全文获取类型
收费全文 | 28175篇 |
免费 | 2189篇 |
国内免费 | 1260篇 |
专业分类
化学 | 26745篇 |
晶体学 | 81篇 |
力学 | 823篇 |
综合类 | 145篇 |
数学 | 463篇 |
物理学 | 3367篇 |
出版年
2024年 | 14篇 |
2023年 | 273篇 |
2022年 | 427篇 |
2021年 | 483篇 |
2020年 | 682篇 |
2019年 | 645篇 |
2018年 | 658篇 |
2017年 | 908篇 |
2016年 | 1044篇 |
2015年 | 1015篇 |
2014年 | 947篇 |
2013年 | 1340篇 |
2012年 | 1793篇 |
2011年 | 1571篇 |
2010年 | 1321篇 |
2009年 | 1532篇 |
2008年 | 1169篇 |
2007年 | 1454篇 |
2006年 | 1307篇 |
2005年 | 1235篇 |
2004年 | 1131篇 |
2003年 | 896篇 |
2002年 | 781篇 |
2001年 | 604篇 |
2000年 | 651篇 |
1999年 | 588篇 |
1998年 | 517篇 |
1997年 | 634篇 |
1996年 | 471篇 |
1995年 | 599篇 |
1994年 | 500篇 |
1993年 | 431篇 |
1992年 | 329篇 |
1991年 | 379篇 |
1990年 | 338篇 |
1989年 | 306篇 |
1988年 | 407篇 |
1987年 | 386篇 |
1986年 | 297篇 |
1985年 | 280篇 |
1984年 | 293篇 |
1983年 | 154篇 |
1982年 | 250篇 |
1981年 | 198篇 |
1980年 | 166篇 |
1979年 | 151篇 |
1978年 | 28篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1975年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Morgan A. Higgins Christopher R. Maroon Jacob Townsend Xinyi Wang Konstantinos D. Vogiatzis Brian K. Long 《Journal of polymer science. Part A, Polymer chemistry》2020,58(18):2644-2653
Polymeric membranes have shown tremendous promise for the separation of CO2 from flue gas streams. However, few systematic studies have been conducted to better understand the impact that chemical functionalities have on membrane-based gas separation performance. To address this gap, we herein describe the synthesis and gas separation performance of a series of vinyl-addition polynorbornenes bearing various CO2-philic functional groups. To facilitate direct comparison between functional groups, each material was designed to maintain a common polymer backbone. Though the incorporation of CO2-philic moieties within a dense polymeric membrane is frequently hypothesized to enhance CO2 solubility, and thereby increase CO2/N2 selectivity, our results demonstrate that the incorporation of CO2-philic groups onto a common polymer backbone do not necessarily result in increased gas separation performance. Experimental and computational results demonstrate that the incorporation of amidoxime groups onto a polynorbornene backbone increase CO2/N2 selectivity, whereas commonly employed ethereal side chains only increased permeability. 相似文献
72.
Ding Tian Taliehsadat Alebrahim Gregory K. Kline Liwen Chen Haiqing Lin Chulsung Bae 《Journal of polymer science. Part A, Polymer chemistry》2020,58(18):2654-2663
Polymeric membrane-based gas separation technology has significant advantages compared with traditional amine-based CO2 separation method. In this work, SEBS block copolymer is used as a polymer matrix to incorporate triethylene oxide (TEO) functionality. The short ethylene oxide segment is chosen to avoid crystallization, which is confirmed by differential scanning calorimetry and wide-angle X-ray scattering characterizations. The gas permeability results reveal that CO2/N2 selectivity increased with increasing content of TEO functional group. The highest CO2 permeability (281 Barrer) and CO2/N2 selectivity (31) were obtained for the membrane with the highest TEO incorporation (57 mol%). Increasing the TEO content in these copolymers results in an increase in CO2 solubility and a decrease in C2H6 solubility. For example, as the grafted TEO content increased from 0 to 57 mol%, the CO2 solubility and CO2/C2H6 solubility selectivity increased from 0.72 to 1.3 cm3(STP)/cm3 atm and 0.47 to 1.3 at 35°C, respectively. The polar ether linkage in TEO-grafted SEBS copolymers exhibits favorable interaction with CO2 and unfavorable interaction with nonpolar C2H6, thus enhancing CO2/C2H6 solubility selectivity. 相似文献
73.
