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941.
Chemoselective Silylative Reduction of Conjugated Nitriles under Metal‐Free Catalytic Conditions: β‐Silyl Amines and Enamines
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Dr. Narasimhulu Gandhamsetty Juhyeon Park Jinseong Jeong Dr. Sung‐Woo Park Dr. Sehoon Park Prof. Dr. Sukbok Chang 《Angewandte Chemie (International ed. in English)》2015,54(23):6832-6836
The B(C6F5)3‐catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β‐silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β‐silyl amine, thus forming a new C(sp3)? Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. 相似文献
942.
Metal‐Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons
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Dr. Ana Sofia Varela Dr. Nastaran Ranjbar Sahraie Julian Steinberg Wen Ju Dr. Hyung‐Suk Oh Prof. Dr. Peter Strasser 《Angewandte Chemie (International ed. in English)》2015,54(37):10758-10762
This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon‐based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low‐area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low‐cost, abundant electrocatalysts for synthetic fuel production from CO2. 相似文献
943.
Dr. Saurabh S. Chitnis Prof. Neil Burford Prof. Jan J. Weigand Dr. Robert McDonald 《Angewandte Chemie (International ed. in English)》2015,54(27):7828-7832
Reactions of triarylphosphines with fluoroantimony(III) triflates give phosphine antimony(III) complexes, which undergo spontaneous reductive elimination of fluorophosphonium cations. The resulting phosphine antimony(I) complexes catenate to give the first examples of cationic antimony bicyclic compounds, [(R3P)4Sb6]4+, featuring a bicyclo[3.1.0]hexastibine framework stabilized by four phosphine ligands. The unprecedented 14‐electron redox process illustrates the generality of the reductive catenation method. 相似文献
944.
Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries
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Dr. Xien Liu Minjoon Park Dr. Min Gyu Kim Shiva Gupta Prof. Gang Wu Prof. Jaephil Cho 《Angewandte Chemie (International ed. in English)》2015,54(33):9654-9658
The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO2 catalysts in primary and rechargeable zinc–air batteries. 相似文献
945.
Heterophase Photocatalysts from Water‐Soluble Conjugated Polyelectrolytes: An Example of Self‐Initiation under Visible Light
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Saman Ghasimi Dr. Simon Prescher Zi Jun Wang Prof. Katharina Landfester Dr. Jiayin Yuan Dr. Kai A. I. Zhang 《Angewandte Chemie (International ed. in English)》2015,54(48):14549-14553
We herein report a new design route to stable, heterophase photocatalysts, which function as highly dispersible conjugated polymer nanoparticles and porous monoliths under visible light in aqueous medium. They were constructed by attachment of the ionic‐liquid species 1‐alkyl‐3‐vinylimidazolium bromide onto the side chains of a photoactive polymer. The structure configuration allows not only photocatalysis in aqueous environment but also a unique self‐initiation radical cross‐linking process to transform the water‐soluble photoactive polymer into a heterophase system, either as nanoparticles or a porous monolith. High photocatalytic activity and reusability of the heterophase system were demonstrated in the degradation of organic dyes and reduction of CrVI into CrIII in water under visible‐light irradiation. 相似文献
946.
Dong‐Gyu Lee Ohhun Gwon Han‐Saem Park Su Hwan Kim Juchan Yang Prof. Sang Kyu Kwak Prof. Guntae Kim Prof. Hyun‐Kon Song 《Angewandte Chemie (International ed. in English)》2015,54(52):15730-15733
The electric conductivity‐dependence of the number of electrons transferred during the oxygen reduction reaction is presented. Intensive properties, such as the number of electrons transferred, are difficult to be considered conductivity‐dependent. Four different perovskite oxide catalysts of different conductivities were investigated with varying carbon contents. More conductive environments surrounding active sites, achieved by more conductive catalysts (providing internal electric pathways) or higher carbon content (providing external electric pathways), resulted in higher number of electrons transferred toward more complete 4e reduction of oxygen, and also changed the rate‐determining steps from two‐step 2e process to a single‐step 1e process. Experimental evidence of the conductivity dependency was described by a microscopic ohmic polarization model based on effective potential localized nearby the active sites. 相似文献
947.
