全文获取类型
收费全文 | 7853篇 |
免费 | 1559篇 |
国内免费 | 944篇 |
专业分类
化学 | 5585篇 |
晶体学 | 116篇 |
力学 | 450篇 |
综合类 | 91篇 |
数学 | 860篇 |
物理学 | 3254篇 |
出版年
2024年 | 33篇 |
2023年 | 246篇 |
2022年 | 390篇 |
2021年 | 382篇 |
2020年 | 452篇 |
2019年 | 426篇 |
2018年 | 355篇 |
2017年 | 326篇 |
2016年 | 446篇 |
2015年 | 454篇 |
2014年 | 483篇 |
2013年 | 651篇 |
2012年 | 727篇 |
2011年 | 714篇 |
2010年 | 511篇 |
2009年 | 468篇 |
2008年 | 448篇 |
2007年 | 401篇 |
2006年 | 344篇 |
2005年 | 303篇 |
2004年 | 259篇 |
2003年 | 215篇 |
2002年 | 185篇 |
2001年 | 156篇 |
2000年 | 111篇 |
1999年 | 140篇 |
1998年 | 107篇 |
1997年 | 93篇 |
1996年 | 92篇 |
1995年 | 76篇 |
1994年 | 65篇 |
1993年 | 44篇 |
1992年 | 35篇 |
1991年 | 46篇 |
1990年 | 41篇 |
1989年 | 27篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1986年 | 16篇 |
1985年 | 13篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1964年 | 1篇 |
1959年 | 2篇 |
1957年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Qin Meng Guo-Ming Wang Huan He Bai-Feng Yang Guo-Yu Yang 《Journal of Cluster Science》2014,25(5):1295-1305
Two new pentaborates [M(dap)3][B5O6(OH)4]2·H2O (M = Co (1) and Ni (2); dap = 1,2-diaminopropane) have been hydrothermally synthesized. Both structures were determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence spectroscopy. Two compounds are isostructural and consist of isolated pentaborate [B5O6(OH)4]? anions and [M(dap)3]2+ complex cations. The anionic [B5O6(OH)4]? groups are linked by extensive hydrogen bonds to form a 3-D supramolecular framework with large channels, in which the transition-metal complex templates are located. The luminescent properties of 1 and 2 were studied, and blue luminescence occurs with an emission maximum at 405 and 408 nm upon excitation at 332 and 328 nm respectively. Crystal data: 1, monoclinic, space group P21/c (No. 14), a = 9.7159(5) Å, b = 29.3372(19) Å, c = 11.5121(6) Å, β = 103.286(5)°, V = 3193.6(3) Å3, Z = 4; 2, monoclinic, space group P21/c, a = 9.7264(4) Å, b = 29.3810(16) Å, c = 11.5185(6) Å, β = 103.249(4)°, V = 3204.0(3) Å3, Z = 4. 相似文献
82.
Meng Li Hong‐Ye Bai Zu‐Lin Da Xu Yan Chao Chen Jin‐Hui Jiang Wei‐Qiang Fan Wei‐Dong Shi 《Crystal Research and Technology》2015,50(3):244-249
CaFe2O4/MgFe2O4 nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe2O4/MgFe2O4 nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe2O4 or MgFe2O4 samples, the prepared CaFe2O4/MgFe2O4 (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe2O4/MgFe2O4 nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity. 相似文献
83.
Meng Zhao Dr. Hong-Jie Peng Bo-Quan Li Dr. Xiao Chen Jin Xie Dr. Xinyan Liu Prof. Qiang Zhang Prof. Jia-Qi Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9096-9102
In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co4N) in working Li-S batteries that renders highly active electrocatalysts (CoSx). Electrochemical cycling induces the transformation from single-crystalline Co4N to polycrystalline CoSx that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co4N enables stable operation of high-rate (10 C, 16.7 mA cm−2) and electrolyte-starved (4.7 μL mgS−1) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds. 相似文献
84.
Mordenite (MOR) has demonstrated potential as a catalyst for alkylation due to high variability, intrinsic porosity, and outstanding stability. However, the contact probability of benzene and methanol has been limited by typical layered structures of MOR and there is no connection between layers. Here, we report the preparedness of H-MOR via a sequential post-treatment method based on a commercial MOR. H-MOR sample had appeared lattice imperfections inferred from characterization means. The samples were tested with benezene methylation reaction. Results show that the high conversion of benzene and the high selectivity of toluene were obtained from the miracle role of lattice imperfections in the H-MOR sample. Sequentially, based on the study of all catalyst structure and physical properties, a plausible reaction mechanism for the selectivity of the desired toluene was proposed. 相似文献
85.
Mingjie Wen Xiru Cao Yongqi Zhang Meng Liang Tianlei Zhang Balaganesh Muthiah Ke Zhou Soumendra K. Roy Makroni Lily 《International journal of quantum chemistry》2020,120(23):e26389
A detailed theoretical study on the reaction mechanisms for the formations of H2O2 + 3O2 from the self-reaction of HO2 radicals under the effect of NH3, H3N···H2O, and H2SO4 catalysts was performed using the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH3-, H3N···H2O-, and H2SO4-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H2O, the efficiencies of NH3, H3N···H2O, and H2SO4 are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO2 + HO2 → H2O2 + 3O2. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere. 相似文献
86.
