全文获取类型
收费全文 | 153362篇 |
免费 | 11164篇 |
国内免费 | 21509篇 |
专业分类
化学 | 113106篇 |
晶体学 | 2852篇 |
力学 | 3819篇 |
综合类 | 1721篇 |
数学 | 20885篇 |
物理学 | 43652篇 |
出版年
2023年 | 1930篇 |
2022年 | 2349篇 |
2021年 | 4011篇 |
2020年 | 4374篇 |
2019年 | 4244篇 |
2018年 | 3557篇 |
2017年 | 4793篇 |
2016年 | 5180篇 |
2015年 | 4508篇 |
2014年 | 6183篇 |
2013年 | 11979篇 |
2012年 | 9621篇 |
2011年 | 9481篇 |
2010年 | 8049篇 |
2009年 | 10620篇 |
2008年 | 10608篇 |
2007年 | 11164篇 |
2006年 | 9845篇 |
2005年 | 7928篇 |
2004年 | 7309篇 |
2003年 | 6129篇 |
2002年 | 5236篇 |
2001年 | 4430篇 |
2000年 | 3787篇 |
1999年 | 3309篇 |
1998年 | 2926篇 |
1997年 | 2376篇 |
1996年 | 2098篇 |
1995年 | 2248篇 |
1994年 | 1982篇 |
1993年 | 1723篇 |
1992年 | 1635篇 |
1991年 | 1159篇 |
1990年 | 915篇 |
1989年 | 839篇 |
1988年 | 730篇 |
1987年 | 583篇 |
1986年 | 526篇 |
1985年 | 598篇 |
1984年 | 504篇 |
1983年 | 285篇 |
1982年 | 502篇 |
1981年 | 668篇 |
1980年 | 589篇 |
1979年 | 613篇 |
1978年 | 502篇 |
1977年 | 377篇 |
1976年 | 317篇 |
1974年 | 124篇 |
1973年 | 213篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
O. Guselnikova J.P. Fraser N. Soldatova E. Sviridova A. Ivanov R. Rodriguez A.Y. Ganin P. Postnikov 《Materials Today Chemistry》2022
Covalent functionalization of 2D materials provides a tailored approach towards tuning of their chemical, optical, and electronic properties making the search for new ways to graft small molecules important. Herein, the reaction with (3,5-bis(trifluoromethyl)phenyl)iodonium salt is revealed as an effective strategy for functionalization of MoTe2 thin films. Upon decomposition of the salt, the generated radicals graft covalently as aryl-(CF3)2 groups at the surface of both metallic (1T’) and semiconducting (2H) polymorphs of MoTe2. Remarkably, the reactivity of the salt is governed by the electronic structure of the given polymorph. While the functionalization of the metallic MoTe2 occurs spontaneously, the semiconducting MoTe2 requires activation by light. The reaction proceeds with the elimination of oxide from the original films yielding the functionalized products that remain protected in ambient conditions, presenting a viable solution to the ageing of MoTe2 in air. 相似文献
22.
在石墨烯的化学气相沉积工艺中,铜箔是决定石墨烯薄膜质量的重要因素。传统铜箔由于制备工艺的限制,存在大量的缺陷,导致石墨烯薄膜的成核密度较高。本工作选用抛光铝板、抛光不锈钢板、微晶玻璃和SiO2/Si作为基材,用热蒸镀法制备了不同粗糙度的铜箔,并详细讨论了以该系列铜箔生长高平整度石墨烯薄膜的条件及铜箔对石墨烯薄膜品质的影响。实验结果表明,铜箔以(111)取向为主,与基材分离后,表面具有纳米级平整度。在生长石墨烯后,从SiO2/Si剥离的铜箔成核密度是4种基材中最小的。同时,从SiO2/Si剥离的铜箔晶体结构变化最不明显,具有良好的结晶性,表面几乎不存在铜晶界缺陷。当压强为3 000 Pa,氢气和甲烷流速分别为300 mL/min和0.5 mL/min时,可以获得约1 mm横向尺寸的石墨烯单晶晶畴。 相似文献
23.
Dr. Waleed Alsalahi Dr. Adam W. Augustyniak Dr. Włodzimierz Tylus Prof. Dr. Anna M. Trzeciak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(6):e202103538
The new nanocomposites, Pd/C/ZrO2, PdO/ZrO2, and Pd/PdO/ZrO2, were prepared by thermal conversion of Pd@UiO-66-Zr−NH2 (MOF) in nitrogen or air atmosphere. The presence of Pd nanoparticles, uniformly distributed on the ZrO2 or C/ZrO2 matrix, was evidenced by transmission electron microscopy, scanning electron microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS) methods. All pyrolysed composites retained the shape of the MOF template. They catalyze carbonylative Suzuki coupling under 1 atm CO with an efficiency significantly higher than the original Pd@UiO-66-Zr−NH2. The most active PdO/ZrO2 composite, formed benzophenone with TOF up to 1600 h−1, while by using Pd@UiO-66-Zr−NH2, much lower TOF values, 51–95 h−1, were achieved. After the reaction, PdO/ZrO2 was recovered with the same composition and catalytic activity. Very good results were also obtained in the transfer hydrogenation of benzophenones to alcohols with Pd/C/ZrO2 and PdO/ZrO2 catalysts under microwave irradiation. 相似文献
24.
