全文获取类型
收费全文 | 2408篇 |
免费 | 417篇 |
国内免费 | 367篇 |
专业分类
化学 | 1882篇 |
晶体学 | 25篇 |
力学 | 12篇 |
综合类 | 7篇 |
数学 | 40篇 |
物理学 | 1226篇 |
出版年
2024年 | 7篇 |
2023年 | 34篇 |
2022年 | 41篇 |
2021年 | 56篇 |
2020年 | 106篇 |
2019年 | 84篇 |
2018年 | 59篇 |
2017年 | 64篇 |
2016年 | 102篇 |
2015年 | 89篇 |
2014年 | 95篇 |
2013年 | 185篇 |
2012年 | 143篇 |
2011年 | 130篇 |
2010年 | 99篇 |
2009年 | 145篇 |
2008年 | 141篇 |
2007年 | 218篇 |
2006年 | 136篇 |
2005年 | 85篇 |
2004年 | 100篇 |
2003年 | 147篇 |
2002年 | 116篇 |
2001年 | 172篇 |
2000年 | 114篇 |
1999年 | 81篇 |
1998年 | 78篇 |
1997年 | 76篇 |
1996年 | 52篇 |
1995年 | 50篇 |
1994年 | 41篇 |
1993年 | 28篇 |
1992年 | 25篇 |
1991年 | 19篇 |
1990年 | 22篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有3192条查询结果,搜索用时 17 毫秒
131.
Li-Dan Lin Prof. Dr. Dan Zhao Prof. Dr. Xin-Xiong Li Prof. Dr. Shou-Tian Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):442-453
During the past decade, research on the design and synthesis of zeolite-like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. 相似文献
132.
Jinjuan Xue Chengjuan Huang Yuqing Zong Jiandong Gu Mingxin Wang Shuaishuai Ma 《应用有机金属化学》2019,33(11)
Fe (III)‐grafted Bi2MoO6 nanoplates (Fe (III)/BMO) with varying small quantity of Fe (III) clusters modification were fabricated through a simple hydrothermal and impregnation process. The characterization results indicate that the modification of Fe (III) clusters on the surface of Bi2MoO6 nanoplates with intimate interfacial contact is beneficial to the expansion of visible light absorption range and the separation of photoinduced carriers during the interface charge transfer process. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) and selective aerobic oxidation of biomass‐derived chemical 5‐hydroxymethylfuraldehyde (HMF) under visible light. The 1.5 wt% Fe (III) clusters‐grafted Bi2MoO6 nanoplates exhibited optimum photocatalytic activity, which is the TC degradation kinetic rate constant is 5.3 times higher than that of bare BMO, and the highest HMF conversion of 32.62% can be obtained with a selectivity of 95.30%. Furthermore, a possible visible light photocatalysis mechanism over Fe (III)/BMO sample has been proposed. This study may supply some insight for the development of visible‐light‐driven Bi2MoO6‐based photocatalysts applicable to both environmental remediation and biomass‐derived chemical transformation. 相似文献
133.
S. A. Gevelyuk I. K. Doycho L. P. Prokopovich E. Rysiakiewics-Pasek E. D. Safronsky 《辐射效应与固体损伤》2013,168(1-6):427-432
We have studied the influence of multiple carbon treatments on the properties of silica porous glasses. Each step of each carbon treatment started with filling the voids of porous glass with carbon. During the following anneal carbon interacted with the walls of the voids. It was shown that low dimensional silicon clusters were formed inside the voids as a result of this reaction. In the experiments the photoluminescence spectra and conductivity of carbon-processed specimens were measured. The size-distribution of voids in porous glasses was calculated from absorption—desorption isotherms. An original technique was proposed that allowed to obtain the size-distribution of silicon clusters from the positions of peaks in the photoluminescence spectra. Correlation between the photoluminescence intensity and the sizes of pores was revealed. The observed oscillations in the shapes of the photoluminescence spectra in subsequent cycles of carbon treatment are explained by changes of the number of clusters corresponding to definite peaks in the size distribution spectra. 相似文献
134.
135.
Xin Cheng Dr. Zi-Yu Li Li-Hui Mou Yi Ren Dr. Qing-Yu Liu Prof. Dr. Xun-Lei Ding Prof. Dr. Sheng-Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16523-16527
The side-on-end-on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V5N5]−) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV). 相似文献
136.
Dr. Johanna Scheck Lisa M. Fuhrer Dr. Baohu Wu Dr. Markus Drechsler Prof. Dr. Denis Gebauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):13002-13007
Hematite (α-Fe2O3) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room-temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase-separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism. 相似文献
137.
138.
《Journal of computational chemistry》2018,39(17):1038-1043
The Kernel energy method (KEM) is a quantum chemical calculation method that has been shown to provide accurate energies for large molecules. KEM performs calculations on subsets of a molecule (called kernels) and so the computational difficulty of KEM calculations scales more softly than full molecule methods. Although KEM provides accurate energies those energies are not required to satisfy the variational theorem. In this article, KEM is extended to provide a full molecule single‐determinant N‐representable one‐body density matrix. A kernel expansion for the one‐body density matrix analogous to the kernel expansion for energy is defined. This matrix is converted to a normalized projector by an algorithm due to Clinton. The resulting single‐determinant N‐representable density matrix maps to a quantum mechanically valid wavefunction which satisfies the variational theorem. The process is demonstrated on clusters of three to twenty water molecules. The resulting energies are more accurate than the straightforward KEM energy results and all violations of the variational theorem are resolved. The N‐representability studied in this article is applicable to the study of quantum crystallography. © 2017 Wiley Periodicals, Inc. 相似文献
139.
140.
《Angewandte Chemie (International ed. in English)》2017,56(43):13253-13258
Reactions of [K(crypt‐222)]2(TlBi3)⋅0.5 en ( 1 b ) with [Ru(cod)(H2CC(Me)CH2)2] ( A ) in 1,2‐diaminoethane (en) led to the formation of two compounds with new bismuth‐rich cluster anions, [K(crypt‐222)]3[Bi9{Ru(cod)}2]⋅1.5 en ( 2 ) and [K(crypt‐222)]2[Tl2Bi6{Ru(cod)}]⋅2 tol ( 3 ), alongside the salt of a binary nido cluster, [K(crypt‐222)]3(Tl4Bi5)⋅2 en ( 4 ). The anions in 2 and 3 are two further examples of rare heterometallic clusters containing Ru atoms. As one cod ligand is retained on each Ru atom in both clusters, the anions may be viewed as intermediates on the way towards larger, ligand‐free intermetalloid clusters. Quantum‐chemical studies provided insight into the bonding situation in these clusters. According to these studies, the anion of 2 features both electron‐precise and electron‐deficient parts. Electrospray ionization mass spectrometry analysis indicated that the clusters undergo stepwise fragmentation. 相似文献