全文获取类型
收费全文 | 2357篇 |
免费 | 287篇 |
国内免费 | 330篇 |
专业分类
化学 | 2894篇 |
晶体学 | 2篇 |
力学 | 3篇 |
综合类 | 9篇 |
物理学 | 66篇 |
出版年
2024年 | 6篇 |
2023年 | 46篇 |
2022年 | 285篇 |
2021年 | 249篇 |
2020年 | 173篇 |
2019年 | 135篇 |
2018年 | 111篇 |
2017年 | 98篇 |
2016年 | 117篇 |
2015年 | 125篇 |
2014年 | 114篇 |
2013年 | 185篇 |
2012年 | 103篇 |
2011年 | 111篇 |
2010年 | 84篇 |
2009年 | 109篇 |
2008年 | 77篇 |
2007年 | 88篇 |
2006年 | 84篇 |
2005年 | 72篇 |
2004年 | 69篇 |
2003年 | 81篇 |
2002年 | 66篇 |
2001年 | 41篇 |
2000年 | 47篇 |
1999年 | 36篇 |
1998年 | 29篇 |
1997年 | 37篇 |
1996年 | 24篇 |
1995年 | 49篇 |
1994年 | 27篇 |
1993年 | 24篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 1篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有2974条查询结果,搜索用时 15 毫秒
271.
Oxidative coupling of methane in a dual-bed reactor comprising of particle/cordierite monolithic catalysts 下载免费PDF全文
A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2/cordierite monolithic catalyst. The reaction performance of the oxidative coupling of methane (OCM) over the dual-bed reactor system was evaluated. The effects of the bed height and operation mode, as well as the reaction parameters such as reaction temperature, CH4/O2 ratio and flowrate of feed gas, on the catalytic performance were investigated. The results indicated that the suggested dual-bed reactor exhibited a good performance for the OCM reaction when the feed gases firstly passed through the particle catalyst bed and then to the monolithic catalyst bed. A CH4 conversion of 38.2% and a C2H4 selectivity of 43.3% could be obtained using the dual-bed reactor with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm. Both the CH4 conversion and C2H4 selectivity have increased by 2.5% and 12.8%, respectively, as compared with the 5%Na2WO4-2%Mn/SiO2 particle catalyst in a conventional single-bed reactor and by 12.9% and 23.0%, respectively, as compared with the 4%Ce-5%Na2WO4-2%Mn/SiO2/cordierite monolithic catalyst in a single-bed reactor. The catalytic performance of the OCM in the dual-bed reactor system has been improved remarkably. 相似文献
272.
Suppressed formation of CO2 and H2O in the oxidative coupling of methane over La2O3/MgO catalyst by surface modification 下载免费PDF全文
Oxidative coupling of methane (OCM) is a promising way to convert methane into C_2 hydrocarbons. However, CO_2 and H_2O are by-products of the reaction. To utilize the higher activity of lanthanum oxide and save its usage, MgO supported La_2O_3 catalyst was prepared. Surface modification of the catalyst with nitric acid was made to suppress the formation of the by-products. Experimental results indicated that the addition of nitric acid increased the surface oxygen species with binding energy of ca. 531.7 eV and at the same time reduced the pore volume of the catalyst. These effects of nitric acid finally led to the increase of C_2 selectivity and the decrease of the by-products formation. Hydrogen selectivity was found about 14%- 18% over the catalysts adopted in this work. 相似文献
273.
Ngoc Ha Nguyen Thanh Hue Tran Minh Tho Nguyen Minh Cam Le 《International journal of quantum chemistry》2010,110(14):2653-2670
The density functional theory using a plane‐waves basis set and pseudopotential has been used to study the reaction pathways for ODH of propane on the V2O5(001) surface. The calculations indicated that propane adsoprtion step was initiated by the insertion of vanadyl oxygen O (1) into methylene C? H bond forming an iso‐propanol structure. This step is the rate‐determining step with an activation energy of 23.3 kcal/mol. The subsequent step involved the abstraction of the second hydrogen by O (1) site leading the formation of propene. This process had an activation energy of 22.5 kcal/mol. The elimination of surface bound water molecule at the O (1) was a barrierless process. The energy required for this process was compensated from O2 dissociative adsorption. Finally, the electronic density of state has been applied to prove the reality of the calculated results. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
274.
