全文获取类型
收费全文 | 6759篇 |
免费 | 251篇 |
国内免费 | 61篇 |
专业分类
化学 | 4755篇 |
晶体学 | 29篇 |
力学 | 159篇 |
数学 | 1119篇 |
物理学 | 1009篇 |
出版年
2024年 | 7篇 |
2023年 | 47篇 |
2022年 | 155篇 |
2021年 | 211篇 |
2020年 | 136篇 |
2019年 | 141篇 |
2018年 | 135篇 |
2017年 | 113篇 |
2016年 | 261篇 |
2015年 | 249篇 |
2014年 | 257篇 |
2013年 | 430篇 |
2012年 | 474篇 |
2011年 | 550篇 |
2010年 | 340篇 |
2009年 | 275篇 |
2008年 | 466篇 |
2007年 | 422篇 |
2006年 | 429篇 |
2005年 | 350篇 |
2004年 | 309篇 |
2003年 | 227篇 |
2002年 | 212篇 |
2001年 | 67篇 |
2000年 | 70篇 |
1999年 | 46篇 |
1998年 | 68篇 |
1997年 | 57篇 |
1996年 | 61篇 |
1995年 | 38篇 |
1994年 | 34篇 |
1993年 | 35篇 |
1992年 | 41篇 |
1991年 | 35篇 |
1990年 | 20篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 33篇 |
1984年 | 34篇 |
1983年 | 19篇 |
1982年 | 22篇 |
1981年 | 23篇 |
1980年 | 17篇 |
1979年 | 15篇 |
1978年 | 20篇 |
1977年 | 16篇 |
1976年 | 6篇 |
1973年 | 10篇 |
排序方式: 共有7071条查询结果,搜索用时 15 毫秒
961.
Reddy BM Lakshmanan P Loridant S Yamada Y Kobayashi T López-Cartes C Rojas TC Fernandez A 《The journal of physical chemistry. B》2006,110(18):9140-9147
The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations. 相似文献
962.
Boglio C Lenoble G Duhayon C Hasenknopf B Thouvenot R Zhang C Howell RC Burton-Pye BP Francesconi LC Lacôte E Thorimbert S Malacria M Afonso C Tabet JC 《Inorganic chemistry》2006,45(3):1389-1398
The incorporation of lanthanides into polyoxometalates provides entry to new classes of potentially useful materials that combine the intrinsic properties of both constituents. To utilize the [alpha1-Ln(H2O)4P2W17O61]7- species in applications of catalysis and development of luminescent materials, the chemistry of this family of lanthanide polyoxometalates in organic solvents has been developed. Organic-soluble polyoxometalate-lanthanide complexes TBA5H2[alpha1-Ln(H2O)4P2W17O61] (Ln = La(III), Sm(III), Eu(III), Yb(III)) were prepared and characterized by elemental analysis, acid-base titration, IR, 31P NMR, and mass spectrometry. The synthetic procedure involves a cation metathesis reaction in aqueous solution under strict pH control. A solid-liquid-phase transfer protocol yielded a unique species (TBA)8K3[Yb(alpha1-YbP2W17O61)2] with three ytterbium ions and two [alpha1-P2W17O61]10- polyoxotungstates. A centrosymmetric dimeric complex [{alpha1-La(H2O)4P2W17O61}2]14- was crystallized from aqueous solution and characterized by X-ray diffraction. ESI mass spectral analysis of the complexes TBA5H2[alpha1-Ln(H2O)4P2W17O61] shows that similar dimers exist in organic solution, in particular for the early lanthanides. Fragmentation in the mass spectrometer of the complexes from dry acetonitrile solution involves double protonation of an oxo ligand and loss of one water molecule. Low mass tungstate fragments combine into [(WO3)n]2- (n = 1-5) ions and their condensation products with phosphate. Reaction of TBA5H2[alpha1-Eu(H2O)4P2W17O61] with 1,10-phenanthroline or 2,2'-bipyridine showed an increase of the europium luminescence. This result is explained by the formation of a ternary complex of [alpha1-Eu(H2O)4P2W17O61]7- and two sensitizing ligands. 相似文献
963.
Santos RC Bernardes CE Diogo HP Piedade MF Canongia Lopes JN Minas da Piedade ME 《The journal of physical chemistry. A》2006,110(6):2299-2307
The energetics of the thermal dimerization of acenaphthylene to give Z- or E-heptacyclene was investigated. The standard molar enthalpy of the formation of monoclinic Z- and E-heptacyclene isomers at 298.15 K was determined as Delta(f)H(m)o (E-C24H16, cr) = 269.3 +/- 5.6 kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, cr) = 317.7 +/- 5.6 kJ x mol(-1), respectively, by microcombustion calorimetry. The corresponding enthalpies of sublimation, Delta(sub)H(m)o (E-C24H16) = (149.0 +/- 3.1) kJ x mol(-1) and Delta(sub)H(m)o (Z-C24H16) = (128.5 +/- 2.3) kJ x mol(-1) were also obtained by Knudsen effusion and Calvet-drop microcalorimetry methods, leading to Delta(f)H(m)o (E-C24H16, g) = (418.3 +/- 6.4) kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, g) = (446.2 +/- 6.1) kJ x mol(-1), respectively. These results, in conjunction with the reported enthalpies of formation of solid and gaseous acenaphthylene, and the entropies of acenaphthylene and both hepatcyclene isomers obtained by the B3LYP/6-31G(d,p) method led to the conclusion that at 298.15 K the thermal dimerization of acenaphthylene is considerably exothermic and exergonic in the solid and gaseous states (although more favorable when the E isomer is the product), suggesting that the nonobservation of the reaction under these conditions is of kinetic nature. A full determination of the molecular and crystal structure of the E dimer by X-ray diffraction is reported for the first time. Finally, molecular dynamics computer simulations on acenaphthylene and the heptacyclene solids were carried out and the results discussed in light of the corresponding structural and Delta(sub)H(m)o data experimentally obtained. 相似文献
964.
