全文获取类型
收费全文 | 1700篇 |
免费 | 112篇 |
国内免费 | 137篇 |
专业分类
化学 | 349篇 |
晶体学 | 1篇 |
力学 | 39篇 |
综合类 | 1篇 |
数学 | 1323篇 |
物理学 | 236篇 |
出版年
2023年 | 74篇 |
2022年 | 17篇 |
2021年 | 20篇 |
2020年 | 22篇 |
2019年 | 19篇 |
2018年 | 24篇 |
2017年 | 20篇 |
2016年 | 19篇 |
2015年 | 26篇 |
2014年 | 62篇 |
2013年 | 213篇 |
2012年 | 81篇 |
2011年 | 116篇 |
2010年 | 86篇 |
2009年 | 159篇 |
2008年 | 108篇 |
2007年 | 127篇 |
2006年 | 102篇 |
2005年 | 78篇 |
2004年 | 85篇 |
2003年 | 85篇 |
2002年 | 51篇 |
2001年 | 36篇 |
2000年 | 25篇 |
1999年 | 40篇 |
1998年 | 35篇 |
1997年 | 27篇 |
1996年 | 21篇 |
1995年 | 16篇 |
1994年 | 19篇 |
1993年 | 13篇 |
1992年 | 9篇 |
1991年 | 11篇 |
1990年 | 10篇 |
1989年 | 4篇 |
1988年 | 12篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 7篇 |
1978年 | 6篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1949条查询结果,搜索用时 31 毫秒
11.
Xiaoyu Liu Haolin Lu Prof. Shengli Zhu Prof. Zhenduo Cui Prof. Zhaoyang Li Prof. Shuilin Wu Prof. Wence Xu Prof. Yanqin Liang Prof. Guankui Long Prof. Hui Jiang 《Angewandte Chemie (International ed. in English)》2023,62(13):e202300800
It is challenging to design one non-noble material with balanced bifunctional performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) for commercial sustainability at a low cost since the different electrocatalytic mechanisms are not easily matchable for each other. Herein, a self-standing hybrid system Ni18Fe12Al70, consisting of Ni2Al3 and Ni3Fe phases, was constructed by laser-assisted aluminum (Al) incorporation towards full water splitting. It was found that the incorporation of Al could effectively tune the morphologies, compositions and phases. The results indicate that Ni18Fe12Al70 delivers an extremely low overpotential to trigger both HER (η100=188 mV) and OER (η100=345 mV) processes and maintains a stable overpotential for 100 h, comparable to state-of-the-art electrocatalysts. The synergistic effect of Ni2Al3 and Ni3Fe alloys on the HER process is confirmed based on theoretical calculation. 相似文献
12.
Shengmei Chen Yiran Ying Shengnan Wang Longtao Ma Haitao Huang Xiaoqi Wang Xu Jin Shengchi Bai Prof. Chunyi Zhi 《Angewandte Chemie (International ed. in English)》2023,62(19):e202301467
Though massive efforts have been devoted to exploring Br-based batteries, the highly soluble Br2/Br3− species causing rigorous “shuttle effect”, leads to severe self-discharge and low Coulombic efficiency. Conventionally, quaternary ammonium salts such as methyl ethyl morpholinium bromide (MEMBr) and tetrapropylammonium bromide (TPABr) are used to fix Br2 and Br3−, but they occupy the mass and volume of battery without capacity contribution. Here, we report an all-active solid interhalogen compound, IBr, as a cathode to address the above challenges, in which the oxidized Br0 is fixed by iodine (I), thoroughly eliminating cross-diffusing Br2/Br3− species during the whole charging and discharging process. The Zn||IBr battery delivers remarkably high energy density of 385.8 Wh kg−1, which is higher than those of I2, MEMBr3, and TPABr3 cathodes. Our work provides new approaches to achieve active solid interhalogen chemistry for high-energy electrochemical energy storage devices. 相似文献
13.