Dr. Zuzanna Wojdyla Prof. Tomasz Borowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202104106
Fe(II)/2-oxoglutarate dependent dioxygenases (ODDs) share a double stranded beta helix (DSBH) fold and utilise a common reactive intermediate, ferryl species, to catalyse oxidative transformations of substrates. Despite the structural similarities, ODDs accept a variety of substrates and facilitate a wide range of reactions, that is hydroxylations, desaturations, (oxa)cyclisations and ring rearrangements. In this review we present and discuss the factors contributing to the observed (regio)selectivities of ODDs. They span from inherent properties of the reactants, that is, substrate molecule and iron cofactor, to the interactions between the substrate and the enzyme's binding cavity; the latter can counterbalance the effect of the former. Based on results of both experimental and computational studies dedicated to ODDs, we also line out the properties of the reactants which promote reaction outcomes other than the “default” hydroxylation. It turns out that the reaction selectivity depends on a delicate balance of interactions between the components of the investigated system. 相似文献
25.
Georgia Ivanova Nadezhda Bozova Nikolay Petkov Dr. Cunbin An Dr. Benlin Hu Monika Mutovska Konstantin Konstantinov Dr. Yulian Zagranyarski Dr. Vladimira Videva Adelina Yordanova Prof. Martin Baumgarten Prof. Anela Ivanova 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(16):e202104411
Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively. 相似文献
26.
本文以咪唑衍生物为配体,通过水热合成法与钴离子制备出两个配位聚合物:{[Co(DTA)(1,4-DIB)(H2O)]·H2O}n(1)和[Co(DTA)(1,3-BMIB)]n(2)(1,4-DIB=1,4-二(1H-咪唑-1-基)苯; 1,3-BMIB=1,3-二(4-甲基-1H-咪唑-1-基)苯;H2DTA=2,5-二甲氧基对苯二甲酸)。利用X射线单晶衍射、粉末衍射、热失重、元素分析、红外光谱以及固体紫外-可见光谱等对两个配合物进行了表征。结构分析证实配合物1和2是通过二维结构堆积成的三维超分子化合物。粉末衍射测试则显示两个配合物在水中有很好的稳定性。固体紫外-可见光谱显示两个配合物属半导体材料,对紫外-可见光有很强的吸收作用。在光催化实验中,配合物1和2可加快亚甲基蓝的降解速度。 相似文献
27.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains 下载免费PDF全文
Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
28.
Photocatalytic CO2 reduction to C1 fuels is considered to be an important way for alleviating increasingly serious energy crisis and environmental pollution. Due to the environment-friendly, simple preparation, easy formation of highly-stable metal-nitrogen(M-Nx) coordination bonds, and suitable band structure, polymeric carbon nitride-based single-atom catalysts(C3N4-based SACs) are expected to become a potential for CO2 reduction under visible-light irradiation. In this review, we summarize the recent advancement on C3N4-based SACs for photocatalytic CO2 reduction to C1 products, including the reaction mechanism for photocatalytic CO2 reduction to C1 products, the structure and synthesis methods of C3N4-based SACs and their applications toward photocatalytic CO2 reduction reaction(CO2RR) for C1 production. The current challenges and future opportunities of C3N4-based SACs for photoreduction of CO2 are also discussed. 相似文献
29.
Peng Zhou Yang Yi Dr. Yuan-Zhao Hua Dr. Shi-Kun Jia Prof. Dr. Min-Can Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103688
The application of dinuclear zinc catalysts in a dearomatization reaction has been developed. Catalytic asymmetric dearomatization [3+2] annulations of 2-nitrobenzofurans or 2-nitrobenzothiophenes with CF3-containing N-unprotected isatin-derived azomethine ylides catalyzed by dinuclear zinc catalysts are realized with excellent diastereomer ratios (dr) of >20 : 1 and enantiomeric excess (ee) of up to 99 %. This protocol provides a practical, straightforward access to structurally diverse pyrrolidinyl spirooxindoles containing a 2,3-fused-dihydrobenzofuran (or dihydrobenzothiphene) moiety, and four contiguous stereocenters. Reactions can be performed on a gram scale. The absolute configuration of products is confirmed by X-ray single crystal structure analysis, and a possible mechanism is proposed. 相似文献
30.
Prof. Dr. Peter Hess 《Chemphyschem》2022,23(6):e202100880
In the periodic table the position of each atom follows the ‘aufbau’ principle of the individual electron shells. The resulting intrinsic periodicity of atomic properties determines the overall behavior of atoms in two-dimensional (2D) bonding and structure formation. Insight into the type and strength of bonding is the key in the discovery of innovative 2D materials. The primary features of 2D bonding and the ensuing monolayer structures of the main-group II–VI elements result from the number of valence electrons and the change of atom size, which determine the type of hybridization. The results reveal the tight connection between strength of bonding and bond length in 2D networks. The predictive power of the periodic table reveals general rules of bonding, the bonding-structure relationship, and allows an assessment of published data of 2D materials. 相似文献