Prof. Akiharu Satake Yuki Suzuki Motonobu Sugimoto Dr. Yusuke Kuramochi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):669-684
Bis(imidazolylporphyrinatozinc) molecules linked through a 1,3-butadiynylene moiety respond to the solvents they are dissolved in to afford exclusively extended (E) or stacked (S) supramolecular polymers. This system is expected to be a solvation/desolvation indicator. However, the principles underlying the solvent-dependent formation of the two types of polymers and the mechanism of the transformation between them are unclear. The formation of the polymers is considered to depend on the two types of complementary coordination bonds that can be formed and the π–π interactions between the porphyrins. In this study, the contributions and solvent dependence of both the coordination bonds and the π–π interactions have been investigated. The results clearly indicate that the coordination bonds are weakly or little solvent-dependent, and that the π–π interactions function effectively only in the inner porphyrins of the S-polymer and are strongly solvent-dependent. Thermodynamic analysis revealed that the formation of the E- or S-polymer in solution is determined by the total energies and the type of solvent used. The transformation of the E- to S-polymer was investigated by gel permeation chromatography. The kinetics of the transformation were also determined. The role of the terminal imidazolylporphyrinatozinc moieties was also investigated: The results indicate that the transformation from the E- to S-polymer occurs by an exchange mechanism between the polymers, induced by attack of terminal free imidazolyl groups on a polymer to zinc porphyrins on other polymers. 相似文献
74.
Bo Wang Dr. Wencheng Du Dr. Yang Yang Dr. Yufei Zhang Dr. Qi Zhang Prof. Xianhong Rui Dr. Hongbo Geng Prof. Cheng Chao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6554-6560
Lithium ion batteries (LIBs) at present still suffer from low rate capability and poor cycle life during fast ion insertion/extraction processes. Searching for high-capacity and stable anode materials is still an ongoing challenge. Herein, a facile strategy for the synthesis of ultrathin GeS2 nanosheets with the thickness of 1.1 nm is reported. When used as anodes for LIBs, the two-dimensional (2D) structure can effectively increase the electrode/electrolyte interface area, facilitate the ion transport, and buffer the volume expansion. Benefiting from these merits, the as-synthesized GeS2 nanosheets deliver high specific capacity (1335 mAh g−1 at 0.15 A g−1), extraordinary rate performance (337 mAh g−1 at 15 A g−1) and stable cycling performance (974 mAh g−1 after 200 cycles at 0.5 A g−1). Importantly, our fabricated Li-ion full cells manifest an impressive specific capacity of 577 mAh g−1 after 50 cycles at 0.1 A g−1 and a high energy density of 361 Wh kg−1 at a power density of 346 W kg−1. Furthermore, the electrochemical reaction mechanism is investigated by the means of ex-situ high-resolution transmission electron microscopy. These results suggest that GeS2 can use to be an alternative anode material and encourage more efforts to develop other high-performance LIBs anodes. 相似文献
75.
Shuhao Zhang Mercedes K. Taylor Lingchang Jiang Prof. Hao Ren Prof. Guangshan Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3205-3221
Light hydrocarbons (C1–C3) are used as basic energy feedstocks and as commodity organic compounds for the production of many industrially necessary chemicals. Due to the nature of the raw materials and production processes, light hydrocarbons are generated as mixtures, but the high-purity single-component products are of vital importance to the petrochemical industry. Consequently, the separation of these C1–C3 products is a crucial industrial procedure that comprises a significant share of the total global energy consumption per year. As a complement to traditional separation methods (distillation, partial hydrogenation, etc.), adsorptive separations using porous solids have received widespread attention due to their lower energy costs and higher efficiency. Extensive research has been devoted to the use of porous materials such as zeolites and metal-organic frameworks (MOFs) as solid adsorbents for these key separations, owing to the high porosity, tunable pore structures, and unsaturated metal sites present in these materials. Recently, porous organic framework (POF) materials composed of organic building blocks linked by covalent bonds have also shown excellent properties in light hydrocarbon adsorption and separation, sparking interest in the use of these materials as adsorbents in separation processes. This Minireview summarizes the recent advances in the use of POFs for light hydrocarbon separations, including the separation of mixtures of methane/ethane, methane/propane, ethylene/ethane, acetylene/ethylene, and propylene/propane, while highlighting the relationships between the structural features of these materials and their separation performances. Finally, the difficulties, challenges, and opportunities associated with leveraging POFs for light hydrocarbon separations are discussed to conclude the review. 相似文献
76.
