全文获取类型
收费全文 | 4304篇 |
免费 | 819篇 |
国内免费 | 486篇 |
专业分类
化学 | 3253篇 |
晶体学 | 37篇 |
力学 | 215篇 |
综合类 | 44篇 |
数学 | 481篇 |
物理学 | 1579篇 |
出版年
2024年 | 2篇 |
2023年 | 74篇 |
2022年 | 94篇 |
2021年 | 111篇 |
2020年 | 176篇 |
2019年 | 193篇 |
2018年 | 154篇 |
2017年 | 125篇 |
2016年 | 236篇 |
2015年 | 201篇 |
2014年 | 254篇 |
2013年 | 299篇 |
2012年 | 362篇 |
2011年 | 366篇 |
2010年 | 272篇 |
2009年 | 291篇 |
2008年 | 307篇 |
2007年 | 268篇 |
2006年 | 254篇 |
2005年 | 223篇 |
2004年 | 163篇 |
2003年 | 143篇 |
2002年 | 174篇 |
2001年 | 151篇 |
2000年 | 90篇 |
1999年 | 102篇 |
1998年 | 61篇 |
1997年 | 58篇 |
1996年 | 67篇 |
1995年 | 43篇 |
1994年 | 54篇 |
1993年 | 32篇 |
1992年 | 20篇 |
1991年 | 42篇 |
1990年 | 37篇 |
1989年 | 29篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 12篇 |
1985年 | 19篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1970年 | 1篇 |
1966年 | 1篇 |
1964年 | 1篇 |
1962年 | 1篇 |
1959年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有5609条查询结果,搜索用时 24 毫秒
31.
Dr. Chi Zhang Dr. Meiling Shao Dr. Dongqing Wu Dr. Zhongyi Li Muzhi Zhao Xiangfei Zhang Prof. Bin Zhai Prof. Yunjun Luo Prof. Xiaoyu Li 《Angewandte Chemie (International ed. in English)》2023,62(52):e202314052
Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E3)-containing cation, [P444E3][N3] and [MIME3][N3]. Compared with the traditional sodium azide (NaN3) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E3 moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers. 相似文献
32.
Jiadong Chen Yulu Zhang Prof. Dr. Shengbiao Tang Prof. Dr. Ying Shao Prof. Dr. Jiangtao Sun 《European journal of organic chemistry》2023,26(32):e202300605
One-step process for the preparation of a 1,3-dienyl-5-ester motif from readily available substrate remains a challenging work in organic synthesis. We herein report the first example of C5-regioselective esterification of unactivated dienyl alcohols, using free carboxylic acids as nucleophiles under mild conditions, providing a series of 1,3-dienyl-5-ester compounds in excellent regioselectivity and E-selectivity. 相似文献
33.
Dr. Peng Dong Tingna Shao Jinlian Li Xiaohui Zhang Prof. Yu Zhao Prof. Xinhong Zhao Prof. Guixian Li 《欧洲无机化学杂志》2023,26(33):e202300483
Cyclohexane epoxide, which contains highly active epoxy groups, plays a crucial role as an intermediate in the preparation of fine chemicals. However, controlling the epoxidation pathway of cyclohexene is challenging due to issues such as the allylic oxidation of cyclohexene and the ring opening of cyclohexane epoxide during the cyclohexene epoxidation process to form cyclohexane oxide. This review focuses on the structure-activity relationships and synthesis processes of various heterogeneous transition metal-based catalysts used in cyclohexene epoxidation reactions, including molybdenum(Mo)-based, tungsten(W)-based, vanadium(V)-based, titanium(Ti)-based, cobalt(Co)-based, and other catalysts. Initially, the mechanism of cyclohexene epoxidation by transition metal-based catalysts is examined from the perspective of catalytic active centers. Subsequently, the current research of cyclohexene epoxidation catalysts is summarized based on the perspective of catalyst support. Additionally, the differences between alkyl hydroperoxide, hydrogen peroxide (H2O2), and oxygen (O2) as oxidants are analyzed. Finally, the main factors influencing catalytic performance are summarized, and reasonable suggestions for catalyst design are proposed. This work provides scientific support for the advancement of the olefin epoxidation industry. 相似文献
34.
