全文获取类型
收费全文 | 2872篇 |
免费 | 615篇 |
国内免费 | 313篇 |
专业分类
化学 | 2011篇 |
晶体学 | 38篇 |
力学 | 143篇 |
综合类 | 25篇 |
数学 | 379篇 |
物理学 | 1204篇 |
出版年
2024年 | 3篇 |
2023年 | 97篇 |
2022年 | 94篇 |
2021年 | 139篇 |
2020年 | 170篇 |
2019年 | 156篇 |
2018年 | 128篇 |
2017年 | 131篇 |
2016年 | 185篇 |
2015年 | 186篇 |
2014年 | 197篇 |
2013年 | 228篇 |
2012年 | 310篇 |
2011年 | 288篇 |
2010年 | 203篇 |
2009年 | 183篇 |
2008年 | 172篇 |
2007年 | 154篇 |
2006年 | 124篇 |
2005年 | 102篇 |
2004年 | 85篇 |
2003年 | 71篇 |
2002年 | 65篇 |
2001年 | 55篇 |
2000年 | 33篇 |
1999年 | 32篇 |
1998年 | 24篇 |
1997年 | 28篇 |
1996年 | 28篇 |
1995年 | 21篇 |
1994年 | 18篇 |
1993年 | 11篇 |
1992年 | 14篇 |
1991年 | 14篇 |
1990年 | 19篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 3篇 |
1974年 | 1篇 |
1959年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有3800条查询结果,搜索用时 593 毫秒
71.
偶合反应化学发光法测定痕量银的研究 总被引:6,自引:0,他引:6
本将Ag(Ⅰ)催化S2O^2-8氧化Mn(Ⅱ)生成MnO^-4的催化反应与LuminolMnO^-4-OH^-的化学发光反应相偶合,建立起一种新的灵敏测定痕量银的化学发光分析法,在所研究的优化条件下,该法测定银的选择性较好,检测限达到3.2×10^-12g/mLAg线性浓度范围为1.0×10^-11-1.0×10^-5g/mLAg,用于水样分析,结果较为满意。 相似文献
72.
纳米银掺杂二氧化硅复合颗粒的制备及表征 总被引:2,自引:0,他引:2
0引言金属纳米颗粒因其粒子尺寸小(1 ̄100nm),比表面积大,表面原子数多,表面能和表面张力随粒径的下降急剧增大而具有量子尺寸效应[1]、小尺寸效应[2]、表面效应[3]及宏观量子隧道效应[4]等,从而出现了不同于常规固体的新奇特性,如:光学性质、磁性质以及电磁学性质[5],使其在催化、信息存储及非线性光学等领域展示了广阔的应用前景[6]。虽然制备金属纳米颗粒的方法有很多[6],但是由于纳米尺寸的金属颗粒具有较高的表面能,容易发生聚集,所以如何保持其稳定性依旧是比较困难的问题。随着纳米科技的发展,人们正尝试用各种方法来解决这个问题:如… 相似文献
73.
Ji-Lai Li Cai-Yun Geng Xu-Ri Huang Chia-Chung Sun 《Theoretical chemistry accounts》2007,117(3):417-429
The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and
transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using
the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction
mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions,
i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism
dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On
the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical
F attacking on the C≡C triple bond in propyne (CH3C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying
intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H2CCCHF + H via transition state TS5/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore,
based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect
that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present
work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons.
This material is available from author via E-mail. 相似文献
74.
Paulus UA Wang Y Kim SH Geng P Wintterlin J Jacobi K Ertl G 《The Journal of chemical physics》2004,121(22):11301-11308
Catalytic CO oxidation on the RuO(2)(110) surface was studied at 300 K by scanning tunneling microscopy (STM), high-resolution electron-energy-loss spectroscopy (HREELS), and thermal desorption spectroscopy (TDS). Upon repeatedly exposing the surface to several 10 L of CO and O(2) at 300 K, STM shows that unreactive features accumulate with each CO and O(2) titration run. HREELS and TDS show formation of increasing amounts of H(2)O, retarded formation of O-cus atoms and incomplete removal of CO-bridge molecules during O(2) dosing, and a changing ratio of single- and double-bonded CO-bridge molecules. It is concluded that H(2)O (presumably from the residual gas) is accumulating at the Ru-cus sites thus blocking them, so that the dissociative adsorption of oxygen is prevented and the CO oxidation reaction is suppressed. Some 10% CO- bridge remains on the surface even during oxygen exposure. Consistent with this interpretation, deactivation of the surface is suppressed at 350 K, at the onset of H(2)O desorption. 相似文献
75.
