全文获取类型
收费全文 | 217篇 |
免费 | 32篇 |
国内免费 | 116篇 |
专业分类
化学 | 349篇 |
综合类 | 1篇 |
物理学 | 15篇 |
出版年
2022年 | 5篇 |
2021年 | 9篇 |
2020年 | 10篇 |
2019年 | 5篇 |
2018年 | 8篇 |
2017年 | 12篇 |
2016年 | 14篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 12篇 |
2012年 | 14篇 |
2011年 | 12篇 |
2010年 | 14篇 |
2009年 | 10篇 |
2008年 | 20篇 |
2007年 | 19篇 |
2006年 | 9篇 |
2005年 | 17篇 |
2004年 | 21篇 |
2003年 | 16篇 |
2002年 | 18篇 |
2001年 | 13篇 |
2000年 | 9篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 7篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 1篇 |
排序方式: 共有365条查询结果,搜索用时 15 毫秒
31.
M. López Granados F. Cabello Galisteo M. Alifanti J.L.G. Fierro 《Applied Surface Science》2006,252(24):8442-8450
This work reports the research carried out by studying aliquots extracted at different axial coordinates from Three Way Catalyst (TWC) monoliths aged under real traffic conditions. Our study focused on the catalytic properties and on several chemical and physical effects caused in the Front and Rear monolith washcoat surfaces by vehicle aging after 60,000 km. Regarding the catalytic properties, all the used aliquots showed poorer activity than their corresponding fresh counterparts. The strongest deactivation was detected for NO and hydrocarbon conversion. CO conversion was less affected and the Rear monolith was as deactivated as the Front one. The characterisation techniques (TXRF, N2 adsorption-desorption isotherms, XRD and H2-TPR) detected - (i) the deposition of P, Zn and Pb; (ii) the formation of CePO4 on account of the Ce from the washcoat; (iii) thermal sintering; (iv) inhibition of the reducibility of Ce oxides - as the main effects brought about by vehicle aging conditions. The deactivation observed at the beginning of the Front monolith was the result of a combination of the former effects. When moving downstream to higher axial coordinates, Pb accumulation and the loss of specific area appeared to be the only probable sources of deactivation. 相似文献
32.
Qingfa Wang Li Wang Yaquan Wang Fei He Zhenhua Li Zhentao Mi 《Reaction Kinetics and Catalysis Letters》2004,81(2):297-304
Deactivated palladium catalysts in the hydrogenation of anthraquinione were regenerated with ethanol, nitric acid, hydrogen
peroxide, boiling water and steam, respectively. The deactivated and regenerated catalysts were characterized by XPS, ICP,
TG, FTIR, TPD, XRD, etc., and studied in the hydrogenation of anthraquinone. The results showed that the main cause of catalyst deactivation is the
coverage of the active component by deposits. The treatments by hydrogen peroxide and boiling water can effectively regenerate
the deactivated catalysts.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
33.
采用TEAOH溶液处理MFI结构ZSM-5分子筛、MWW结构MCM-22分子筛,NaOH溶液处理TON结构ZSM-22分子筛、CHA结构SSZ-13分子筛得到四种结构的扩孔分子筛。在反应温度480℃、反应压力0.1 MPa、甲醇与水质量比1∶1、甲醇质量空速1.5 h~(-1)的条件下,考察了四种扩孔分子筛的甲醇制丙烯(MTP)催化性能,并采用XRD、N_2吸附-脱附、NH_3-TPD、TG、UV-Raman和GC-M S等方法表征催化剂的物化性质及M TP反应2 h后的分子筛积炭性质。结果表明,四种分子筛扩孔改性后均出现介孔,其中,T-ZSM-5分子筛在MTP反应中寿命最长;T-MCM-22分子筛寿命次之且失活速率慢;而一维孔道结构N-ZSM-22分子筛和八元环尺寸较小的N-SSZ-13分子筛均失活迅速。受拓扑结构和孔道扩散的影响,MTP反应2 h后,分子筛积炭量增加的顺序为T-ZSM-5N-ZSM-22T-MCM-22N-SSZ-13且可溶焦分子质量随积炭量增加而增重,即从五甲基苯增重到菲、芘等多环芳烃。 相似文献
34.