Junxiong Wu Prof. Francesco Ciucci Prof. Jang-Kyo Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6296-6319
The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS2) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS2 are first introduced. Then, typical synthetic methods for MoS2 and MoS2-based composites are presented. Furthermore, the recent progress in the design of diverse MoS2-based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS2-based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems. 相似文献
77.
Yichen Zhou Mingmin Jia Dr. Xiongfei Zhang Prof. Dr. Jianfeng Yao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7918-7922
Zeolite ZIF-8 has been etched with acid to form microporous ZIF-8-E crystals. These were then introduced into a polyethersulfone (PES) membrane matrix to enhance its CO2/N2 separation performance. Open through pores of size about 100 nm formed in the ZIF-8 crystals allow the ingrowth of polyethersulfone chains, ensuring a reduction in the number of nonselective voids, thereby achieving better interaction between ZIF-8-E and PES. As a result, the CO2/N2 separation performance of the ZIF-8-E/PES membrane increased significantly, showing a CO2 permeability of 15.7 Barrer and a CO2/N2 ideal selectivity of 6.5. 相似文献
78.
Duloxetine (DLX) is a widely used antidepressant drug belonging to the class of selective serotonin and norepinephrine reuptake inhibitors (SNRIs); its efficacy has been demonstrated in the treatment of not only major depressive disorders but also diabetic neuropathic pain, generalized anxiety disorder, fibromyalgia or stress urinary incontinence. It is a chiral substance and is used in therapy in the form of the enantiopure S‐DLX, which is twice as active as R‐DLX. Several methods have been published for the achiral and chiral determination of DLX in pharmaceuticals, biological materials and environmental samples, the majority using liquid chromatography and capillary electrophoresis coupled with different detection techniques (UV detection, fluorescence, mass spectrometry). The aim of the current review is to provide a systematic survey of the analytical techniques used for the determination of DLX from different matrices. 相似文献
79.
Helical carbon nanotubes currently cost ~15,000–19,000 USD/kg commercially and are ~10–15 times the price of straight carbon nanotubes of similar dimensions. They have not previously been made from the greenhouse gas CO2 nor had new variants of the helical morphology been demonstrated. In this study, a novel, inexpensive electrosynthesis of these helical nanocarbon materials from CO2 is presented. This material may be produced by molten carbon growth conditions that (1) maximize torsional stresses, such as those that may occur during rapid, nucleated carbon reduction, (2) enhance defects that cause formation of heptagonal, rather than the conventional hexagonal building blocks of graphene cylindrical walls, and (3) uniformly control those enhanced defects to repeatedly induce a uniform spiral conformation. These conditions are achieved with at least two of the following experimental conditions: (i) high electrolysis current density, (ii) sp3 defect-inducing agents, such as added oxide, and (iii) controlled concentration of iron added to the electrolyte or cathode. Here, it is shown with SEM, TEM, EDX, XRF, and Raman spectroscopy that a molten controlled electrolyte carbonate synthesis to induce defect formation, and a high rate of electrolysis (0.6 A/cm2) leads to a high yield of helical nanotubes, helical nanofibers, or helical nanoplatelet carbon morphologies. 相似文献
80.
Hexagonal boron phosphide and boron arsenide van der Waals heterostructure as high-efficiency solar cell 下载免费PDF全文
The rapid development of two-dimensional (2D) materials offers new opportunities for 2D ultra-thin excitonic solar cells (XSCs). The construction of van der Waals heterostructure (vdWH) is a recognised and effective method of integrating the properties of single-layer 2D materials, creating particularly superior performance. Here, the prospects of h-BP/h-BAs vdW heterostructures in 2D excitonic solar cells are assessed. We systematically investigate the electronic properties and optical properties of heterogeneous structures by using the density functional theory (DFT) and first-principles calculations. The results indicate that the heterogeneous structure has good optoelectronic properties, such as a suitable direct bandgap and excellent optical absorption properties. The calculation of the phonon spectrum also confirms the well-defined kinetic stability of the heterstructure. We design the heterogeneous structure as a model for solar cells, and calculate its solar cell power conversion efficiency which reaches up to 16.51% and is higher than the highest efficiency reported in organic solar cells (11.7%). Our work illustrates the potential of h-BP/h-BAs heterostructure as a candidate for high-efficiency 2D excitonic solar cells. 相似文献