《印度化学会志》2023,100(1):100857
Recently, the use of CZTS as the basis for other generation of low cost thin films solar cells has stimulated further researches. Its excellent p-type absorber nature, relatively high absorption coefficient and ideal energy band-gap of 1.5eV motivated these efforts. Additionally, CZTS consist of earth-abundant, cheap and non-toxic elements with very low manufacturing cost. Initially, copper indium gallium selenide (CIGS) solar cell device emerged but suffered limitations in further development because of rare indium and gallium in the device structure therefore, CZTS is recently preferred as an alternative to CIGS commercial solar cell absorber layer. In this work, solution mixture of CZTS and PVA was deposited on a substrate at temperature of 150 °C. Sensitive spray pyrolysis was used to grow the thin films where calculated amount of the precursor mixture was allowed to fall and be deposited on a heated substrate to form CZTS/PVA thin films. Subsequently, the thin film samples were annealed at a temperature of 200oCfor 1 h to achieving pure crystalline thin film formation. SEM, XRD analysis, Optical, Solid State properties and Raman analysis were studied. The XRD analysis showed that the thin films fell into the pure kesterite structure of CZTS. Results show that produced thin films exhibited higher absorption coefficient and optical conductivity than pure CZTS, 106 m?1 and 1014(S?1) against 104cm?1 and 1012(S?1) respectively. The band-gap is between 1.53eV and 1.73eV. Using a PVA concentration of 0.05 M yielded highest absorbance and optical conductivity with lowest real dielectric constant and transmittance. These improved optical, electrical and solid state properties suitably qualify these thin films as absorber layer material for solar cell applications. 相似文献
14.
Taichi Mitsumoto Dr. Yuya Ashida Dr. Kazuya Arashiba Dr. Shogo Kuriyama Akihito Egi Prof. Dr. Hiromasa Tanaka Prof. Dr. Kazunari Yoshizawa Prof. Dr. Yoshiaki Nishibayashi 《Angewandte Chemie (International ed. in English)》2023,62(43):e202306631
We newly designed and prepared a novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum-imide complexes bearing various substituted pyridine-based PNP-type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification. 相似文献
15.
Xiao-Yu Li Dr. Tao Wang Yu-Chen Cai Zhao-Dong Meng Jing-Wen Nan Dr. Jin-Yu Ye Prof. Dr. Jun Yi Prof. Dr. Dong-Ping Zhan Prof. Dr. Na Tian Prof. Dr. Zhi-You Zhou Prof. Dr. Shi-Gang Sun 《Angewandte Chemie (International ed. in English)》2023,62(14):e202218669
Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton transfer rate and then tune electrocatalytic performance. However, the mechanism for regulating proton transfer remains ambiguous. Here, we quantify the cation effect on proton diffusion in solution by hydrogen evolution on microelectrodes, revealing the rate can be suppressed by more than 10 times. Different from the prevalent opinions that proton transport is slowed down by modified electric field, we found water structure imposes a more evident effect on kinetics. FTIR test and path integral molecular dynamics simulation indicate that proton prefers to wander within the hydration shell of cations rather than to hop rapidly along water wires. Low connectivity of water networks disrupted by cations corrupts the fast-moving path in bulk water. This study highlights the promising way for regulating proton kinetics via a modified water structure. 相似文献
16.
Jindou Tian Prof. Dr. Qihui Chen Prof. Dr. Feilong Jiang Prof. Dr. Daqiang Yuan Prof. Dr. Maochun Hong 《Angewandte Chemie (International ed. in English)》2023,62(7):e202215253
Developing practical storage technologies for acetylene (C2H2) is important but challenging because C2H2 is useful but explosive. Here, a novel metal–organic framework (MOF) ( FJI-H36 ) with adaptive channels was prepared. It can effectively capture C2H2 (159.9 cm3 cm−3) at 1 atm and 298 K, possessing a record-high storage density (561 g L−1) but a very low adsorption enthalpy (28 kJ mol−1) among all the reported MOFs. Structural analyses show that such excellent adsorption performance comes from the synergism of active sites, flexible framework, and matched pores; where the adsorbed-C2H2 can drive FJI-H36 to undergo induced-fit transformations step by step, including deformation/reconstruction of channels, contraction of pores, and transformation of active sites, finally leading to dense packing of C2H2. Moreover, FJI-H36 has excellent chemical stability and recyclability, and can be prepared on a large scale, enabling it as a practical adsorbent for C2H2. This will provide a useful strategy for developing practical and efficient adsorbents for C2H2 storage. 相似文献
17.
