全文获取类型
收费全文 | 23894篇 |
免费 | 3106篇 |
国内免费 | 2526篇 |
专业分类
化学 | 5872篇 |
晶体学 | 104篇 |
力学 | 1132篇 |
综合类 | 207篇 |
数学 | 2009篇 |
物理学 | 7737篇 |
综合类 | 12465篇 |
出版年
2024年 | 91篇 |
2023年 | 285篇 |
2022年 | 494篇 |
2021年 | 540篇 |
2020年 | 586篇 |
2019年 | 492篇 |
2018年 | 514篇 |
2017年 | 620篇 |
2016年 | 706篇 |
2015年 | 781篇 |
2014年 | 1215篇 |
2013年 | 1406篇 |
2012年 | 1409篇 |
2011年 | 1533篇 |
2010年 | 1256篇 |
2009年 | 1531篇 |
2008年 | 1540篇 |
2007年 | 1819篇 |
2006年 | 1549篇 |
2005年 | 1465篇 |
2004年 | 1160篇 |
2003年 | 1071篇 |
2002年 | 1062篇 |
2001年 | 867篇 |
2000年 | 793篇 |
1999年 | 724篇 |
1998年 | 544篇 |
1997年 | 510篇 |
1996年 | 435篇 |
1995年 | 370篇 |
1994年 | 360篇 |
1993年 | 307篇 |
1992年 | 272篇 |
1991年 | 224篇 |
1990年 | 196篇 |
1989年 | 205篇 |
1988年 | 158篇 |
1987年 | 115篇 |
1986年 | 54篇 |
1985年 | 64篇 |
1984年 | 39篇 |
1983年 | 17篇 |
1982年 | 37篇 |
1981年 | 22篇 |
1980年 | 11篇 |
1979年 | 18篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1974年 | 6篇 |
1973年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Shiori Komai Mitsuhiro Hirano Naofumi Ohtsu 《Surface and interface analysis : SIA》2020,52(12):823-828
The Sr 3d X-ray photoelectron spectroscopy (XPS) spectrum of Sr-containing hydroxyapatite (SHAp) overlaps completely with the P 2p spectrum. Thus, the chemical state identification of Sr in SHAp is a challenging task. In this work, the Sr 3d spectrum was isolated from the overlapping spectra for analyzing the chemical state of Sr using a generic peak-fitting method. The SHAp layers containing various Sr concentrations were produced on a Ti substrate using a chemical treatment process with a calcium phosphate slurry that included Sr (NO3)2. The distribution of the constituent elements changed according to the Sr concentration, implying that the chemical state of Sr varied with concentration. The isolation of the Sr 3d XPS spectrum was conducted via spectral deconvolution using the P 2p spectrum corresponding to HAp. The isolated Sr 3d spectrum revealed that the chemical state of Sr was in SrO and Sr-substituted HAp states, and their ratio varied with the Sr concentration in the layer. The SrO to Sr-substituted HAp ratios affected the Sr ion releasing behavior from the SHAp layer, supporting the validity of the obtained analytical results. 相似文献
992.
993.
Martin Rentschler Sirma Iglesias Marie-Ann Schmid Dr. Cunming Liu Dr. Stefanie Tschierlei Dr. Wolfgang Frey Dr. Xiaoyi Zhang Dr. Michael Karnahl Dr. Dooshaye Moonshiram 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9527-9536
A systematic series of four novel homo- and heteroleptic CuI photosensitizers based on tetradentate 1,10-phenanthroline ligands of the type X^N^N^X containing two additional donor moieties in the 2,9-position (X=SMe or OMe) were designed. Their solid-state structures were assessed by X-ray diffraction. Cyclic voltammetry, UV-vis absorption, emission and X-ray absorption spectroscopy were then used to determine their electrochemical, photophysical and structural features in solution. Following, time-resolved X-ray absorption spectroscopy in the picosecond time scale, coupled with time-dependent density functional theory calculations, provided in-depth information on the excited state electron configurations. For the first time, a significant shortening of the Cu−X distance and a change in the coordination mode to a pentacoordinated geometry is shown in the excited states of the two homoleptic complexes. These findings are important with respect to a precise understanding of the excited state structures and a further stabilization of this type of photosensitizers. 相似文献
994.
