全文获取类型
收费全文 | 8249篇 |
免费 | 567篇 |
国内免费 | 3555篇 |
专业分类
化学 | 11207篇 |
晶体学 | 45篇 |
力学 | 98篇 |
综合类 | 87篇 |
数学 | 337篇 |
物理学 | 597篇 |
出版年
2024年 | 25篇 |
2023年 | 119篇 |
2022年 | 254篇 |
2021年 | 276篇 |
2020年 | 379篇 |
2019年 | 401篇 |
2018年 | 343篇 |
2017年 | 344篇 |
2016年 | 349篇 |
2015年 | 356篇 |
2014年 | 517篇 |
2013年 | 700篇 |
2012年 | 512篇 |
2011年 | 597篇 |
2010年 | 498篇 |
2009年 | 484篇 |
2008年 | 589篇 |
2007年 | 591篇 |
2006年 | 508篇 |
2005年 | 501篇 |
2004年 | 539篇 |
2003年 | 442篇 |
2002年 | 342篇 |
2001年 | 332篇 |
2000年 | 342篇 |
1999年 | 268篇 |
1998年 | 255篇 |
1997年 | 279篇 |
1996年 | 208篇 |
1995年 | 203篇 |
1994年 | 177篇 |
1993年 | 204篇 |
1992年 | 129篇 |
1991年 | 78篇 |
1990年 | 73篇 |
1989年 | 53篇 |
1988年 | 33篇 |
1987年 | 18篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
201.
Conversion ofn-hexane has been applied as a test reaction to study differences between the series of Pt−Sn/γ-Al2O3 catalysts obtainedvia different methods of preparation. Preliminary results of catalytic experiments have been compared with some changes occurring
on the catalysts surfaces as the results of the preparation technique applied. It has been found that catalysts with the second
metal (Sn) introduced to the support by the coprecipitation technique were much more stable in comparison to the catalysts
where the tin component has been added by the impregnation method, however, we have not observed large differences in catalytic
activity. 相似文献
202.
Masayuki Yamane 《Journal of Sol-Gel Science and Technology》1997,8(1-3):483-487
A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between
two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film
formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only
the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO3 or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte
such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic
base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization
of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic
acids, can diffuse in. 相似文献
203.
与贵金属铂基电化学氧还原反应(ORR)催化剂相比,廉价的非贵金属催化剂引起了广泛的关注。本文以壳聚糖作为一种富含氮和碳元素的生物质资源,利用碳浴法成功制备了氮掺杂碳原位负载铜纳米颗粒(Cu/N-C)催化剂。纯壳聚糖碳化得到的样品N-C的比表面积为67.5 m2·g-1、平均孔径0.14 nm、平均孔体积8.00 m2·g-1,与之相比,Cu/N-C比表面积可达607.3 m2·g-1、平均孔径为2.5 nm、平均孔体积为0.40 cm3·g-1。通过密度泛函理论(DFT)进行计算表明,Cu(111)/N-C的自由能值低于N-C,更有利于氧还原催化进行。在0.1 mol·L-1 KOH的介质中,Cu/N-C不仅表现出优异的起始和半波电势(分别为0.96 V和0.84 V),而且还表现出了优异的抗甲醇性能和稳定性,并且Cu元素掺杂量达到1.67wt.%。 相似文献
204.
