全文获取类型
收费全文 | 3186篇 |
免费 | 100篇 |
国内免费 | 175篇 |
专业分类
化学 | 3340篇 |
晶体学 | 31篇 |
综合类 | 1篇 |
数学 | 7篇 |
物理学 | 82篇 |
出版年
2024年 | 1篇 |
2023年 | 36篇 |
2022年 | 22篇 |
2021年 | 30篇 |
2020年 | 55篇 |
2019年 | 88篇 |
2018年 | 88篇 |
2017年 | 100篇 |
2016年 | 96篇 |
2015年 | 71篇 |
2014年 | 146篇 |
2013年 | 423篇 |
2012年 | 122篇 |
2011年 | 158篇 |
2010年 | 177篇 |
2009年 | 174篇 |
2008年 | 216篇 |
2007年 | 227篇 |
2006年 | 192篇 |
2005年 | 185篇 |
2004年 | 158篇 |
2003年 | 159篇 |
2002年 | 84篇 |
2001年 | 55篇 |
2000年 | 40篇 |
1999年 | 24篇 |
1998年 | 27篇 |
1997年 | 25篇 |
1996年 | 30篇 |
1995年 | 40篇 |
1994年 | 47篇 |
1993年 | 29篇 |
1992年 | 31篇 |
1991年 | 17篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 14篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有3461条查询结果,搜索用时 215 毫秒
1.
催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向. 相似文献
2.
《Mendeleev Communications》2022,32(3):395-396
A new method for assembling 1,3-selenazolines by the iodine- mediated reaction of the simplest building blocks such as elemental selenium, alkenes and acetonitrile has been discovered. A proposed mechanism includes the addition of the intermediate selenium iodides to alkene with subsequent solvent interception by the formed seleniranium ion. 相似文献
3.
Dr. Qian Zhang Dr. Ning Liu Hongchang Mo Dr. Xianming Lu Yao Wang Dr. Minghui Xu Prof. Yuanjie Shu 《ChemistryOpen》2019,8(5):571-579
An azide terminated ethylene oxide-tetrahydrofuran copolymer with urethane segments (ATUPET) as a novel binder pre-polymer, has been prepared through ethylene oxide-tetrahydrofuran random copolymer (PET) end-capping modification via one-pot method. The structure characterization of the modifier has been analyzed by FTIR, 1H NMR, 13C NMR and GPC. In comparison with PET, ATUPET has a slightly higher viscosity because it has additional hydrogen bonding interaction generated by the urethane in ATUPET. Triazole cross-linked elastomers based on ATUPET with various functional molar ratios were prepared using tripropargylamine as a curing agent and cross-linker. Mechanical properties indicate that the modulus E and tensile strength σb exhibit a parabolic dependence with the increase in R. At around the stoichiometric ratio, the modulus E and tensile strength σb reach a maximum and the elongation at break exhibit an acceptable value at the same time. Swelling tests demonstrate that the apparent cross-linking densities (N0) have a maximum value at the stoichiometric ratio. Thermal analysis shows that the ATUPET prepolymer and its polytriazoles elastomers exhibit a satisfactory stability. The results demonstrated that ATUPET might be a promising polymeric binder for future propellant formulations especially in the field of isocyanate-free curing technology. 相似文献
4.
《中国化学快报》2019,30(11):1951-1954
Utilization of intermolecular Friedel-Crafts and intramolecular condensation reaction,novel 1,3-di-(pyridine-2-yl)benzene(N,C,N terdentate) skeleton with electro-withdrawing group in 6' position of pyridyl and a cyclization between 6' position of pyridyl and 6 position of benzyl ring were firstly designed and synthesized.The structures of these novel N,C,N terdentate were confirmed by NMR,MS and X-ray single crystalanalyses.The photophysical properties of these compounds were briefly explored. 相似文献
5.
Anna Peterson Mari-Liis Ludvig Jevgenija Martõnova Sandra Kaabel Paul Kerner Merle Uudsemaa 《Supramolecular chemistry》2020,32(5):313-319
ABSTRACT We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K a = 111 ± 3 M–1) and in methanol (K a = 2020 ± 70 M–1). 相似文献
6.
Dayang Yu Guoliang Mao Huaixun Cai Shuhua Wang Jiandang Liu Pengju Pan Yongzhong Bao 《Journal of polymer science. Part A, Polymer chemistry》2021,59(9):754-763
2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene (PDD-TFE) copolymer is a good candidate to prepare gas separation membranes with excellent permeability due to its free volume characteristics. However, the influence of PDD-TFE copolymer structure on its free volume characteristics is less studied. In this paper, PDD-TFE copolymers with different compositions and molecular weights were synthesized, and their free volume characteristics were analyzed by positron annihilation lifetime spectroscopy and a molecular dynamics simulation. It indicated that the molar fraction of PDD in copolymers had a significant effect on free volume characteristics, while the molecular weight of copolymers exerted a slight influence on free volume when the molecular weight exceeded a critical region (intrinsic viscosity [η] > 68 ml g−1). PDD-TFE copolymers with greater PDD molar fractions (i.e., 72% and 84%) showed bimodal distributions in positron lifetime and free volume size distributions, while PDD-TFE copolymers with lower PDD molar fractions (i.e., 27% and 35%) exhibited a single peak. The long-lifetime parameter τ3 was assigned to micro-cavities formed by [-(TFE)y-PDD-] segments and τ4 was attributed to micro-cavities formed by [-(PDD)x-TFE-] segments. The cis and trans transitions of PDD led to a local multilayer spiral structure with a 2.6–4.3 Å layer spacing, which would also increase the free volume of copolymers. 相似文献
7.
Chunhong Wang Qi Cui Zhixin Zhang Prof. Zhu-Jun Yao Dr. Shaozhong Wang Prof. Zhi-Xiang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9821-9826
1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally. 相似文献
8.
9.
HZSM‐5‐supported Brönsted and Lewis acidic ionic solid 1,3‐disulfoimidazolium chlorozincate materials ([dsim]2[ZnCl4]@HZSM‐5) were synthesized with various ratios (3, 6, 9, 17 and 50% w/w). The heterogeneous materials were characterized via a variety of spectroscopic techniques. Dual acidity of these materials was determined using specified techniques. These acidic solids were examined as stable heterogeneous catalysts for the Fischer indole reaction of equimolar amounts of phenylhydrazine hydrochloride and various aliphatic or aromatic ketones at 80–90°C in neat condition to produce substituted indole derivatives. The efficient 17% ionic salt‐loaded HZSM‐5 composite was easily reused for ten consecutive cycles with a slight loss of its activity. The recycled catalyst was further analysed using powder X‐ray diffraction and inductively coupled plasma optical emission spectrometric techniques. 相似文献
10.