995.
通过高温固相法合成了一系列Sr3La2-xGe3O12:xSm^3+(0≤x≤0.04)红色荧光粉,并对样品的形貌、元素组成、晶体结构、发光性能及热稳定性进行了探究。结果表明:样品Sr3La2Ge3O12:xSm^3+为较宽尺寸分布的颗粒,且结构中仅含有Sr、La、Ge、O、Sm等元素。样品Sr3La1.97Ge3O12:0.03Sm^3+的Rietveld结构精修图与实测XRD图完全吻合,具有六方晶系结构。漫反射测试结果显示基质Sr3La2Ge3O12的带宽为5.54 eV,属于宽带隙材料。在404 nm激发下,样品Sr3La2-xGe3O12:xSm^3+(0≤x≤0.04)的最大发射峰位于601nm处,属于Sm^3+的6H5/2→4L13/2能级跃迁。此外,样品Sr3La1.97Ge3O12:0.03Sm^3+的发光性能最佳,其CIE色坐标为(0.5321,0.4601),色纯度高达94.2%,在298-473 K范围内具有较好的热稳定性,测试温度达到423 K时发射强度仍为室温时的81.6%。 相似文献
996.
《中国化学快报》2020,31(11):2965-2969
In the active layer of organic solar cells (OSCs), the lifetime of triplet excitons is one of the decisive factors in the diffusion length and therefore has important impact on the power conversion efficiency of the devices. Herein, we have investigated singlet excited state relaxation dynamics and their triplet exciton lifetimes of two thiophene-coupled perylene diimides (PDI) dyads (2PDI-Th and fused-2PDI-Th), in order to provide a unique explanation in depth on their different performances in OSC devices. From the transient absorption (TA) spectra, the singlet excitons of 2PDI-Th form excimers in the time scale of 1.5 ps. Then the excimers go into the triplet state via intersystem crossing (ISC). In fused-2PDI-Th, triplet excitons are generated directly from the singlet excited excitons via the efficient ISC. Density functional theory (DFT) calculations further support the formation of excimers. DFT results indicate that 2PDI-Th exhibits an H-typed molecular configuration which is beneficial to form the excimers, while fused-2PDI-Th gives a twisted X-shaped configuration in the optimized ground and excited state. In steady-state emission spectra, 2PDI-Th shows abroad and featureless spectral characteristics of the excimers with a decay time of 840 ps, which is much shorter than those of PDI (5.5 ns) and fused-2PDI-Th (3.3 ns). The triplet lifetime (67 μs) of fused-2PDI-Th is factor of 3 longer than that of 2PDI-Th (22 μs). These results demonstrate that ring-fused structure is an efficient strategy to eliminate excimer formation and prolong the lifetime of triplet excitons, which provides a new insight for design of optoelectronic molecules for high efficiency organic solar cells. 相似文献
997.
所谓凝聚态,一般意义上是指液态和固态,而凝聚态化学,即是在固相和液相中的各种化学过程。在无机材料,特别是无机纳米与多孔材料的合成制备中,凝聚态化学过程贯穿其中,几乎无处不在。在固相材料合成过程中,通过液相中的各种化学反应以获得目标固体材料的所需组分和物相,也许就是无机材料合成中一个最基本的凝聚态化学问题;而多孔如微孔或介孔材料合成中,更涉及伴随组分和物相形成过程中的孔结构形成与调控;进一步,在制备面向实际应用如催化剂和药物载体时,则在以上的各项要求之外,还必须考虑材料的表面活性位、缺陷等关键因素,以及颗粒尺寸、分散性和形貌等几何和物理特性。本文以无机氧化物为对象,讨论了无机材料在凝聚态化学合成过程中的几个侧面,包括纳米颗粒和粉体的化学合成方法,多孔材料的合成和多孔复相结构的合成调控,以及多级孔结构沸石的合成制备与催化性能,以期能加深对材料合成中凝聚态化学过程的认识,并期待以凝聚态化学为指导,进一步推动无机材料特别是纳米多孔材料合成的发展。 相似文献
998.