Dr. Yanhui Wang Dr. Maroua Bouchneb Rimeh Mighri Dr. Johan G. Alauzun Dr. P. Hubert Mutin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2670-2682
Several non-hydrolytic sol–gel syntheses involving different precursors, oxygen donors, and conditions have been screened aiming to selectively produce mesoporous t-ZrO2 or m-ZrO2 with significant specific surface areas. The in situ water formation was systematically investigated by Karl Fisher titration of the syneresis liquids. XRD and nitrogen physisorption were employed to characterize the structure and texture of the ZrO2 samples. Significant amounts of water were found in several cases, notably in the reactions of Zr(OnPr)4 with ketones (acetone, 2-pentanone, acetophenone), and of ZrCl4 with alcohols (benzyl alcohol, ethanol) or acetone. Conversely, the reactions of Zr(OnPr)4 with acetic anhydride or benzyl alcohol at moderate temperature (200 °C) and of ZrCl4 with diisopropyl ether appear strictly non-hydrolytic. Although reaction time and reaction temperature were also important parameters, the presence of water played a crucial role on the structure of the final zirconia: t-ZrO2 is favored in strictly non-hydrolytic routes, while m-ZrO2 is favored in the presence of significant amounts of water. 1H and 13C NMR analysis of the syneresis liquids allowed us to identify the main reactions responsible for the formation of water and of the oxide network. The morphology of the most interesting ZrO2 samples was further investigated by electron microscopy (SEM, TEM). 相似文献
205.
Sambath Baskaran Prof. Cong-Qiao Xu Ya-Fei Jiang Yang-Gang Wang Prof. Dr. Jun Li 《Chemphyschem》2021,22(4):378-385
Single-atom catalysts (SACs) have attracted extensive attention owing to their high catalytic activity. The development of efficient SACs is crucial for applications in heterogeneous catalysis. In this article, the geometric configuration, electronic structure, stabilitiy and catalytic performance of phosphorene (Pn) supported single metal atoms (M=Ru, Rh, Pd, Ir, Pt, and Au) have been systematically investigated using density functional theory calculations and ab initio molecular dynamics simulations. The single atoms are found to occupy the hollow site of phosphorene. Among the catalysts studied, Ru-decorated phosphorene is determined to be a potential catalyst by evaluating adsorption energies of gaseous molecules. Various mechanisms including the Eley-Rideal (ER), Langmuir-Hinshelwood (LH) and trimolecular Eley-Rideal (TER) mechanisms are considered to validate the most favourable reaction pathway. Our results reveal that Ru−Pn exhibits outstanding catalytic activity toward CO oxidation reaction via TER mechanism with the corresponding rate-determining energy barrier of 0.44 eV, making it a very promising SAC for CO oxidation under mild conditions. Overall, this work may provide a new avenue for the design and fabrication of two-dimensional materials supported SACs for low-temperature CO oxidation. 相似文献
206.
K. Sai Bhavani T. Anusha J. V. Shanmukha Kumar Pradeep Kumar Brahman 《Electroanalysis》2021,33(1):97-110
Direct alcohol fuel cells (DAFCs) have been recently playing a pivotal role in electrochemical energy sources and portable electronics. Research in DAFCs has proceeded to engage major attention due to their high catalytic activity, long-term stability, portability, and low cost. Herein, we present a facile surfactant-free route to anchor bimetallic Pd−W nanoparticles supported fullerene-C60 catalyst (Pd-W@Fullerene-C60) for high-performance electrooxidation of alcohols (methanol & ethanol) for DAFCs applications. Structural, elemental composition, and morphological analysis of the proposed catalyst were carried out using UV-Vis spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy-dispersive x-ray spectroscopy (EDX). Electrochemical properties such as electrochemical activity, electrochemical active surface area (ECSA), and long-term stability of the Pd-W@Fullerene-C60 catalyst for ethanol and methanol oxidation in the alkaline medium were explored by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry (CA). Results revealed that the proposed catalyst showed enlarged ECSA, tremendous electrocatalytic activity, high poison tolerance limit, good reproducibility, and enhanced long-term stability as compared to the monometallic catalyst and commercially available catalyst (Pt/C) towards ethanol and methanol oxidation reaction. This enhanced potentiality of the Pd-W@Fullerene-C60 catalyst is due to the synergistic effect of W−Pd nanoparticles and excellent electron kinetic from fullerene support material. These findings strongly suggest the Pd-W@Fullerene-C60 catalyst as potential anode material for the alcohol oxidation reaction. 相似文献
207.