N. Kent Dalley Weiming Jiang Krzysztof E. Krakowiak Geng Wu D. Wade Walke Jerald S. Bradshaw Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(3):299-308
Hydrazino-crown ethers have been synthesized in only 3 or 4 steps starting from 1,2-diacetylhydrazine. The X-ray crystal structure of protonated hydrazino-19-crown-7 (2) showed that one of the hydrazino nitrogen atoms was directed outside the ring cavity. A solvent methanol molecule is held in the cavity of the host ligand by three hydrogen bonds involving two hydrogen atoms bonded to nitrogens of the ligand and the alcohol hydrogen of the methanol. The logK values for the interaction of2 with CH3NH
+
3
, Ag+, Pb2+, and Cd2+ were much less than those for the interaction of symmetrical triaza-l8-crown-6 (5) with the same cations. Hydrazino-crown2 reduced silver ions to silver metal when a solution of2 and silver ions in DMSO was allowed to stand for several days. 相似文献
76.
Geng ZhiYuan Yao Kun Wang YongCheng Fang Ran Zhang XingHui Jia BaoLi 《中国科学B辑(英文版)》2007,50(3):335-344
The mechanisms of theion reaction of alkylidenegermylene with oxirane and thiirane have been characterized detail in using density functional theory, as well as ab initio method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies were calculated by CCSD(T)/6-311G(d)//B3LYP/6-311G(d,p) method for the involved conformations. The results show that the reaction pathways for both reactions consist of two ways: (1) the reactants can yield bent products (P1; P4) by syn-isomers; (2) the reactants can also yield three-membered products (P2; P5) by anti-isomers, which then further react with oxirane and thiirane to form the ultimate products (P3-1, P3-2; P6). Furthermore, a comparison with alkylidenecarbene, oxirane, and thiirane was done. 相似文献
77.
Yu Mao Wenxuan Zhao Shuo Lu Lei Yu Yi Wang Yong Liang Shengyang Ni Yi Pan 《Chemical science》2020,11(19):4939
Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation. 相似文献
78.
Yanchen Liu Chenchen Wang Shuo Zhao Lin Zhang Kai Zhang Fujun Li Jun Chen 《Chemical science》2021,12(3):1062
Layered manganese-based oxides are promising candidates as cathode materials for sodium-ion batteries (SIBs) due to their low cost and high specific capacity. However, the Jahn–Teller distortion from high-spin Mn3+ induces detrimental lattice strain and severe structural degradation during sodiation and desodiation. Herein, lithium is introduced to partially substitute manganese ions to form distorted P′2-Na0.67Li0.05Mn0.95O2, which leads to restrained anisotropic change of Mn–O bond lengths and reinforced bond strength in the [MnO6] octahedra by mitigation of Jahn–Teller distortion and contraction of MnO2 layers. This ensures the structural stability during charge and discharge of P′2-Na0.67Li0.05Mn0.95O2 and Na+/vacancy disordering for facile Na+ diffusion in the Na layers with a low activation energy barrier of ∼0.53 eV. It exhibits a high specific capacity of 192.2 mA h g−1, good cycling stability (90.3% capacity retention after 100 cycles) and superior rate capability (118.5 mA h g−1 at 1.0 A g−1), as well as smooth charge/discharge profiles. This strategy is effective to tune the crystal structure of layered oxide cathodes for SIBs with high performance.Li-Substitution in P′2-Na0.67MnO2 mitigates the anisotropic change of Mn–O bonds and Na/vacancy ordering, and hence significantly promotes its cycling stability and rate capability as a cathode material for sodium-ion batteries. 相似文献
79.
Hongyang Su Lanlan Chen Yizhen Chen Prof. Rui Si Yuting Wu Xiaonan Wu Dr. Zhigang Geng Prof. Wenhua Zhang Prof. Jie Zeng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20591-20596
Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH3). Reported herein is a novel Fe-MoS2 catalyst with Fe atomically dispersed onto MoS2 nanosheets, imitating natural nitrogenase, to boost N2 electroreduction into NH3 at room temperature. The Fe-MoS2 nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mgcat.−1 h−1 for NH3 at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N2 was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS2 with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N2 into NH3. This work provides new ideas for the design of catalysts for N2 electroreduction and strengthens the understanding about N2 activation over Mo-based catalysts. 相似文献
80.
Ru‐Jong Jeng Geng‐Sheng Lo Chih‐Ping Chen Ying‐Ling Liu Ging‐Ho Hsiue Wen‐Chiung Su 《先进技术聚合物》2003,14(2):147-156
Epoxy resins modified by an organosoluble phosphorus‐containing bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide; BMPPPO) were prepared by simultaneously curing epoxy/diaminodiphenylmethane (DDM), and BMPPPO. The resulted epoxy resins were found to exhibit glass transition temperatures as high as 212 °C, thermal stability at temperatures over 350 °C, and excellent flame retardancy with Limited oxygen index (LOI) values around 40. Incorporation of BMPPPO into epoxy resins via the thermosetting blend was demonstrated to be an effective way to enhance the thermal properties and flame retardancy simultaneously. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献