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氧化镁晶格中锂离子的存在:通过红外光谱进行表面表征以及对丙烷氧化转化的反应活性

Presence of lithium ions in MgO lattice: surface characterization by infrared spectroscopy and reactivity towards oxidative conversion of propane.

作者信息

Trionfetti Cristiano, Babich Igor V, Seshan K, Lefferts Leon

机构信息

Catalytic Processes and Materials Group, Faculty of Science and Technology, IMPACT, MESA+ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands.

出版信息

Langmuir. 2008 Aug 5;24(15):8220-8. doi: 10.1021/la8006316. Epub 2008 Jul 3.

Abstract

The surface morphology of Li-promoted MgO catalysts prepared using the sol-gel method (sg) and wet impregnation procedure (imp), respectively, has been studied by low-temperature infrared spectroscopy of adsorbed CO molecules. The results show that step sites, as unselective catalytic centers, are the major features existing on the surface of pure MgO, and those are active toward the oxidative conversion of propane. However, the concentration of these sites is drastically reduced by the incorporation of lithium ions in the MgO lattice. In fact, the incorporated Li (+) ions tend to move into the surface region and occupy sites associated with lower coordination number (e.g., step sites). Li/MgO-sg catalysts are characterized by a higher concentration of incorporation of lithium compared to Li/MgO-imp. In the case of oxidative dehydrogenation/cracking of propane, Li/MgO-sg catalysts show higher activity and selectivity to olefins compared to materials prepared using wet impregnation. Catalytic performance differs strongly regarding (i) the amount of olefins formed, and (ii) the ratio of C(3)H(6)/C(2)H(4). It is shown that high density of active sites is essential for further oxidative dehydrogenation of propyl radicals to propylene and suppression of cracking reactions pathway.

摘要

分别采用溶胶-凝胶法(sg)和湿浸渍法(imp)制备的锂促进氧化镁催化剂的表面形态,已通过吸附CO分子的低温红外光谱进行了研究。结果表明,台阶位点作为非选择性催化中心,是纯氧化镁表面存在的主要特征,并且对丙烷的氧化转化具有活性。然而,氧化镁晶格中锂离子的掺入极大地降低了这些位点的浓度。实际上,掺入的Li(+)离子倾向于移动到表面区域并占据与较低配位数相关的位点(例如台阶位点)。与Li/MgO-imp相比,Li/MgO-sg催化剂的特征在于锂的掺入浓度更高。在丙烷氧化脱氢/裂解的情况下,与使用湿浸渍法制备的材料相比,Li/MgO-sg催化剂对烯烃表现出更高的活性和选择性。催化性能在(i)形成的烯烃量和(ii)C(3)H(6)/C(2)H(4)的比例方面有很大差异。结果表明,高密度的活性位点对于丙基自由基进一步氧化脱氢生成丙烯以及抑制裂解反应途径至关重要。

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