Dr. Xiaolong Zu Yuan Zhao Dr. Xiaodong Li Runhua Chen Weiwei Shao Li Li Panzhe Qiao Prof. Wensheng Yan Prof. Yang Pan Qian Xu Prof. Junfa Zhu Prof. Yongfu Sun Prof. Yi Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202215247
Herein, we first design a model of reversible redox-switching metal–organic framework single-unit-cell sheets, where the abundant metal single sites benefit for highly selective CO2 reduction, while the reversible redox-switching metal sites can effectively activate CO2 molecules. Taking the synthetic Cu-MOF single-unit-cell sheets as an example, synchrotron-radiation quasi in situ X-ray photoelectron spectra unravel the reversible switching CuII/CuI single sites initially accept photoexcited electrons and then donate them to CO2 molecules, which favors the rate-liming activation into CO2δ−, verified by in situ FTIR spectra and Gibbs free energy calculations. As an outcome, Cu-MOF single-unit-cell sheets achieve near 100 % selectivity for CO2 photoreduction to CO with a high rate of 860 μmol g−1 h−1 without any sacrifice reagent or photosensitizer, where both the activity and selectivity outperform previously reported photocatalysts evaluated under similar conditions. 相似文献
35.
Haodong Nie Kaiqiang Wei Yi Li Yan Liu Yajie Zhao Hui Huang Mingwang Shao Yang Liu Zhenhui Kang 《中国化学快报》2021,32(7):2283-2286
Overall water photo-splitting is a prospective ideal pathway to produce ultra-clean H_2 energy by semiconductors.However,the band structure of many semiconductors cannot satisfy the requirement of H_2 and O_2 production at the same time.Herein,we illustrate that carbon dots(CDs)/Bi_2 WO_6 photocatalyst with compensatory photo-electronic effect has enhanced activity for overall water photo-splitting without any sacrificial agent.In this complex photocatalytic system,the photo-potential provided by CDs makes the CDs/Bi_2 WO6(C-BWO) composite could satisfy the band structure conditions for overall water photo-splitting.The C-BWO composite(3 wt% CDs content) exhibits optimized hydrogen evolution(oxygen evolution) of 0.28 μmol/h(0.12 μmol/h) with an approximate 2:1(H_2:O_2) stoichiometry at normal pressure.We further employed the in-situ transient photovoltage(TPV) technique to study the photoelectron extraction and the interface charge transfer kinetics of this composite catalyst. 相似文献
36.
Xiaomin Kang Guodong Fu Xuewan Wang Lin Shao Weili Li Chi-Wing Tsang Xiao-Ying Lu Xian-Zhu Fu Jing-Li Luo 《中国化学快报》2021,32(2):938-942
Numerous scientists are in the pursuit of energy storage materials with high energy and high power density by assembly of electrochemically active materials into conductive scaffolds, owing to the emerging need for next-generation energy storage devices. In this architectures, the active materials bonded to the conductive scaffold can provide a robust and free-standing structure, which is crucial to the fabrication of materials with high gravimetric capacity. Thus, hierarchical copper-cobalt-nickel ternary oxide (CuCoNi-oxide) nanowire arrays grown from copper foam were successfully fabricated as free-standing anode materials for lithium ion batteries (LIBs). CuCoNi-oxide nanowire arrays could provide more active sites owing to the hyperbranched structure, leading to a better specific capacity of 1191 mAh/g, cycle performance of 73% retention in comparison to CuO nanowire structure, which exhibited a specific capacity of 1029 mAh/g and capacity retention of 43%, respectively. 相似文献
37.
Chao Rong Wu Yan-Wei Lu Ling Xu Wei-Feng Wang Chang-Yun Shao Chang-Lun 《Chemistry of Natural Compounds》2021,57(2):343-345
Chemistry of Natural Compounds - Benzomalvins B, C, and E (1, 2, and 3) were simultaneously obtained from the marine fungus Aspergillus sp. isolated from the soft coral Sinularia sp., collected... 相似文献
38.
Rui-Jia Chen Jun-Jie Wang Li Han Yu-Cheng Gu Zhi-Ping Xu Jia-Gao Cheng Xu-Sheng Shao Xiao-Yong Xu Zhong Li 《Journal of heterocyclic chemistry》2021,58(7):1429-1436
A series of diamide derivatives containing α-amino acids were designed and synthesized. These compounds were evaluated for their insecticidal activities against Plutella xylostella, Mythimna separate, Myzus persicae, and Tetranychus cinnabarinus. Most of the title compounds containing an l -phenylglycine skeleton were endowed with good activities at the concentration of 500 mg·L−1. Compounds ( R)-A6 showed a potential value for further optimization as an insecticidal lead with the LC50 value of 86.8 mg·L−1. 相似文献
39.