Adams N De Gans BJ Kozodaev D Sanchez C Bastiaansen CW Broer DJ Schubert US 《Journal of combinatorial chemistry》2006,8(2):184-191
A methodology for the rapid design, screening, and optimization of coating systems with surface relief structures, using a combination of statistical experimental design, high-throughput experimentation, data mining, and graphical and mathematical optimization routines was developed. The methodology was applied to photopolymers used in photoembossing applications. A library of 72 films was prepared by dispensing a given amount of sample onto a chemically patterned substrate consisting of hydrophilic areas separated by fluorinated hydrophobic barriers. Film composition and film processing conditions were determined using statistical experimental design. The surface topology of the films was characterized by automated AFM. Subsequently, models explaining the dependence of surface topologies on sample composition and processing parameters were developed and used for screening a virtual 4000-membered in silico library of photopolymer lacquers. Simple graphical optimization or Pareto algorithms were subsequently used to find an ensemble of formulations, which were optimal with respect to a predefined set of properties, such as aspect ratio and shape of the relief structures. 相似文献
965.
Castillo-Rodriguez Judith Pereyra Carlos Javier Valente Paulo Seré Andrés Marotti Ricardo E. Hevia Samuel A. Dalchiele Enrique A. del Rio Quero Rodrigo 《Journal of Solid State Electrochemistry》2020,24(4):797-808
Journal of Solid State Electrochemistry - Transparent conductive oxide electrodes and specifically SnO2:F/glass are widely employed substrates in the preparation of optoelectronic devices. This... 相似文献
966.
Lin Zhang Ivan Merino-Garcia Jonathan Albo Carlos M. Sánchez-Sánchez 《Current Opinion in Electrochemistry》2020
The electrochemical CO2 reduction reaction (CO2RR) either to generate multicarbon (C2+) or single carbon (C1) value-added products provides an effective and promising approach to mitigate the high CO2 concentration in the atmosphere and promote energy storage. However, cost-effectiveness of catalytic materials limits practical application of this technology in the short term. Herein, we summarize and discuss recent and advanced works on cost-effective oxide-derived copper catalysts for the generation of C2+ products (hydrocarbons and alcohols) and transition metal–nitrogen–doped carbon electrocatalytic materials for C1 compounds production from CO2RR. We think they represent suitable electrocatalyst candidates for scaling up electrochemical CO2 conversion. This short review may provide inspiration for the future design and development of innovative active, cost-effective, selective and stable electrocatalysts with improved properties for either the production of C2+ (alcohols, hydrocarbons) or carbon monoxide from CO2RR. 相似文献
967.
Samuel C. Perry Pui-ki Leung Ling Wang Carlos Ponce de León 《Current Opinion in Electrochemistry》2020
CO2 reduction processes continue to be developed for electrosynthesis, energy storage applications, and environmental remediation. A number of promising materials have shown high activity and selectivity to target reduction products. However, the progress has been mainly at a small laboratory scale, and the technical challenges of large scale CO2 reduction have not been considered adequately. This review covers recent advancements in catalyst materials and cell designs. The leading materials for CO2 reduction to a number of useful products are presented with their corresponding cell and reactor designs. The latest efforts to progress to industrially relevant scales are discussed, along with the challenges that must be met for carbon dioxide reduction to be a viable route for mass scale production. 相似文献
968.
969.
Ruzzarin Anelise Lima da Cruz Paulo Alberto de Almeida Rangel Johnny da Silva Carlos José Iwahara Akira Lopes Ricardo Tadeu 《Journal of Radioanalytical and Nuclear Chemistry》2020,323(2):721-729
Journal of Radioanalytical and Nuclear Chemistry - A procedure for characterizing the activity amount of 125I seed was developed in order to establish a secondary standard activity measurement... 相似文献
970.
Carvalho Patricia R. Munita Casimiro S. Neves Eduardo G. Zimpel Carlos A. 《Journal of Radioanalytical and Nuclear Chemistry》2020,324(3):1053-1058
Journal of Radioanalytical and Nuclear Chemistry - This research aims to contribute to the discussion of ceramic objects found at the Monte Castelo shellmound, an archaeological site located at... 相似文献