35.
Hiroshi Sekine Masaaki Ohshima Hideki Kurokawa Hiroshi Miura 《Reaction Kinetics and Catalysis Letters》2008,95(1):99-105
The liquid phase hydrogenation of naphthalene was performed in the presence of CO over a commercial Ni/SiO2-Al2O3 catalyst. Naphthalene was hydrogenated even in the presence of CO at elevated temperatures, accompanying the hydrogenation
of CO. Two activation energy values were obtained for the naphthalene hydrogenation depending on the reaction temperature.
FT-IR measurement of the adsorbed CO was also carried out. Hydrogenation of the adsorbed CO created sites active for naphthalene
hydrogenation. 相似文献
36.
浆态床合成二甲醚复合催化剂失活原因探索 总被引:3,自引:0,他引:3
在反应温度260 ℃、压力5.0 MPa的条件下,对浆态床反应器中二甲醚合成复合催化剂的失活规律进行了研究.结果表明,Cu基催化剂失活较快是导致浆态床二甲醚合成催化剂不稳定的主要原因.通过分析Cu基催化剂在浆态床反应器和固定床反应器中的活性变化规律,发现在浆态床反应器中不能及时导出反应体系的H2O对催化剂的毒副作用导致了浆态床Cu基催化剂快速失活.对失活催化剂进行的TPR、XRD和SEM-EDS表征结果可以看出,Cu粒子的长大和积炭是Cu基催化剂失活的重要原因,与已有文献报道不同的是并未发现明显的Cu元素流失. 相似文献
37.
一步合成二甲醚催化剂烧结失活和原位再生的研究 总被引:1,自引:0,他引:1
采用共沉淀沉积法制备了CuOZnOAl2O3/γ Al2O3 HZSM 5复合催化剂,考察了其对CO加氢直接合成二甲醚的催化性能,研究了催化剂的失活和再生,并用H2-TPR、XRD、TPO、N2O化学吸附等表征方法对反应前后和再生后催化剂的物化性质进行了表征。结果表明,一步合成二甲醚催化剂的失活主要是由于活性位Cu晶粒的烧结长大;反应温度和原料气的组成是影响催化剂失活的因素,在低于220℃下,以N2/H2/CO/CO2为原料气会显著降低催化剂的失活速率。研究使用的氧化还原循环的再生方法能够使Cu晶粒发生再分散,并使失活的催化剂恢复了75%以上的活性。 相似文献
38.
Qing Zhang Huifang Wang Guosong Sun Kelin Huang Weiping Fang Yiquan Yang 《天然气化学杂志》2008,17(4):355-358
Activated carbon-supported Ni catalysts for vapor phase carbonylation of ethanol to propionic acid in the presence of ethyl iodide as promoter were investigated. Under optimum reaction conditions, the conversions of carbon monoxide and ethanol were measured to be 81.4% and 98.4%, respectively, while the selectivity for propionic acid was found to be 98.65%. The catalyst was stable within 48 h on stream. XRD and XPS methods were used to characterize the structures and surface properties of the fresh and tested catalysts. The characterization results indicated that aggregation of nickel particles and formation of nickel iodide on the catalyst surface should be responsible for the deactivation of the catalysts. 相似文献
39.
State‐of‐the‐Art and Progress in Method of Moments for the Model‐Based Reversible‐Deactivation Radical Polymerization 下载免费PDF全文
Reversible‐deactivation radical polymerization (RDRP) techniques have received lots of interest for the past 20 years, not only owing to their simple, mild reaction conditions and broad applicability, but also their accessibility to produce polymeric materials with well‐defined structures. Modeling is widely applied to optimize the polymerization conditions and processes. In addition, there are numerous literatures on the kinetic and reactor models for RDRP processes, which show the accessibility on polymerization kinetics insight, process optimization, and controlling over chain microstructure with predetermined molecular weight and low dispersity, copolymer composition distribution, and sequence distribution. This review highlights the facility of the method of moments in the modeling field and presents a summary of the present state‐of‐the‐art and future perspectives focusing on the model‐based RDRP processes based on the method of moments. Summary on the current status and challenges is discussed briefly.
40.