Bimetallic CuCo composites are prepared by calcinating copper hexacyanocobaltate precursor in N2 atmosphere. The CuCo modified electrodes are fabricated for nonenzymatic glucose sensing in the alkaline electrolyte. The glucose can be directly electro-oxidized on the surface of the electrode catalyst mediated by the redox couples of Cu and Co. The optimal glucose sensor exhibits a high sensitivity (567 μA ⋅ mM−1 ⋅ cm−2) in the range up to 825 μM with a detection limit of 3 μM and acceptable selectivity. The sensor can also be applied in serum samples. This work provides a facile and easily-scalable synthesis method of electrocatalysts for nonenzymatic glucose sensors. 相似文献
208.
Emad M. Hussien Mohamed Rizk Amira M. Daoud Rasha Th. El-Eryan 《Electroanalysis》2021,33(7):1771-1777
Simple, sensitive, accurate and inexpensive differential pulse (DPV) and square wave (SWV) voltammetric methods utilizing zeolite modified carbon paste electrode (ZMCPE) were developed for the determination of Oxymetazoline hydrochloride (OXM) in nasal drops. Various experimental parameters were optimized using cyclic voltammetry (CV). Calibration curves were linear over the concentration ranges 9.8×10−8–3.6×10−6 M and 9.8×10−6–9×10−5 M for DPV and SWV, respectively. The DPV method showed a limit of detection (LOD) of 1.04×10−7 M. The method was applied for the determination of OXM in pharmaceutical formulation with an average recovery of 101.18 % (%RSD=0.41, n=9). 相似文献
209.
Demet Uzun 《Electroanalysis》2021,33(7):1699-1706
In this present study, to determine paracetamol, an electroanalytical method is presented using differential pulse voltammetry (DPV) at 3-amino-4H-1,2,4-triazole (3AT) coated glassy carbon (GC) electrode. The electrochemical characterization and electron transfer behavior of this prepared electrode in the mixture of K4[Fe(CN)6]/K3[Fe(CN)6] contains 0.1 M KCl was confirmed by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods. Furthermore, scanning electron microscopy (SEM) was used to observe morphological structures of the bare and modified surfaces. The effect of pH was studied on the redox reaction of paracetamol in phosphate buffer in the range of pH 3.0–9.0. The limit of detection was 0.043 μM (3 s/m) for 3AT-GC electrode. The developed electrode was successfully utilized in pharmaceutical samples. 相似文献
210.
A sensitive, low-cost, and simple electrochemical sensor based on Zn−Al layered double hydroxide (Zn−Al LDH) combined with a polymer film of methyl red (PMR) to modify a GCE has been created for the first time. Using cyclic voltammetry (CV), the electrochemical characteristics of the newly fabricated sensor were investigated. The characterised PMR/Zn−Al LDH/GCE shows high electro-catalytic activity towards the vitamin C (AA) and aspirin (ASA) oxidation. Schematic fabrication of PMR/Zn−Al LDH/GCE for the determination of AA or ASA was presented. The new sensor demonstrated superior analytical efficiency for the simultaneous identification of AA and ASA traces in well-spaced anodic peaks, even in the presence of certain intervening species. According to experimental results, the fabricated sensor represented two well-separated oxidation peaks for AA and ASA oxidation with potential difference of 799 mV (vs. Ag/AgCl). The linear dependences of the anodic peak currents of AA and ASA on their concentrations in the ranges of 0.10–53.17 μM are good. The detection limits of AA and ASA at the PMR/Zn−Al LDH/GCE were found to be 1.26 and 1.27 μM, respectively. Meanwhile, the quantification limits of AA and ASA were calculated as 4.21 and 4.25 μM, respectively. On other hand, the limit of detection (LODs) of AA and ASA oxidation were determined to be 0.47 and 0.21 μM, respectively, according to DPV method. The effect of scan rate (100 to 800 mV/s) on the anodic peak currents of AA and ASA was examined. A sensing model mechanism has been suggested and discussed in detail. Finally, the proposed sensor displayed a good reproducibility, stability and selectivity. The developed sensor was eventually used to successfully detect AA and ASA in urine samples. 相似文献