy of kBT (where kB is the Boltzmann’s constant and T is the absolute temperature) play a significant role. The self-assembly of viruses, including protein folding and the formation of a protein capsid and lipid bilayer membrane, is controlled by hydrophobic forces (i.e., the repulsing forces between hydrophobic particles and regions of molecules) in a water environment. Hydrophobic forces are entropic, and they are driven by a system’s tendency to attain the maximum disordered state. On the other hand, in information systems, entropic forces are responsible for erasing information, if the energy barrier between two states of a switch is on the order of kBT, which is referred to as Landauer’s principle. We treated hydrophobic interactions responsible for the self-assembly of viruses as an information-processing mechanism. We further showed a similarity of these submicron-scale processes with the self-assembly in colloidal crystals, droplet clusters, and liquid marbles.  相似文献   
9.
为利用3D荧光技术实现基于贮藏室气体荧光信息的香蕉腐败早期预警,选取两批不同贮藏日期的香蕉贮藏室气体进行三维荧光数据采集。首先对荧光数据进行了预处理:为消除三维荧光仪整体漂移现象,对得到的三维荧光数据进行去除漂移处理;利用matlab中eemscat工具包对瑞利与拉曼散射进行去除处理,有效消除了瑞利散射和拉曼散射的不利影响;运用Savitzky-Golar(SG)进行数据平滑处理,减少了噪声对荧光信号的干扰。同时,对三维荧光数据进行初步筛选,去除了荧光强度接近于0的发射波长,以及利用三阶高斯混合分布对不同激发波长下的发射光谱进行拟合去除了离散性较大的激发波长。然后针对荧光数据的特征表征,提出了一种基于Wilks Λ统计量融合间隔偏最小二乘法(iPLS)的荧光数据特征选择策略。具体是:用Wilks Λ统计量进行特征激发波长的选取,初步选出了5个特征激发波长;根据初选的特征激发波长用iPLS结合pH值及相对电导率进行了特征发射波段的选取,结果每个特征激发波长下均选出包含14个波长的特征发射波段。为进一步减少分析变量个数,根据选出的特征发射波长,运用Wilks Λ统计量再次进行特征激发波长反选,最终得到了3个特征激发波长。考虑到各特征激发波长下对应14个特征发射波长,故可选出42个特征发射波长。最后基于香蕉在贮藏中其品质变化具有时变特点,根据42个特征发射波长使用系统聚类分析法(SCA)进行香蕉腐败基准界定,得到两批香蕉均在贮藏的第5天出现品质突变。因此选用第5天贮藏室气体荧光信息来表征香蕉的腐败情况。另外,利用主成分分析(PCA)初步探索了用第1主成分实现香蕉早期腐败的预警。结果表明:文中提出的三维荧光数据特征波长的选择策略是能够有效降低光谱数据的复杂度,同时给出的早期腐败预警方法是可行的。  相似文献   
10.
本文研究线型/圈型网络上单台车辆分群调度问题。给定一个线型/圈型网络,若干客户分布其中。所有客户被划分成若干个子集,每个子集称为一个群。每个客户有一个释放时间和一个服务时间。给定一台车辆,其需要服务所有客户,且每个群内的客户连续服务。问题的要求是计算一个时间表,使得车辆能够按要求服务完所有客户并返回初始出发位置所花费的时间最少。针对该问题,就线型网络和圈型网络,分别给出一个7/4和一个13/7近似算法。  相似文献   
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