全文获取类型
收费全文 | 11969篇 |
免费 | 1974篇 |
国内免费 | 2003篇 |
专业分类
化学 | 11588篇 |
晶体学 | 357篇 |
力学 | 381篇 |
综合类 | 100篇 |
数学 | 1046篇 |
物理学 | 2474篇 |
出版年
2024年 | 35篇 |
2023年 | 197篇 |
2022年 | 329篇 |
2021年 | 565篇 |
2020年 | 772篇 |
2019年 | 568篇 |
2018年 | 500篇 |
2017年 | 453篇 |
2016年 | 680篇 |
2015年 | 682篇 |
2014年 | 701篇 |
2013年 | 1229篇 |
2012年 | 721篇 |
2011年 | 666篇 |
2010年 | 613篇 |
2009年 | 719篇 |
2008年 | 744篇 |
2007年 | 806篇 |
2006年 | 732篇 |
2005年 | 663篇 |
2004年 | 626篇 |
2003年 | 517篇 |
2002年 | 368篇 |
2001年 | 257篇 |
2000年 | 259篇 |
1999年 | 232篇 |
1998年 | 201篇 |
1997年 | 181篇 |
1996年 | 174篇 |
1995年 | 161篇 |
1994年 | 95篇 |
1993年 | 77篇 |
1992年 | 65篇 |
1991年 | 44篇 |
1990年 | 40篇 |
1989年 | 30篇 |
1988年 | 27篇 |
1987年 | 30篇 |
1986年 | 23篇 |
1985年 | 43篇 |
1984年 | 25篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 12篇 |
1976年 | 6篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 281 毫秒
991.
研究了钴块中氢含量的测定方法。采用石英坩埚加载样品,热抽取法进行测定。不加任何助熔剂,分析功率为100%,匹配的分析时间为110 s,比较水平设定为0.1%。在选定的参数下,样品能在完全熔融状态下释放出全部氢。方法加标回收率为80%~119%,测定结果的相对标准偏差小于15%(n=6),检出限为0.5μg/g。热抽取法的精密度优于熔融法的精密度,满足微量气体分析的要求。 相似文献
992.
建立惰气熔融-热导法测定钕铁硼永磁材料中氢的分析方法。当氧-氢比例大于50:1时,CO对氢的测定结果产生一定的干扰,加入舒茨试剂可消除此干扰。采用标准坩埚,称样0.05g,熔融功率为2.85 kW,选择高纯镍篮和锡片做助熔剂,钕铁硼中氢释放完全。以普通钢铁参考物质建立氢校准曲线,线性相关系数r~2=0.9999,检出限为0.75μg/g。该法用于钕铁硼样品中氢的测定,测定结果与脉冲熔融飞行时间质谱-气体元素分析仪测定结果基本一致,测定结果的相对标准偏差为1.4%(n=5)。该方法可以准确测定钕铁硼永磁材料中的氢,能满足日常分析的要求。 相似文献
993.
Lisi Xie Dr. Jia Tian Yingjie Ouyang Xinai Guo Prof. Dr. Weian Zhang Prof. Dr. Ulf-Peter Apfel Prof. Dr. Wei Zhang Prof. Dr. Rui Cao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):15978-15982
Molecular design to improve catalyst performance is significant but challenging. In enzymes, residue groups that are close to reaction centers play critical roles in regulating activities. Using this bioinspired strategy, three water-soluble polymers were designed with appending Co porphyrins and different side-chain groups to mimic enzyme reaction centers and activity-controlling residue groups, respectively. With these polymers, high hydrogen evolution efficiency was achieved in neutral aqueous media for electro- (turnover frequency >2.3×104 s−1) and photocatalysis (turnover number >2.7×104). Porphyrin units are surrounded and protected by polymer chains, and more importantly, the activity can be tuned with different side-chain groups. Therefore, instead of revising molecular structures that is difficult from both design and synthesis points of view, polymers can be used to improve molecular solubility and stability and simultaneously regulate activity by using side-chain groups. 相似文献
994.
Meng Zhao Dr. Hong-Jie Peng Bo-Quan Li Dr. Xiao Chen Jin Xie Dr. Xinyan Liu Prof. Qiang Zhang Prof. Jia-Qi Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9096-9102
In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co4N) in working Li-S batteries that renders highly active electrocatalysts (CoSx). Electrochemical cycling induces the transformation from single-crystalline Co4N to polycrystalline CoSx that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co4N enables stable operation of high-rate (10 C, 16.7 mA cm−2) and electrolyte-starved (4.7 μL mgS−1) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds. 相似文献
995.
Dr. Ding Yi Fei Lu Fengchu Zhang Dr. Shoujie Liu Dr. Bo Zhou Denglei Gao Prof. Xi Wang Prof. Jiannian Yao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):15989-15993
Single-atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single-atom-doped titania enables tunable hydrogen evolution reaction (HER) activity. First-principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping-induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single-atom-doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets. 相似文献
996.
