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51.
《Tetrahedron》2019,75(28):3856-3863
Without employing any transition metal, organic solvent and base, a facile, economical and environmentally friendly strategy has been developed for the α-hydroxylation of β-keto esters and β-keto amides with peroxides via radical cross-coupling reaction in water under open-air conditions. This protocol allows a convenient access to various α-hydroxy-β-keto esters and α-hydroxy-β-keto amides with up to 92% yield (34 examples). Moreover, the reaction was successfully scaled up to gram quantity and mechanistic studies showed the radical pathway was involved in this hydroxylation. 相似文献
52.
Yuliya Terentyeva Ye. Yu. Stepanenko A. M. Rashevska P. Yu. Koval 《Molecular Crystals and Liquid Crystals》2020,698(1):65-77
AbstractThe results of an experimental study of luminescence of an aqueous solution of adenosine triphosphate (ATP) at room temperature are presented. High-temperature fluorescence of low- and high-concentrated solution was experimentally detected and analyzed. The shape of the fluorescence spectrum, the excited state lifetime and the temperature behavior of the emission intensity indicate the formation in the high-concentrated solution of rather stable dimer-like complexes, which can form excimer states. 相似文献
53.
A series of carbon-coated, nitrogen-doped titanium dioxide photocatalysts was produced and characterized. N-doped TiO2 powder samples were prepared using a sol-gel method and subsequently used for making doped-TiO2 thin films on glass substrates. Carbon layers were coated on the films by a thermal decomposition method using catechol. Diffuse reflectance spectra and Mott-Schottky analyses of the samples proved that nitrogen doping and carbon coating can slightly lower the band gap of TiO2, broaden its absorption to visible light and enhance its n-type character. According to photocatalytic tests against model contaminants, carbon-coated nitrogen-doped TiO2 films have better performance than simple TiO2 on the degradation of Rhodamine B dye molecules, but are poorly effective for degrading 4-chlorophenol molecules. Several possible explanations are proposed for this result, supported by scavenging experiments. This reveals the importance of a broad substrate scope when assessing new photocatalytic materials for water treatment, something which is often overlooked in many literature studies. 相似文献
54.
Understanding water reduction towards H2 generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H2 production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H2 production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H2 production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H2 production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV. 相似文献
55.
《Arabian Journal of Chemistry》2020,13(4):4869-4881
Herein, we report for the first time, an eco-compatible hydrothermal route for the synthesis of carbon enriched mesoporous material (CuO NFs@MP) using fruit waste (Pulp) obtained from Citrus limetta’s (Mausambi) decorated irregular shaped CuO nanoflakes (NFs). The CuO NFs@MP nanocomposite was fully characterized through several spectroscopic-cum-analytical techniques such as TEM and XPS, which further confirmed the presence of CuO NFs. CuO NFs@MP could serve as an excellent catalyst for N-Arylation reaction and also paves promising peroxidase mimic activity. The preliminary results indicated that CuO NFs@MP shows the catalytic advantage of higher yields, shorter reaction time and greener conditions. Simultaneously, the oxidation of colorless TMB with H2O2 into blue-green colored ox-TMB was also observed in 60 s with CuO NFs@MP. The present nanocomposite is easy to synthesize, economical, retrievable and a reusable catalyst for synthesizing a varied range of N-Arylated products and could also mimic peroxidase without significant loss of activity. 相似文献
56.
57.
金属配合物中的水簇研究为研究宏观意义上的水以及与蛋白质分子有关的水分子提供了有效途径。本文合成了一个含有阴离子水簇的带状超分子配合物[Co(2,2-bipy)2(N3)2](N3)0.5Cl0.5·2H2O(1,2, 2-bipy=2, 2-联吡啶)。单晶结构解析表明,配合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.822 54(7) nm,b=1.175 58(9) nm,c=1.237 06(10) nm,α=91.379 0(10)°,β=92.151 0(10)°,γ=108.119 0(10)°,V=1.135 27(16) nm3,由一个单核[Co(2,2-bipy)2(N3)2]+配合物阳离子、两个非配位水分子、0.5个游离的叠氮离子和0.5个氯离子组成,叠氮离子和氯离子位置无序,占有率各为50%。两个客体水分子通过强烈的分子间氢键作用形成了环状水四聚体,且与无序的N-3和Cl-通过氢键作用形成了一个[(H2O)4(N3)Cl]2- 阴离子水簇。此外,本文基于密度泛函理论(DFT)对配合物[Co(2,2-bipy)2(N3)2]+阳离子进行了量子化学计算,分析了其单点能和原子电荷,并计算了中心金属离子的氧化态,计算结果与实验相吻合。 相似文献
58.
59.
Hydrogen Spillover Enhanced Hydroxyl Formation and Catalytic Activity Toward CO Oxidation at the Metal/Oxide Interface 下载免费PDF全文
Yuekang Jin Guanghui Sun Feng Xiong Liangbing Ding Prof. Dr. Weixin Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4252-4256
H2‐promoted catalytic activity of oxide‐supported metal catalysts in low‐temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt?FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low‐temperature CO oxidation, which provides a molecular‐level understanding of both H2‐promoted catalytic activity of metal/oxide ensembles in low‐temperature CO oxidation and hydrogen spillover. 相似文献
60.
Back Cover: Tailoring Intermolecular Interactions for Efficient Room‐Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices (Angew. Chem. Int. Ed. 42/2014) 下载免费PDF全文
Sungbaek Seo Jaehun Jung Prof. Dr. Jinsang Kim 《Angewandte Chemie (International ed. in English)》2014,53(42):11382-11382