Yanan Chang Zhangyu Ma Xuyun Lu Shasha Wang Prof. Jianchun Bao Prof. Ying Liu Prof. Chao Ma 《Angewandte Chemie (International ed. in English)》2023,62(41):e202310163
The rational design of advanced nanohybrids (NHs) with optimized interface electronic environment and rapid reaction kinetics is pivotal to electrocatalytic schedule. Herein, we developed a multiple heterogeneous Co9S8/Co3S4/Cu2S nanoparticle in which Co3S4 germinates between Co9S8 and Cu2S. Using high-angle annular-dark-field imaging and theoretical calculation, it was found that the integration of Co9S8 and Cu2S tends to trigger the interface phase transition of Co9S8, leading to Co3S4 interlayer due to the low formation energy of Co3S4/Cu2S (−7.61 eV) than Co9S8/Cu2S (−5.86 eV). Such phase transition not only lowers the energy barrier of oxygen evolution reaction (OER, from 0.335 eV to 0.297 eV), but also increases charge carrier density (from 7.76×1014 to 2.09×1015 cm−3), and creates more active sites. Compared to Co9S8 and Cu2S, the Co9S8/Co3S4/Cu2S NHs also demonstrate notable photothermal effect that can heat the catalyst locally, offset the endothermic enthalpy change of OER, and promote carrier migrate, reaction intermediates adsorption/deprotonation to improve reaction kinetics. Profiting from these favorable factors, the Co9S8/Co3S4/Cu2S catalyst only requires an OER overpotential of 181 mV and overall water splitting cell voltage of 1.43 V to driven 10 mA cm−2 under the irradiation of near-infrared light, outperforming those without light irradiation and many reported Co-based catalysts. 相似文献
18.
ChangYan Hu Dr. Ying Li Dr. Dong Wang Dr. Chunjin Wu Feng Chen Linghong Zhang Prof. Fang Wan Prof. Weibo Hua Prof. Yan Sun Prof. Benhe Zhong Dr. Zhenguo Wu Prof. Xiaodong Guo 《Angewandte Chemie (International ed. in English)》2023,62(46):e202312310
Na2Ti6O13 (NTO) with high safety has been regarded as a promising anode candidate for sodium-ion batteries. In the present study, integrated modification of migration channels broadening, charge density re-distribution, and oxygen vacancies regulation are realized in case of Nb-doping and have obtained significantly enhanced cycling performance with 92 % reversible capacity retained after 3000 cycles at 3000 mA g−1. Moreover, unexpected low-temperature performance with a high discharge capacity of 143 mAh g−1 at 100 mA g−1 under −15 °C is also achieved in the full cell. Theoretical investigation suggests that Nb preferentially replaces Ti3 sites, which effectively improves structural stability and lowers the diffusion energy barrier. What's more important, both the in situ X-ray diffraction (XRD) and in situ Raman furtherly confirm the robust spring effect of the Ti−O bond, making special charge compensation mechanism and respective regulation strategy to conquer the sluggish transport kinetics and low conductivity, which plays a key role in promoting electrochemical performance. 相似文献
19.
Hongbin Dai Prof. Ran Hong Yafei Ma Dr. Xiaoxiao Cheng Prof. Wei Zhang 《Angewandte Chemie (International ed. in English)》2023,62(50):e202314848
Precise control over the chirality and morphologies of polymer assemblies, a remaining challenge for both chemists and materials scientists, is receiving ever-increasing attention in the recent years. Herein, we report the subtle manipulation of the achiral spacers from the chiral stereocenter to the azobenzene (Azo) unit, of which the chiroptical consistency or chiroptical inversion of self-assemblies could be successfully controlled and present “two-fold” odd-even effect. Furthermore, morphological transitions from 0D spherical micelles, 1D worms, and nanowires to 3D vesicles, spindle- and dumbbell-shaped vesicles were also unexpectedly found to exhibit odd-even correlations. These observations were collectively elucidated by mesomorphic properties, stacking modes, chiroptical dynamics, and stimuli-responsive behaviors. Negligible modifications to the spacer structures can enable remarkable modulation of supramolecular chirality and anisotropic topologies in polymer assemblies, which is of great significance for the design of complex chiral functional polymers. 相似文献
20.
研究了H2O对Ni/MgAlO催化剂上丙酮加氢为异丙醇的催化反应的影响。结果发现,在丙酮中添加少量H2O可提高丙酮转化率,但超过5%的H2O量则会显著降低催化剂活性。吸附量热结果表明,催化剂表面吸附少量H2O会明显降低异丙醇的吸附热,但对丙酮吸附热的影响较小,这也许是反应体系中少量的H2O能促进丙酮加氢活性的原因之一。当催化剂表面吸附较多H2O后,丙酮、异丙醇和H2的吸附热都降低了,因此反而抑制了丙酮的加氢反应。此外,红外光谱结果表明,预吸附水抑制了催化剂表面异丙醇脱氢生成丙酮,并抑制吸附的丙酮在表面生成烯醇盐或异丙叉丙酮等物种,这也许是少量水能促进丙酮加氢生成异丙醇的另一个重要原因。 相似文献