全文获取类型
收费全文 | 1206篇 |
免费 | 103篇 |
国内免费 | 372篇 |
专业分类
化学 | 1328篇 |
晶体学 | 6篇 |
力学 | 6篇 |
综合类 | 12篇 |
物理学 | 329篇 |
出版年
2024年 | 2篇 |
2023年 | 22篇 |
2022年 | 31篇 |
2021年 | 40篇 |
2020年 | 56篇 |
2019年 | 45篇 |
2018年 | 37篇 |
2017年 | 65篇 |
2016年 | 53篇 |
2015年 | 41篇 |
2014年 | 53篇 |
2013年 | 80篇 |
2012年 | 70篇 |
2011年 | 74篇 |
2010年 | 67篇 |
2009年 | 109篇 |
2008年 | 113篇 |
2007年 | 104篇 |
2006年 | 94篇 |
2005年 | 81篇 |
2004年 | 80篇 |
2003年 | 45篇 |
2002年 | 49篇 |
2001年 | 38篇 |
2000年 | 33篇 |
1999年 | 26篇 |
1998年 | 32篇 |
1997年 | 29篇 |
1996年 | 26篇 |
1995年 | 18篇 |
1994年 | 18篇 |
1993年 | 12篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1681条查询结果,搜索用时 10 毫秒
61.
利用俄歇电子能谱(AES)和程序升温脱附谱(TDS)研究了NO2在Ag/Pt(110)双金属表面的吸附和分解.室温下NO2 在Ag/Pt(110)双金属表面发生解离吸附, 生成NO(ads)和O(ads)表面吸附物种. 在升温过程中NO(ads)物种发生脱附或者进一步分解. 500 K时NO2在Ag/Pt(110)双金属表面发生解离吸附生成O(ads)表面吸附物种. Pt 向Ag传递电子, 从而削弱Pt-O键的强度, 降低O(ads)从Pt 表面的并合脱附温度. 发现能够形成具有稳定组成的Ag/Pt(110)合金结构, 其表现出与Pt(110)-(1×2)相似的解离吸附NO2能力, 但与O(ads)的结合明显弱于Pt(110)-(1×2). 该AgPt(110)合金结构是可能的低温催化直接分解氮氧化物活性结构. 相似文献
62.
Henry A. Nkabyo D. Hannekom Jean McKenzie 《Journal of Coordination Chemistry》2014,67(23-24):4039-4060
Irradiation cis-[M(Ln-S,O)2] complexes (M = PtII, PdII) derived from N,N-dialkyl-N′-benzoylthioureas (HLn) with various sources of intense visible polychromatic or monochromatic light with λ < 500 nm leads to light-induced cis?→?trans isomerization in organic solvents. In all cases, white light derived from several sources or monochromatic blue-violet laser 405 nm light, efficiently results in substantial amounts of the trans isomer appearing in solution, as shown by 1H NMR and/or reversed-phase HPLC separation in dilute solutions at room temperature. The extent and relative rates of cis/trans isomerization induced by in situ laser light (λ = 405 nm) of cis-[Pd(L2-S,O)2] was directly monitored by 1H NMR and 195Pt NMR spectroscopy of selected cis-[Pt(L-S,O)2] compounds in chloroform-d; both with and without light irradiation allows the δ(195Pt) chemical shifts cis/trans isomer pairs to be recorded. The cis/trans isomers appear to be in a photo-thermal equilibrium between the thermodynamically favored cis isomer and its trans counterpart. In the dark, the trans isomer reverts back to the cis complex in what is probably a thermal process. The light-induced cis/trans process is the key to preparing and isolating the rare trans complexes which cannot be prepared by conventional synthesis as confirmed by the first example of trans-[Pd(L-S,O)2] characterized by single-crystal X-ray diffraction, deliberately prepared after photo-induced isomerization in acetonitrile solution. 相似文献
63.
合成了2个新配体4-(4-硫代乙酸)甲苯基-6-苯基-2,2’-联吡啶HC^N^N(PhCH2SCOCH3)(L3)和6-(4-硫代乙酸)甲苯基-2,2’-联吡啶HC^N^N(CH2SCOCH3)(L5)及其发光的铂(Ⅱ)配合物ClPtC^N^N(PhCH2SCOCH3)(C3)和ClPtC^N^N(CH2SCOCH3)(C5).通过1H NMR谱和质谱对它们的结构进行了表征,采用X射线单晶衍射分析确定了C3的晶体结构.利用紫外-可见吸收光谱、发射光谱及激发态寿命测定研究了它们的光物理性质和电化学性质,以及配合物作为光敏剂在光催化制氢中的应用.通过系列配合物产氢效率的比较,揭示了它们的产氢效率和激发态寿命的关系. 相似文献
64.
