全文获取类型
收费全文 | 3186篇 |
免费 | 603篇 |
国内免费 | 519篇 |
专业分类
化学 | 2457篇 |
晶体学 | 34篇 |
力学 | 144篇 |
综合类 | 29篇 |
数学 | 395篇 |
物理学 | 1249篇 |
出版年
2024年 | 8篇 |
2023年 | 82篇 |
2022年 | 90篇 |
2021年 | 128篇 |
2020年 | 155篇 |
2019年 | 161篇 |
2018年 | 142篇 |
2017年 | 132篇 |
2016年 | 175篇 |
2015年 | 200篇 |
2014年 | 198篇 |
2013年 | 243篇 |
2012年 | 287篇 |
2011年 | 304篇 |
2010年 | 234篇 |
2009年 | 224篇 |
2008年 | 241篇 |
2007年 | 182篇 |
2006年 | 175篇 |
2005年 | 153篇 |
2004年 | 98篇 |
2003年 | 62篇 |
2002年 | 79篇 |
2001年 | 47篇 |
2000年 | 55篇 |
1999年 | 60篇 |
1998年 | 31篇 |
1997年 | 51篇 |
1996年 | 63篇 |
1995年 | 59篇 |
1994年 | 45篇 |
1993年 | 40篇 |
1992年 | 19篇 |
1991年 | 27篇 |
1990年 | 15篇 |
1989年 | 13篇 |
1988年 | 10篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1965年 | 3篇 |
1936年 | 1篇 |
排序方式: 共有4308条查询结果,搜索用时 15 毫秒
41.
Dr. Ziyang Song Dr. Ling Miao Dr. Yaokang Lv Prof. Lihua Gan Prof. Mingxian Liu 《Angewandte Chemie (International ed. in English)》2023,62(38):e202309446
Organic small molecules as high-capacity cathodes for Zn-organic batteries have inspired numerous interests, but are trapped by their easy-dissolution in electrolytes. Here we knit ultrastable lock-and-key hydrogen-bonding networks between 2, 7-dinitropyrene-4, 5, 9, 10-tetraone (DNPT) and NH4+ charge carrier. DNPT with octuple-active carbonyl/nitro centers (H-bond acceptor) are redox-exclusively accessible for flexible tetrahedral NH4+ ions (H-bond donator) but exclude larger and rigid Zn2+, due to a lower activation energy (0.14 vs. 0.31 eV). NH4+ coordinated H-bonding chemistry conquers the stability barrier of DNPT in electrolyte, and gives fast diffusion kinetics of non-metallic charge carrier. A stable two-step 4e− NH4+ coordination with DNPT cathode harvests a high capacity (320 mAh g−1), a high-rate capability (50 A g−1) and an ultralong life (60,000 cycles). This finding points to a new paradigm for H-bond stabilized organic small molecules to design advanced zinc batteries. 相似文献
42.
Cheng Cheng Dr. Wei Ren Fei Miao Xuantong Chen Xiaoxiao Chen Prof. Hui Zhang 《Angewandte Chemie (International ed. in English)》2023,62(10):e202218510
Generating FeIV=O on single-atom catalysts by Fenton-like reaction has been established for water treatment; however, the FeIV=O generation pathway and oxidation behavior remain obscure. Employing an Fe−N−C catalyst with a typical Fe−N4 moiety to activate peroxymonosulfate (PMS), we demonstrate that generating FeIV=O is mediated by an Fe−N−C−PMS* complex—a well-recognized nonradical species for induction of electron-transfer oxidation—and we determined that adjacent Fe sites with a specific Fe1−Fe1 distance are required. After the Fe atoms with an Fe1-Fe1 distance <4 Å are PMS-saturated, Fe−N−C−PMS* formed on Fe sites with an Fe1-Fe1 distance of 4–5 Å can coordinate with the adjacent FeII−N4, forming an inter-complex with enhanced charge transfer to produce FeIV=O. FeIV=O enables the Fenton-like system to efficiently oxidize various pollutants in a substrate-specific, pH-tolerant, and sustainable manner, where its prominent contribution manifests for pollutants with higher one-electron oxidation potential. 相似文献
43.
Wei Zong Haiqi Gao Yue Ouyang Kaibin Chu Hele Guo Leiqian Zhang Wei Zhang Ruwei Chen Yuhang Dai Fei Guo Jiexin Zhu Zhenfang Zhang Chumei Ye Dr. Yue-E. Miao Prof. Johan Hofkens Dr. Feili Lai Prof. Tianxi Liu 《Angewandte Chemie (International ed. in English)》2023,62(27):e202218122
Competition from hydrogen/oxygen evolution reactions and low solubility of N2 in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe3C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe3C/Fe@PCNF-F away from water infiltration and endow a N2 molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust “quasi-solid–gas” state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe3C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH3 yield rate up to 29.2 μg h−1 mg−1cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO3− yield rate up to 15.7 μg h−1 mg−1cat. and FE up to 3.4 % in nitrogen oxidation reaction). 相似文献
44.