A 1,10-phenanthroline based polymer named PPPhen(i.e., polymer from pyrene 1,10-phenanthrolin) was prepared by the Friedel-Crafts reaction of 1,10-phenanthroline and pyrene cross-linked with dimethoxymethane. The related Pd catalyst Pd@PPPhen was prepared by supporting Pd nanoparticles(NPs) on the PPPhen material. PPPhen and Pd@PPPhen were characterized by means of scanning electron microscopy(SEM), transmission electron microscopy, N2 adsorption-desorption, Fourier-transform infrared and X-ray photoelectron spectroscopy analyses. The results showed that PPPhen polymer was highly porous and that the phenanthroline group can enhance the stability of the Pd nanoparticles. Pd@PPPhen also exhibited good catalytic activity in the aerobic oxidation of alcohols to aldehydes and ketones, and Pd@PPPhen was recyclable with durable activity and retentive structures. 相似文献
87.
Xiangchuan Meng Zhi Xing Xiaotian Hu Zengqi Huang Ting Hu Licheng Tan Fengyu Li Yiwang Chen 《Angewandte Chemie (International ed. in English)》2020,59(38):16602-16608
Perovskite solar cells (PSCs) are a promising photovoltaic technology for stretchable applications because of their flexible, light‐weight, and low‐cost characteristics. However, the fragility of crystals and poor crystallinity of perovskite on stretchable substrates results in performance loss. In fact, grain boundary defects are the “Achilles’ heel” of optoelectronic and mechanical stability. We incorporate a self‐healing polyurethane (s‐PU) with dynamic oxime–carbamate bonds as a scaffold into the perovskite films, which simultaneously enhances crystallinity and passivates the grain boundary of the perovskite films. The stretchable PSCs with s‐PU deliver a stabilized efficiency of 19.15 % with negligible hysteresis, which is comparable to the performance on rigid substrates. The PSCs can maintain over 90 % of their initial efficiency after 3000 hours in air because of their self‐encapsulating structure. Importantly, the self‐healing function of the s‐PU scaffold was verified in situ. The s‐PU can release mechanical stress and repair cracks at the grain boundary on multiple levels. The devices recover 88 % of their original efficiency after 1000 cycles at 20 % stretch. We believe that this ingenious growth strategy for crystalline semiconductors will facilitate development of flexible and stretchable electronics. 相似文献
88.
Hai‐Long Qian Fan‐Lin Meng Cheng‐Xiong Yang Xiu‐Ping Yan 《Angewandte Chemie (International ed. in English)》2020,59(40):17607-17613
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)?H???Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications. 相似文献
89.
Yuan Haifeng Zhao Yan Yang Chan Zhang Cheng Yang Yue Meng Hongmin Huan Shuangyan Song Guosheng Zhang Xiaobing 《中国科学:化学(英文版)》2020,63(7):924-935
For chemotherapy, drug delivery systems often suffer from the inefficient drug loading capability, which usually cause systems toxicity and extra burden to excrete carrier itself. Moreover, the cancer therapeutic efficacy is also greatly limited by the specificity of tumor microenvironment for reactive oxygen species(ROS) based cancer therapeutic strategy(e.g., chemodynamic therapy). Herein, we have developed metal-drug coordination nanoplatform that can not only be responsive to tumor microenvironment but also modulate it, so as to achieve efficient treatment of cancer. Excitingly, by employing small molecule drug(6-thioguanine) as ligand copper ions, we achieve a high drug loading rate(60.1%) and 100% of utilization of metal-drug coordination nanoplatform(Cu-TG). Interestingly, Cu-TG possessed high-efficiently horseradish peroxidase-like, glutathione peroxidase-like and catalase-like activity. Under the tumor microenvironment, Cu-TG exhibited the self-reinforcing circular catalysis that is able to amplify the cellular oxidative stress, inducing notable cancer cellular apoptosis. Moreover, Cu-TG could be activated with glutathione(GSH) and facilitated for GSH triggered 6-TG release, higher selective therapeutic effect toward cancer cells, and GSH activated T_1 weight-magnetic resonance imaging. Based on the above properties, Cu-TG exhibited magnetic resonance imaging(MRI) guiding, efficient and synergistic combination of chemodynamic and chemotherapy with self-reinforcing therapeutic outcomes in vivo. 相似文献
90.
Silica-supported polystannazane–copper complex has been prepared and used as a catalyst for the oxidation of methanol. The results showed that the catalyst could catalyze the oxidation of methanol to formaldehyde at a high yield and selectivity at 30°C and under 1 atm mild conditions. The N/Cu mole ratio in the complex, temperature and the amount of NaOH additive had much influence on the catalytic activity. The complex was stable during the reaction and could be used repeatedly. 相似文献