Bin Ran Chaozhan Chen Bo Liu Minbo Lan Huaying Chen Yonggang Zhu 《Electrophoresis》2022,43(20):2033-2043
The detection of cancer biomarkers is of great significance for the early screening of cancer. Detecting the content of sarcosine in blood or urine has been considered to provide a basis for the diagnosis of prostate cancer. However, it still lacks simple, high-precision and wide-ranging sarcosine detection methods. In this work, a Ti3C2TX/Pt–Pd nanocomposite with high stability and excellent electrochemical performance has been synthesized by a facile one-step alcohol reduction and then used on a glassy carbon electrode (GCE) with sarcosine oxidase (SOx) to form a sarcosine biosensor (GCE/Ti3C2TX/Pt–Pd/SOx). The prominent electrocatalytic activity and biocompatibility of Ti3C2TX/Pt–Pd enable the SOx to be highly active and sensitive to sarcosine. Under the optimized conditions, the prepared biosensor has a wide linear detection range to sarcosine from 1 to 1000 µM with a low limit of detection of 0.16 µM (S/N = 3) and a sensitivity of 84.1 µA/mM cm2. Besides, the reliable response in serum samples shows its potential in the early diagnosis of prostate cancer. More importantly, the successful construction and application of the amperometric biosensor based on Ti3C2TX/Pt–Pd will provide a meaningful reference for detecting other cancer biomarkers. 相似文献
65.
Alkaline water electrolysis despite having a variety of choices for anodic oxygen evolution reaction (OER) catalysts out of non-precious metals suffers significantly due to the poor kinetics of cathodic hydrogen evolution reaction (HER) even with the state-of-the-art Pt and equally active Ru. The Volmer-step (water dissociation (WD) coupled proton adsorption) of alkaline HER is mostly the rate-determining step (RDS) and costs most of the work required. In this review, recent developments in improving the HER kinetics of Pt and Ru with Volmer-step promotors and electronic structure modulators have been comprehensively analyzed and critically presented with the challenges and prospects. 相似文献
66.
Here, polymelamine formaldehyde was decorated on the surface of reduced graphene oxide whose surface was then electrodeposited with a sub-monolayer of platinum nanoparticles. The nanocomposite thus prepared was characterized using several spectroscopic methods. Using the nanocomposite as a potential electrocatalyst for carbon dioxide reduction, the products were detected by Raman spectroscopy, gas chromatography, 13C-NMR spectroscopy, and gas chromatography-mass spectrometry. The analytical results identified methanol as the main product of CO2 reduction. Moreover, analysis of the liquid products confirmed methanol as the predominant product with a current density of 0.4 mA/cm and a Faradaic efficiency of 93 %. 相似文献
67.
Herein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd–Pt alloy/multi-walled carbon nanotubes (Pd–Pt/CNTs) nanocomposites. A good number of Pd–Pt alloy nanoparticles with an average of 3.4 ± 0.5 nm were supported on sidewalls of CNTs with uniform distribution. The composition of the Pd–Pt/CNTs nanocomposites could also be easily controlled, which provided a possible approach for the preparation of other architectures with anticipated properties. The Pd–Pt/CNTs nanocomposites were extensively studied by electron microscopy, induced coupled plasma atomic emission spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and applied for the ethanol and methanol electro-oxidation reaction in alkaline medium. The electrochemical results indicated that the nanocomposites had better electrocatalytic activities and stabilities, showing promising applications for fuel cells. 相似文献
68.
螯合辅助溶剂挥发共组装法制备的炭-氧化铝复合材料为载体,分别使用水、乙醇或二者混合物为氯铂酸的分散介质,浸渍制备炭-氧化铝复合材料负载Pt催化剂.通过XRD,N2物理吸附以及TEM表征可知,乙醇作为浸渍溶剂时,最有利于Pt的分散,而混合溶剂浸渍制备的催化剂Pt颗粒最大.2-氧-4-苯基丁酸乙酯不对称加氢反应结果表明,氯铂酸水溶液浸渍得到的催化剂Pt纳米粒子的粒径有利于获得高的光学选择性,催化剂经辛可尼丁修饰后,以乙酸为反应溶剂,可获得最高84.8%的光学选择性.此外,该催化剂重复利用性能优异,可以重复利用22次,活性没有下降. 相似文献
69.
70.
Complex 3D microparticle, as an emerging and attractive field, has attracted more and more attention due to its versatile morphologies and broad range of applications. In this review, we provide an overall recent progress in 3D microparticles fabricated by microfluidic lithography. This review will focus on the synthesis mechanisms, synthesis process, the resultant 3D microparticles, and their applications. Finally, we will look into the future trends in complex 3D microparticles. This review will be beneficial for researchers in numerous fields, including functional materials, sensors, encryption, and biomedical engineering. 相似文献