全文获取类型
收费全文 | 2225篇 |
免费 | 298篇 |
国内免费 | 538篇 |
专业分类
化学 | 1729篇 |
晶体学 | 56篇 |
力学 | 112篇 |
综合类 | 28篇 |
数学 | 385篇 |
物理学 | 751篇 |
出版年
2024年 | 5篇 |
2023年 | 21篇 |
2022年 | 48篇 |
2021年 | 60篇 |
2020年 | 78篇 |
2019年 | 79篇 |
2018年 | 68篇 |
2017年 | 83篇 |
2016年 | 89篇 |
2015年 | 82篇 |
2014年 | 108篇 |
2013年 | 183篇 |
2012年 | 177篇 |
2011年 | 121篇 |
2010年 | 132篇 |
2009年 | 155篇 |
2008年 | 172篇 |
2007年 | 174篇 |
2006年 | 158篇 |
2005年 | 136篇 |
2004年 | 120篇 |
2003年 | 93篇 |
2002年 | 115篇 |
2001年 | 98篇 |
2000年 | 81篇 |
1999年 | 61篇 |
1998年 | 60篇 |
1997年 | 61篇 |
1996年 | 43篇 |
1995年 | 40篇 |
1994年 | 24篇 |
1993年 | 26篇 |
1992年 | 22篇 |
1991年 | 17篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有3061条查询结果,搜索用时 0 毫秒
121.
A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu)were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11O19-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%. 相似文献
122.
CH4,CO2和O2制合成气反应中载体对Ni催化剂抗氧化性能的影响 总被引:7,自引:0,他引:7
在CH4、CO2 催化氧化制合成气反应中, Ni/Al2O3 催化剂在高温下生成NiAl2O4 尖晶石,是导致催化剂失活的一个重要因素. 通过向载体(Al2O3)中添加各种氧化物, 使得催化剂的抗氧化性能得到改善. 并运用TPR、XRD对催化剂进行表征, 发现催化剂的抗氧化性顺序为: Ni/CaO-Al2O3 > Ni/MgO-Al2O3 > Ni/CeO2-Al2O3 > Ni/La2O3-Al2O3 > Ni/Y2O3-Al2O3 > Ni/TiO2-Al2O3> Ni/Al2O3> Ni/Fe2O3-Al2O3. 相似文献
123.
本文通过简单的一步水热法得到Ni2P-NiS双助催化剂,之后采用溶剂蒸发法将Ni2P-NiS与g-C3N4纳米片结合构建获得无贵金属的Ni2P-NiS/g-C3N4异质结。研究结果表明,优化后的复合材料具有良好的光催化产氢活性,其产氢速率最高可到6892.7 μmol·g-1·h-1,分别为g-C3N4 (150 μmol·g-1·h-1)、15%NiS/g-C3N4 (914.5 μmol·g-1·h-1)和15%Ni2P/g-C3N4 (1565.9 μmol·g-1·h-1)的46.1、7.5和4.4倍。这主要归因于Ni2P-NiS相比Ni2P和NiS单体具有更好的载流子转移能力,其与g-C3N4形成的肖特基势垒能有效促进光生载流子在二者界面上的分离,同时Ni2P-NiS能进一步降低析氢过电势,进而显著增强了表面析氢反应动力学。本研究为开发稳定、高效的非贵金属产氢助剂提供了实验基础。 相似文献
124.
Prof. Makoto Tadokoro Masaki Itoh Ryota Nishimura Kensuke Sekiguchi Dr. Norihisa Hoshino Dr. Hajime Kamebuchi Prof. Jun Miyazaki Dr. Fumiya Kobayashi Prof. Motohiro Mizuno Prof. Tomoyuki Akutagawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201397
A new H-bonded crystal [RuIII(Him)3(Im)3] with three imidazole (Him) and three imidazolate (Im−) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the RuIII complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10−5 S cm−1 at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [RuIII(Him)3(Im)3] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state 2H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered. 相似文献
125.
《天然气化学杂志》2014,(6):761-770
Highly coke-resisting ZrO2-decorated Ni/A1203 catalysts for CO methanation were prepared by a two-step process. The support was first loaded with NiO by impregnating method and then modified with ZrO2 by deposition-precipitation method (IM-DP). Nitrogen adsorption- desorption, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetdc analysis, H2 temperature- programmed reduction and desorption, NH3 temperature-programmed desorption, and zeta potential analysis were employed to characterize the samples. The results revealed that, compared with the catalysts with the same composition prepared by co-impregnation (CI) and sequential impregnation (SI) methods, the Ni/A1203 catalyst prepared by IM-DP showed much enhanced catalytic performance for syngas methanation under the condition of atmospheric pressure and a high weight hourly space velocity of 120000 mL.g-1 .h-1. In a 80 h life time test under the condition of 300-600 ~C and 3.0 MPa, this catalyst showed high stability and resistance to coking, and the amount of deposited carbon was only 0.4 wt%. On the contrary, the deposited carbon over the catalyst without ZrO2 reached 1.5 wt% after a 60 h life time test. The improved catalytic performance was attributed to the selective deposition of ZrO2 nanoparticles on the surface of NiO rather than A1203, which could he well controlled via changing the electrostatic interaction in the DP procedure. This unique structure could enhance the dissociation of CO2 and generate surface oxygen intermediates, thus preventing carbon deposition on the Ni particles in syngas methanation. 相似文献
126.