Synthesis of Nitrogen‐Doped Mesoporous Carbon Spheres with Extra‐Large Pores through Assembly of Diblock Copolymer Micelles
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Jing Tang Dr. Jian Liu Dr. Cuiling Li Yunqi Li Prof. Moses O. Tade Prof. Sheng Dai Prof. Yusuke Yamauchi 《Angewandte Chemie (International ed. in English)》2015,54(2):588-593
The synthesis of highly nitrogen‐doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self‐polymerization of dopamine (DA) and spontaneous co‐assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16 nm) and small particle sizes (ca. 200 nm). The large pores and small dimensions of the N‐heteroatom‐doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity. 相似文献
948.
Ionic Liquids as Precursors for Efficient Mesoporous Iron‐Nitrogen‐Doped Oxygen Reduction Electrocatalysts
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Dr. Zelong Li Dr. Guanglan Li Prof. Luhua Jiang Jinlei Li Prof. Gongquan Sun Prof. Chungu Xia Prof. Fuwei Li 《Angewandte Chemie (International ed. in English)》2015,54(5):1494-1498
A ferrocene‐based ionic liquid (Fe‐IL) is used as a metal‐containing feedstock with a nitrogen‐enriched ionic liquid (N‐IL) as a compatible nitrogen content modulator to prepare a novel type of non‐precious‐metal–nitrogen–carbon (M‐N‐C) catalysts, which feature ordered mesoporous structure consisting of uniform iron oxide nanoparticles embedded into N‐enriched carbons. The catalyst Fe10@NOMC exhibits comparable catalytic activity but superior long‐term stability to 20 wt % Pt/C for ORR with four‐electron transfer pathway under alkaline conditions. Such outstanding catalytic performance is ascribed to the populated Fe (Fe3O4) and N (N2) active sites with synergetic chemical coupling as well as the ordered mesoporous structure and high surface area endowed by both the versatile precursors and the synthetic strategy, which also open new avenues for the development of M‐N‐C catalytic materials. 相似文献
949.
Vignesh Nayak Mannekote Shivanna Jyothi Prof. R Geetha Balakrishna Dr. Mahesh Padaki Prof. Ahmad Fauzi Ismail 《ChemistryOpen》2015,4(3):278-287
Herein we present a new approach for the complete removal of CrVI species, through reduction of CrVI to CrIII, followed by adsorption of CrIII. Reduction of chromium from water is an important challenge, as CrIV is one of the most toxic substances emitted from industrial processes. Chitosan (CS) thin films were developed on plain polysulfone (PSf) and PSf/TiO2 membrane substrates by a temperature-induced technique using polyvinyl alcohol as a binder. Structure property elucidation was carried out by X-ray diffraction, microscopy, spectroscopy, contact angle measurement, and water uptake studies. The increase in hydrophilicity followed the order: PSf < PSf/TiO2 < PSf/TiO2/CS membranes. Use of this thin-film composite membrane for chromium removal was investigated with regards to the effects of light and pH. The observations reveal 100 % reduction of CrVI to CrIII through electrons and protons donated from OH and NH2 groups of the CS layer; the reduced CrIII species are adsorbed onto the CS layer via complexation to give chromium-free water. 相似文献
950.
Mechanical polishing,surface roughness,near‐surface deformation,and electrochemical corrosion of Alloy 690TT
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The effects of mechanical grinding/polishing, surface roughness, and near‐surface deformation on the electrochemical corrosion behavior of thermally treated (TT) Alloy 690 were studied in a sodium chloride solution. The X‐ray photoelectron spectroscopy and transmission electron microscopy analyses revealed that mechanical grinding/polishing can change the ratio of the elements at the surface of the as‐received Alloy 690TT specimen by removing its Cr‐rich outer layer and causing deformation at the near‐surface microstructure, something which has a direct impact on the rate of the oxygen reduction reaction (ORR), the pitting potential (Epit), and the corrosion potential (Ecorr) of Alloy 690TT. It was observed that the ratio of Cr in the surface is a significant factor that controls the rate of the ORR and the corrosion parameters such as Ecorr. Higher amounts of Cr at the surface accelerate the ORR. The near‐surface deformation shifts the Epit values towards less positive potentials. It was also found that due to the different near‐surface chemical composition of the as‐received Alloy 690TT specimen compared with the ground and the polished specimens, the surface roughness parameters do not have a regular correlation with the rate of the ORR and the values of the Ecorr and the Epit. Only the passive current density increases when the surface roughness is increased. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献