Liangxu Lin Liang Huang Chang Wu Yu Gao Naihua Miao Chao Wu Aaron T. Marshall Yi Zhao Jiazhao Wang Jun Chen Shixue Dou Gordon G. Wallace Wei Huang 《Angewandte Chemie (International ed. in English)》2023,62(49):e202315182
The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e− ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e− ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H2O2 production. The work here gives not only new understandings on the 2e− ORR catalysis, but also the robust catalyst which can be directly used in industry. 相似文献
45.
Shanshan Sun Litao Wang Jiasheng Wang Wenjing Lv Qinghua Yu Dong Pei Siqi Han Xingyu Li Miao Wang Sheng Liu Xiangao Quan Mei Lv 《Journal of separation science》2023,46(16):2200935
In this work, homochiral reduced imine cage was covalently bonded to the surface of the silica to prepare a novel high-performance liquid chromatography stationary phase, which was applied for the multiple separation modes such as normal phase, reversed-phase, ion exchange, and hydrophilic interaction chromatography. The successful preparation of the homochiral reduced imine cage bonded silica stationary phase was confirmed by performing a series of methods including X-ray photoelectron spectroscopy, thermogravimetric analysis, and infrared spectroscopy. From the extracted results of the chiral resolution in normal phase and reversed-phase modes, it was demonstrated that seven chiral compounds were successfully separated, among which the resolution of 1-phenylethanol reached the value of 3.97. Moreover, the multifunctional chromatographic performance of the new molecular cage stationary phase was systematically investigated in the modes of reversed-phase, ion exchange, and hydrophilic interaction chromatography for the separation and analysis of a total of 59 compounds in eight classes. This work demonstrated that the homochiral reduced imine cage not only achieved multiseparation modes and multiseparation functions performance with high stability, but also expanded the application of the organic molecular cage in the field of liquid chromatography. 相似文献
46.
Miao Zhu Qin Zhou He Cheng Prof. Dr. Ye Sha Prof. Dr. Vladimir I. Bregadze Prof. Dr. Hong Yan Prof. Dr. Zhe Sun Prof. Dr. Xiang Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202213470
The combination of carbon-based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace-like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o-carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido-o-carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid-state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging. 相似文献
47.
研究了低功率超声(US, <38 W)对NaClO氧化非离子型碘代X射线造影剂—碘帕醇(IPM)的增强作用及机理, 考察了NaClO添加浓度和超声功率的影响, 分析并计算了体系中的主要活性物种及其贡献. 采用高效液相色谱/串联质谱(HPLC/MS/MS)对降解产物进行分析, 推测IPM的降解路径. 结果表明, 低功率US显著增强了NaClO对IPM的氧化效果, 在25 ℃, pH=5.8, NaClO浓度为0.12 mmol/L条件下, 10 mg/L IPM在60 min的降解率达到85.8%. 其中NaClO氧化、 HO·和活性氯自由基(RCSs)是US/NaClO增强IPM降解的主要原因, 自由基分析计算它们的贡献率分别为15.82%, 4.65%和79.53%. NaClO浓度在0~0.24 mmol/L范围内, IPM的降解率随NaClO浓度升高而增加, 60 min后降解率由4.75%增加到91.12%; 超声功率为28.5 W, 降解率达到最高. 在 15~45 ℃温度范围内, IPM的降解过程符合表观一级反应动力学, 反应活化能(Ea)为59.03 kJ/mol. HPLC/MS/MS共检测出5种中间产物, 结合密度泛函理论(DFT)计算结果, 初步推测了IPM在US/NaClO体系中的降解途径和机理. 相似文献
48.
近年来,具有聚集诱导发光(aggregation-induced emission,AIE)特性的化合物由于在聚集态或固态发光量子效率较高而受到很多关注.含氟的功能化合物,由于氟原子的存在,往往具有独特的结构和物理、化学及生物学性质.根据中心金属和配体的种类,汇总了具有A IE性质的且含有氟代配体的有机金属配合物的研究进展.这些含氟有机金属配合物主要是铱、铂、金配合物,在发光器件、化学传感、细胞成像、数据存储等方面具有潜在应用.还简要讨论了相关研究的发展前景. 相似文献
49.
有机太阳能电池具有低成本、柔性和质量轻等优势, 是一种有应用前景的光伏技术, 受到人们的广泛关注. 有机太阳能电池的光敏活性层通常由p-型有机半导体(包括小分子和高分子)与n-型有机半导体(包括小分子和高分子)共混而成. 小分子给体/高分子受体型有机太阳能电池具有形貌热稳定性优异的特点, 值得深入研究. 本综述旨在总结小分子给体/高分子受体型有机太阳能电池的研究进展, 分别介绍了基于酰亚胺基、氰基和含硼氮配位键(B←N)的高分子受体的活性层材料体系的发展状况. 在器件性能方面, 通过分子设计、相分离形貌调控, 改善了小分子给体/高分子受体的匹配性, 将该类电池的能量转换效率从最初的0.29%提升至目前的9.51%, 为性能的进一步提升总结了经验; 在稳定性方面, 基于该体系形貌热稳定性优异的特点, 开发出高温耐受型有机太阳能电池器件. 最后, 展望了小分子给体/高分子受体型有机太阳能电池的未来发展方向和前景. 相似文献
50.