采用等体积浸渍法制备了高镍负载量的13%Ni/SiO2(13Ni/Si)催化剂和低镍负载量的7%Ni-2%Ce/SiO2(7Ni-2Ce/Si)催化剂.通过N2物理吸附、XRD、FT-IR、TEM、H2-TPR/TPD等技术对催化剂进行表征,在连续流动微反装置上考察了催化剂的CO甲烷化活性.结果表明,在7Ni-2Ce/Si催化剂中NiO、CeO2和SiO2之间产生的相互作用,改变了Ni-O-Si键的化学环境,促进了氧化镍物种的分散和还原,进而提高了催化剂的活性比表面积,同时在催化剂表面形成了新的中等强度的CO吸附中心.与高镍负载量的13Ni/Si催化剂相比,低镍负载量的7Ni-2Ce/Si表现出更高的CO吸附能力和甲烷化活性.常压下,在CO体积分数1%和空速7 000 h-1的反应条件下,低镍负载量的7Ni-2Ce/Si催化剂上CO完全甲烷化最低温度为230 ℃,比高镍负载量的13Ni/Si低了30 ℃. 相似文献
127.
建立了ICP-AES法测定红土镍矿中Ni;Ca;Ti;Mn;Cu;Co;Cr;Zn和P含量的方法。样品用HCl、HNO3溶解,加入HF和HClO4,加热至HClO4烟冒尽,用HCl溶解盐类,过滤,采用ICP-AES法同时测定滤液中Ni、Ca、Mn、Cu、Co、Zn、P;残渣经灼烧、挥硅、K2S2O7熔融、HCl浸取,所得溶液与滤液合并,测定溶液中Cr和Ti含量。方法检出限:P为0.022μg/mL,其它元素在0.0032~0.0085μg/mL之间,方法的精密度(n=7)在1.4%~2.9%之间。分析结果与分光光度法、XRF法和AAS法分析结果的相对误差:Ni、Cu、Co、Cr小于5%,Ti和Mn小于10%,Zn小于15%,Ca和P小于19%。 相似文献
128.
129.
非负载镍催化剂的2-乙基蒽醌加氢活性及其氢吸脱附性质 总被引:4,自引:0,他引:4
分别制备了金属镍粉、兰尼镍、Ni-B非晶态合金及镧掺杂的Ni-B非晶态合金(Ni-B-La)催化剂,研究了催化剂的氢吸附和脱附性质以及对2-乙基蒽醌加氢反应的催化性能. 结果表明,金属镍粉、兰尼镍和Ni-B催化剂表面均具有两种氢吸附位: 弱吸附位和强吸附位. Ni-B-La催化剂表面只有氢的强吸附位,其强吸附氢量与兰尼镍相当. 推测只有氢的强吸附位是2-乙基蒽醌加氢反应的活性中心,并且Ni-B-La催化剂上的强吸附氢较兰尼镍上的更活泼,因而Ni-B-La非晶态合金催化剂对加氢反应的催化活性高于兰尼镍. 相似文献
130.
Assessing the biocompatibility of NiTi shape memory alloys used for medical applications 总被引:3,自引:0,他引:3
Es-Souni M Es-Souni M Fischer-Brandies H 《Analytical and bioanalytical chemistry》2005,381(3):557-567
The present paper reviews aspects related to the biocompatibility of NiTi shape memory alloys used for medical applications. These smart metallic materials, which are characterised by outstanding mechanical properties, have been gaining increasing importance over the last two decades in many minimal invasive surgery and diagnostic applications, as well as for other uses, such as in orthodontic appliances. Due to the presence of high amounts of Ni, the cytotoxicity of such alloys is under scrutiny. In this review paper we analyse work published on the biocompatibility of NiTi alloys, considering aspects related to: (1) corrosion properties and the different methods used to test them, as well as specimen surface states; (2) biocompatibility tests in vitro and in vivo; (3) the release of Ni ions. It is shown that NiTi shape memory alloys are generally characterised by good corrosion properties, in most cases superior to those of conventional stainless steel or Co–Cr–Mo-based biomedical materials. The majority of biocompatibility studies suggest that these alloys have low cytotoxicity (both in vitro and in vivo) as well as low genotoxicity. The release of Ni ions depends on the surface state and the surface chemistry. Smooth surfaces with well-controlled structures and chemistries of the outermost protective TiO2 layer lead to negligible release of Ni ions, with concentrations below the normal human daily intake. 相似文献