全文获取类型
收费全文 | 18298篇 |
免费 | 3397篇 |
国内免费 | 2878篇 |
专业分类
化学 | 13293篇 |
晶体学 | 241篇 |
力学 | 1365篇 |
综合类 | 225篇 |
数学 | 2039篇 |
物理学 | 7410篇 |
出版年
2024年 | 7篇 |
2023年 | 371篇 |
2022年 | 422篇 |
2021年 | 558篇 |
2020年 | 772篇 |
2019年 | 680篇 |
2018年 | 599篇 |
2017年 | 572篇 |
2016年 | 844篇 |
2015年 | 864篇 |
2014年 | 1039篇 |
2013年 | 1267篇 |
2012年 | 1670篇 |
2011年 | 1745篇 |
2010年 | 1212篇 |
2009年 | 1134篇 |
2008年 | 1330篇 |
2007年 | 1161篇 |
2006年 | 1176篇 |
2005年 | 960篇 |
2004年 | 740篇 |
2003年 | 601篇 |
2002年 | 592篇 |
2001年 | 500篇 |
2000年 | 451篇 |
1999年 | 469篇 |
1998年 | 336篇 |
1997年 | 303篇 |
1996年 | 347篇 |
1995年 | 299篇 |
1994年 | 288篇 |
1993年 | 212篇 |
1992年 | 200篇 |
1991年 | 161篇 |
1990年 | 142篇 |
1989年 | 126篇 |
1988年 | 113篇 |
1987年 | 70篇 |
1986年 | 62篇 |
1985年 | 48篇 |
1984年 | 35篇 |
1983年 | 31篇 |
1982年 | 13篇 |
1981年 | 22篇 |
1980年 | 8篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1957年 | 5篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
81.
Qing Liu Yibin Liu Hua Zheng Chunmei Li Yi Zhang Qiuyu Zhang 《Journal of polymer science. Part A, Polymer chemistry》2020,58(8):1092-1104
Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material. 相似文献
82.
Yaochen Zheng Jian Liu Yan Guo Qian Zhang Xuan Gao Zhengguo Gao Tao He Qingfu Ban 《Journal of polymer science. Part A, Polymer chemistry》2020,58(12):1664-1674
Cationic compounds often serve as antibacterial materials for a wide range of applications. However, the relationship of topology−antibacterial activity has been rarely revealed. Herein, three cationic polythioethers (CPTEs) with hyperbranched topologies are well designed and facilely synthesized via an all-click chemistry strategy (including thiol-ene and epoxy-amine additions). These as-prepared CPTEs were found to exhibited outstanding antibacterial activity against Escherichia coli and Staphylococcus aureus with minimum inhibitory concentrations against E. coli of 7.3, 14.6, and 14.6 μg ml−1, and against S. aureus of 14.6, 29.2, and 29.2 μg ml−1, respectively. The antibacterial activity is coincident with their degree of branching (DB, their DB values of 0.81, 0.48, and 0.27), which is mainly attributed to the inherent three-dimensional structure. The present strategy reveals the relationship of polymer topology and antibacterial activity, providing a novel possibility for designing and/or synthesis of high-efficiency antibacterial agents. 相似文献
83.
Dr. Yiteng Zheng Ziyu Tang Prof. Simon G. Podkolzin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5174-5179
The development of improved technologies for biomass processing into transportation fuels and industrial chemicals is hindered due to a lack of efficient catalysts for selective oxygen removal. Here we report that platinum nanoparticles decorated with subnanometer molybdenum clusters can efficiently catalyze hydrodeoxygenation of acetic acid, which serves as a model biomass compound. In contrast with monometallic Mo catalysts that are inactive and monometallic Pt catalysts that have low activities and selectivities, bimetallic Pt–Mo catalysts exhibit synergistic effects with high activities and selectivities. The maximum activity occurs at a Pt to Mo molar ratio of three. Although Mo atoms themselves are catalytically inactive, they serve as preferential binding anchors for oxygen atoms while a catalytic transformation proceeds on neighboring surface Pt atoms. Beyond biomass processing, Pt–Mo nanoparticles are promising catalysts for a wide variety of reactions that require a transformation of molecules with an oxygen atom and, more broadly, in other fields of science and technology that require tuning of surface–oxygen interactions. 相似文献
84.
Dr. Zheng-Guang Wu Xiang-Ji Liao Li Yuan Prof. Yi Wang Prof. You-Xuan Zheng Prof. Jing-Lin Zuo Prof. Yi Pan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5694-5700
Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the CuI-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide–alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide–alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide–alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science. 相似文献
85.
Guiqiang Cao Zhikang Wang Da Bi Prof. Jing Zheng Prof. Qingxue Lai Prof. Yanyu Liang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10314-10320
Lithium-sulfur batteries have been considered as potential electrochemical energy-storage devices owing to their satisfactory theoretical energy density. Nonetheless, the inferior conversion efficiency of polysulfides in essence leads to fast capacity decay during the discharge/charge cycle. In this work, it is successfully demonstrated that the conversion efficiency of lithium polysulfides is remarkably enhanced by employing a well-distributed atomic-scale Fe-based catalyst immobilized on nitrogen-doped graphene (Fe@NG) as a coating of separator in lithium-sulfur batteries. The quantitative electrocatalytic efficiency of the conversion of lithium polysulfides is determined through cyclic voltammetry. It is also proven that the Fe-NX configuration with highly catalytic activity is quite beneficial for the conversion of lithium polysulfides. In addition, the adsorption and permeation experiments distinctly indicate that the strong anchoring effect, originated from the charge redistribution of N doping into the graphene matrix, inhibits the movement of lithium polysulfides. Thanks to these advantages, if the as-prepared Fe@NG catalyst is combined with polypropylene and applied as a separator (Fe@NG/PP) in Li-S batteries, a high initial capacity (1616 mA h g−1 at 0.1 C), excellent capacity retention (93 % at 0.2 C, 70 % at 2 C), and superb rate performance (820 mA h g−1 at 2 C) are achieved. 相似文献
86.
Xinxin Lin Prof. Zheng Fang Cuilian Zeng Chenlong Zhu Xinyan Pang Chengkou Liu Wei He Jindian Duan Ning Qin Prof. Kai Guo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13738-13742
A non-oxidant and metal-free strategy for synthesizing iso-coumarin by using a continuous electrochemical microreactor to initiate an oxidative cyclization reaction of o-(1-alkynyl) benzoate and radicals. This efficient and clean continuous electrosynthesis method not only avoids the complicated gas protection operation and production of by-products in the batch processes, but also help to overcome the difficulty that batch metal catalysis and electrocatalysis are difficult to scale up, and has the potential for pilot-scale experiment. 相似文献
87.
Dr. Wei Zheng Xiao-Lei Yang Dr. Gui-Yuan Wu Prof. Lin Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11695-11700
In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing. 相似文献
88.
Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor
Dengchao Zheng Hao Wen Xun Sun Xin Guan Jie Zhang Wenli Tian Hao Feng Dr. Hongjing Wang Prof. Yadong Yao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17149-17155
In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm−2 (specific capacity C: 1178 C g−1) at 2 mA cm−2 in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg−1 at 143.8 Wkg−1 power density with a capacitance retention of 83.6 % after 5000 cycles. 相似文献
89.