阴离子交换膜(AEM)燃料电池因具有使用非贵金属作为催化剂的优点而受到广泛关注.然而,在碱性体系中,AEM燃料电池中氢氧化反应(HOR)的反应动力学比在酸性介质中的慢两个数量级.针对HOR在碱中动力学缓慢的问题,有两种主要的理论来解释,(1)pH相关的氢结合能作为主要影响因素来控制HOR动力学的理论;(2)质子和氢氧根离子的吸附共同作为影响因子来控制HOR在碱性条件下的动力学的双功能理论.本文首先讨论了在碱性电解质中可能的HOR反应机理及其Tafel性能变化.除了传统的Tafel-Volmer和Heyrovsky-Volmer-HOR机理外,还讨论了最新提出的氢氧根离子吸附参与的HOR机理来说明在酸性和碱性介质中HOR机理的差异.然后,总结了具有代表性的碱性HOR催化剂(如贵金属、合金、金属间化合物、镍基合金、碳化物、氮化物等),简要介绍了它们相应的HOR反应机理,从而进一步理解在碱性介质中不同基元反应步骤给HOR性能带来的差异.最后,提出了一种未来设计HOR碱性催化剂的可行性方案,为今后碱性环境下的HOR催化剂设计提供参考. 相似文献
40.
随着社会发展,传统化石能源消耗加剧,人类迫切需要开发新型的清洁能源.半导体光催化分解水产氢是一种非常具有潜力解决能源危机的清洁技术.目前,金属硫化物半导体有着合适的能带结构和高效的光催化产氢能力而得到了广泛的研究.通常,为了提高光催化剂产氢性能,添加贵金属助催化剂是一个行之有效的方法.但是贵金属昂贵的价格限制了其大规模的应用,因此有必要研究储量丰富,价格低廉的高效助催化剂.Ni2P,CoP,Co2P,MoP,Cu3P等过渡金属磷化物具有价格低廉,优异的稳定性和催化性能而被用作电催化产氢的催化剂.通常,用于电催化产氢的催化剂往往可以作为光催化产氢的助催化剂.众所周知,催化性能与材料的形貌密切相关,因此,具有棒状、中空、片状等形貌的金属硫化物被制备并用于光催化产氢.然而,四足状结构的金属硫化物研究较少.在已有的Ni2P(NP)相关研究中,仅合成了纳米颗粒状的NP.本文成功合成了四足状Cd0.9Zn0.1S(CZS)和珊瑚状形貌的NP,进一步得到一系列Ni2P-Cd0.9Zn0.1S(NPCZS)光催化剂,采用XRD,SEM,TEM,XPS和ICP-AES测试了样品的结构、形貌、表面成分和元素含量,并测试了样品的光催化产氢性能.采用水热法合成的CZS样品具有特殊的四足状形貌,足部由纳米棒组成.XRD结果表明,四足状CZS中立方相(WZ)和六方相(ZB)共存.经TEM进一步分析,发现CZS中心部位呈ZB相结构,而足部却是WZ相.经光催化性能测试,这种新型四足状CZS表现出优异的光催化产氢性能.进一步通过超声或研磨破坏四足状结构后,发现CZS的产氢性能显著下降,说明四足状形貌是材料性能提高的关键.通过分析WZ和ZB两物相的价带顶和导带底的电位发现,ZB/WZ间形成的同质结可以加速光生载流子的分离和传输.NP也采用水热法制备,其具有珊瑚状形貌.该形貌具有高的比表面积,可以提供更多的活性位点,进一步提高了材料的光催化性能.光催化性能测试表明,NP负载量为12 wt%的NPCZS-12样品表现出很好的产氢性能(l.88 mmol h-1),是纯CZS的1.43倍.同时,NPCZS-12具有良好的光稳定性和循环使用性能.结合光催化实验、光谱实验、表面光电压和电化学测试的结果发现,四足状形貌、同质结和NP助催化剂的协同效应是NPCZS具有良好光催化性能的主要原因. 相似文献