Dr. Linzhou Zhuang Dr. Yi Jia Hongli Liu Zhiheng Li Dr. Mengran Li Dr. Longzhou Zhang Dr. Xin Wang Prof. Dongjiang Yang Prof. Zhonghua Zhu Prof. Xiangdong Yao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14772-14778
The oxygen vacancies of defective iron–cobalt oxide (FeCoOx-Vo) nanosheets are modified by the homogeneously distributed sulfur (S) atoms. S atoms can not only effectively stabilize oxygen vacancies (Vo), but also form the Co−S coordination with Co active site in the Vo, which can modulate the electronic structure of the active site, enabling FeCoOx-Vo-S to exhibit much superior OER activity. FeCoOx-Vo-S exhibits a mass activity of 2440.0 A g−1 at 1.5 V vs. RHE in 1.0 m KOH, 25.4 times higher than that of RuO2. The Tafel slope is as low as 21.0 mV dec−1, indicative of its excellent charge transfer rate. When FeCoOx-Vo-S (anode catalyst) is paired with the defective CoP3/Ni2P (cathode catalyst) for overall water splitting, current densities of as high as 249.0 mA cm−2 and 406.0 mA cm−2 at a cell voltage of 2.0 V and 2.3 V, respectively, can be achieved. 相似文献
997.
Bingqing Lin Xi Wu Prof. Dr. Lin Xie Yongqiang Kang Prof. Dr. Hongda Du Prof. Dr. Feiyu Kang Prof. Dr. Jia Li Prof. Dr. Lin Gan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20528-20532
Resolving interstitial hydrogen atoms at the surfaces and interfaces is crucial for understanding the mechanical and physicochemical properties of metal hydrides. Although palladium (Pd) hydrides hold important applications in hydrogen storage and electrocatalysis, the atomic position of interstitial hydrogen at Pd hydride near surfaces still remains undetermined. We report the first direct imaging of subsurface hydrogen atoms absorbed in Pd nanoparticles by using differentiated and integrated differential phase contrast within an aberration-corrected scanning transmission electron microscope. In contrast to the well-established octahedral interstitial sites for hydrogen in the bulk, subsurface hydrogen atoms are directly identified to occupy the tetrahedral interstices. DFT calculations show that the amount and the occupation type of subsurface hydrogen atoms play an indispensable role in fine-tuning the electronic structure and associated chemical reactivity of the Pd surface. 相似文献
998.
Yi-Fan Wang Yiyu Liang Yan-Fang Wu Jian Yang Xu Zhang Dr. Dandan Cai Dr. Xu Peng Dr. Mohamedally Kurmoo Prof. Dr. Ming-Hua Zeng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13334-13339
The in situ tracking of the pyrolysis of a binary molecular cluster [Zn7(μ3-CH3O)6(L)6][ZnLCl2]2 is presented with one brucite disk and two mononuclear fragments (L=mmimp: 2-methoxy-6-((methylimino)-methyl)phenolate) to porous carbon using TG-MS from 30 to 900 °C. Following up the spilled gas product during the decomposed reaction of zinc cluster along the temperature rising, and in conjunction with XRD, SEM, BET and other materials characterization, where three key steps were observed: 1) cleavage of the bulky external ligand; 2) reduction of ZnO and 3) volatilization of Zn. The real-time-dependent phase-sequential evolution of the remaining products and the processing of pore forming template transformation are proposed simultaneously. The porous carbon structure featuring a uniform nano-sized pore distribution synthesized at 900 °C with the highest surface area of 1644 m2 g−1 and pore volume of 0.926 cm3 g−1 exhibits the best known capacitance of 662 F g−1 at 0.5 A g−1. 相似文献
999.
Susith R. Galle Kankanamge Jianbo Ma Dr. Robert T. Mackin Dr. Fedra M. Leonik Prof. Carol M. Taylor Prof. Igor V. Rubtsov Prof. Daniel G. Kuroda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17160-17165
Hydrogen bonds (H bonds) play a major role in defining the structure and properties of many substances, as well as phenomena and processes. Traditional H bonds are ubiquitous in nature, yet the demonstration of weak H bonds that occur between a highly polarized C−H group and an electron-rich oxygen atom, has proven elusive. Detailed here are linear and nonlinear IR spectroscopy experiments that reveal the presence of H bonds between the chloroform C−H group and an amide carbonyl oxygen atom in solution at room temperature. Evidence is provided for an amide solvation shell featuring two clearly distinguishable chloroform arrangements that undergo chemical exchange with a time scale of about 2 ps. Furthermore, the enthalpy of breaking the hydrogen bond is found to be 6–20 kJ mol−1. Ab-initio computations support the findings of two distinct solvation shells formed by three chloroform molecules, where one thermally undergoes hydrogen-bond making and breaking. 相似文献
1000.
Jiaxi Zhang Longhai Zhang Li Du Huolin L. Xin John B. Goodenough Zhiming Cui 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(40):17641-17646
A group of newly reported antiperovskite nitrides CuxIn1−xNNi3 (0≤x≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu0.4In0.6NNi3 shows the highest intrinsic performance among all developed catalysts with an overpotential of merely 42 mV at 10 mA cmgeo−2. Stability tests at a high current density of 100 mA cmgeo−2 show its super-stable performance with only 7 mV increase in overpotential after more than 60 hours of measurement, surpassing commercial Pt/C (increase of 170 mV). By partial substitution, the derived antiperovskite nitride achieves a smaller kinetic barrier of water dissociation compared to the unsubstituted InNNi3 and CuNNi3, revealed by first-principle calculations. It is found that the partially substituted CuxIn1−xNNi3 possesses a thermal neutral and desirable Gibbs free energy of hydrogen for HER, ascribed to the tailoring of the energy of d-band center arose by the A-site (A=Cu or In) substitution and a resulting optimization of adsorbate interactions. 相似文献