M.-S. Lee K.S. Han J. Lee Y. Shin T.C. Kaspar Y. Chen M.H. Engelhard K.T. Mueller V. Murugesan 《Materials Today Chemistry》2020
Surface reactivity and ion transfer processes of anatase TiO2 nanocrystals were studied using lithium bis(trifluoromethylsulfone)imide (LiTFSI) as a probing molecule. Analysis of synthesized anatase TiO2 by electron microscopy reveals aggregated nanoparticles (average size ~8 nm) with significant defects (holes and cracks). With the introduction of LiTFSI salt, the Li+-adsorption propensity towards the surface along the anatase (100) step edge plane is evident in both x-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) analysis. Ab initio molecular dynamics (AIMD) analysis corroborates the site-preferential interaction of Li+ cations with oxygen vacancies and the thermodynamically favorable transport through the (100) step edge plane. Using 7Li nuclear magnetic resonance (NMR) chemical shift and relaxometry measurements, the presence of Li+ cations near the interface between TiO2 and the bulk LiTFSI phase was identified, and subsequent diffusion properties were analyzed. The lower activation energy derived from NMR analysis reveals enhanced mobility of Li+ cations along the surface, in good agreement with AIMD calculations. On the other hand, the TFSI– anion interaction with defect sites leads to CF3 bond dissociation and subsequent generation of carbonyl fluoride-type species. The multimodal spectroscopic analysis including NMR, electron paramagnetic resonance (EPR), and x-ray photoelectron spectroscopy (XPS) confirms the decomposition of TFSI– anions near the anatase surface. The reaction mechanism and electronic structure of interfacial constituents were simulated using AIMD calculations. Overall, this work demonstrates the role of defects at the anatase nanoparticle surface on charge transfer and interfacial reaction processes. 相似文献
999.
Dr. Baoyan Xing Dr. Sai Ge Prof. Jianguo Zhao Dr. Hui Yang Dr. Jie Song Dr. Yu Geng Dr. Yuying Qiao Prof. Ling Gu Prof. Peide Han Prof. Guibin Ma 《ChemistryOpen》2020,9(10):1018-1026
Solid-state NMR analysis on wurtzite alloyed CdSe1−xSx crystalline nanoparticles and nanobelts provides evidence that the 113Cd NMR chemical shift is not affected by the varying sizes of nanoparticles, but is sensitive to the S/Se anion molar ratios. A linear correlation is observed between 113Cd NMR chemical shifts and the sulfur component for the alloyed CdSe1−xSx (0<x<1) system both in nanoparticles and nanobelts (δCd=169.71⋅XS+529.21). Based on this correlation, a rapid and applied approach has been developed to determine the composition of the alloyed nanoscalar materials utilizing 113Cd NMR spectroscopy. The observed results from this system confirm that one can use 113Cd NMR spectroscopy not only to determine the composition but also the phase separation of nanomaterial semiconductors without destruction of the sample structures. In addition, some observed correlations are discussed in detail. 相似文献
1000.
Jilai Li Caiyun Geng Thomas Weiske Helmut Schwarz 《Angewandte Chemie (International ed. in English)》2020,59(30):12308-12314
[V2O]+ remains “invisible” in the thermal gas‐phase reaction of bare [V2]+ with CO2 giving rise to [V2O2]+; this is because the [V2O]+ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V2O]+ and its involvement in the [V2]+ → [V2O2]+ chemistry are demonstrated by a cross‐over labeling experiment with a 1:1 mixture of C16O2/C18O2, generating the product ions [V216O2]+, [V216O18O]+, and [V218O2]+ in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V2]+ versus [V2O]+ towards CO2. 相似文献