Judith Cudaj 《Tetrahedron letters》2010,51(23):3092-3094
We present a total synthesis of the fungal natural product graphislactone G, a chlorinated resorcylic lactone. The key step is a Suzuki coupling used for the construction of the central biaryl bond. Graphislactone G was prepared in 13 steps with 22% yield starting with orcinol and phloroglucinic acid, where the longest linear sequence consists of nine steps. 相似文献
275.
276.
WANG Ye AN DongLi & ZHANG QingHong State Key Laboratory of Physical Chemistry of Solid Surfaces National Engineering Laboratory for Green Chemical Productions of Alcohols Ethers Esters 《中国科学:化学》2010,(2)
Selective oxidation or oxidative functionalization of methane and ethane by both homogeneous and heterogeneous catalysis is presented concerning: (1) selective oxidation of methane and ethane to organic oxygenates by hydrogen peroxide in a water medium in the presence of homogeneous osmium catalysts, (2) selective oxidation of methane to formaldehyde over highly dispersed iron and copper heterogeneous catalysts, (3) selective oxidation of ethane to acetaldehyde and formaldehyde over supported molybdenum cat... 相似文献
277.
Fátima C.M. Portugal Moisés L. Pinto João Pires J.M.F. Nogueira 《Journal of chromatography. A》2010,1217(23):3707-3710
Polyurethane (PU) foams were applied for stir bar sorptive extraction of five triazinic metabolites (desethyl-2-hydroxyatrazine, desisopropylatrazine, desethylatrazine, 2-hydroxyatrazine and desethylterbuthylazine) in water matrices, followed by liquid desorption and high performance liquid chromatography with diode array detection (SBSE(PU)-LD/HPLC-DAD). The optimum conditions for SBSE(PU)-LD were 5 h of extraction (1000 rpm) and 5% (v/v) of methanol for the analysis of desethyl-2-hydroxyatrazine and 2-hydroxyatrazine, 15% (w/v) of sodium chloride for the remaining compounds and acetonitrile as back-extraction solvent (5 mL) under ultrasonic treatment (60 min). The methodology provided recoveries up to 26.3%, remarkable precision (RSD < 2.4%), excellent linear dynamic ranges between 5.0 and 122.1 μg/L (r2 > 0.9993) and convenient detection limits (0.4-1.3 μg/L). The proposed method was applied in the analysis of triazinic metabolites in tap, river and ground waters, with remarkable performance and negligible matrix effects. The comparison of the recoveries obtained by PU and commercial stir bars was also performed, where the yields achieved with the former were up to ten times higher proving that PU is appropriate for analysis at trace level of this type of polar compounds in water matrices. 相似文献
278.
介孔氧化铝负载钒催化剂上丙烷氧化脱氢制丙烯 总被引:6,自引:0,他引:6
采用浸渍法制备了介孔氧化铝 (m-Al2O3) 负载钒催化剂 (V/m-Al2O3), 并考察了其催化丙烷氧化脱氢制丙烯反应活性. 通过 N2 吸附-脱附、透射电镜、X 射线粉末衍射、紫外-可见漫反射光谱、氢-程序升温还原和氨-程序升温脱附对催化剂进行了表征. 结果表明, 介孔氧化铝具有大比表面积、窄孔径分布和两维六方相结构, 在其上负载适量的 V 可实现 V 活性物种的高分散及催化剂的弱酸性, 从而有利于提高丙烷转化率和丙烯选择性. 与共合成法制备的含 V 介孔氧化铝 V/m-Al2O3(C) 和浸渍法制备的 V/?-Al2O3 相比, V/m-Al2O3 表现出更高的催化活性. 这与载体较弱的酸性和较大的比表面积以及 V 物种的高分散有关. 相似文献
279.
280.
以9,9'-螺二芴和不同链长的二烷氧基苯为单体, 以FeCl3为催化剂, 采用化学氧化法合成了一系列聚合物发光材料. 溶解度测试表明, 共聚物在二氯甲烷、四氢呋喃(THF)、氯仿等极性溶剂中具有良好的溶解性. 利用核磁共振氢谱(1H NMR)、傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱和荧光(PL)光谱研究了共聚物的化学结构和发光性能, 结果表明共聚物在二甲基亚砜(DMSO)中均发射蓝色荧光, 最大吸收和荧光发射峰分别为356和413 nm. 以硫酸奎宁溶液作为参比, 测得共聚物的荧光量子效率为0.69至0.77. 通过循环伏安法(CV)测得所合成的三种共聚物的最高占有分子轨道(HOMO)能级均位于-5.85至-5.69 eV之间. 相似文献