Święs Aneta, Rutkowska Małgorzata, Kowalczyk Andrzej, Díaz Urbano, Palomares Antonio E, Chmielarz Lucjan
Faculty of Chemistry, Jagiellonian University in Kraków, Gronostajowa 2, 30-387 Kraków, Poland.
Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avd. de los Naranjos s/n, 46022 Valencia, Spain.
Materials (Basel). 2020 Oct 30;13(21):4885. doi: 10.3390/ma13214885.
Ferrierites and their delaminated forms (ITQ-6), containing aluminum or titanium in the zeolite framework, were synthetized and modified with copper by an ion-exchange method. The obtained samples were characterized with respect to their chemical composition (ICP-OES), structure (XRD, UV-Vis DRS), textural parameters (N-sorption), surface acidity (NH-TPD), form and reducibility of deposited copper species (UV-Vis DRS and H-TPR). Ferrierites and delaminated ITQ-6 zeolites modified with copper were studied as catalysts for the selective catalytic oxidation of ammonia to dinitrogen (NH-SCO). It was shown that aggregated copper oxide species, which were preferentially formed on Ti-zeolites, were catalytically active in direct low-temperature ammonia oxidation to NO, while copper introduced into Al-zeolites was present mainly in the form of monomeric copper cations catalytically active in selective reduction of NO by ammonia to dinitrogen. It was postulated that ammonia oxidation in the presence of the studied catalysts proceeds according to the internal-selective catalytic reduction mechanism (i-SCR) and therefore the suitable ratio between aggregated copper oxide species and monomeric copper cations is necessary to obtain active and selective catalysts for the NH-SCO process. Cu/Al-ITQ-6 presented the best catalytic properties possibly due to the most optimal ratio of these copper species.
合成了含有沸石骨架铝或钛的镁碱沸石及其脱层形式(ITQ-6),并通过离子交换法用铜进行改性。通过化学组成(电感耦合等离子体发射光谱法)、结构(X射线衍射、紫外可见漫反射光谱)、织构参数(氮吸附)、表面酸度(氨程序升温脱附)、沉积铜物种的形态和还原性(紫外可见漫反射光谱和氢程序升温还原)对所得样品进行了表征。研究了用铜改性的镁碱沸石和脱层ITQ-6沸石作为氨选择性催化氧化为氮气(NH-SCO)的催化剂。结果表明,优先在钛沸石上形成的聚集氧化铜物种在直接低温氨氧化为一氧化氮中具有催化活性,而引入铝沸石中的铜主要以单体铜阳离子的形式存在,在氨选择性还原一氧化氮为氮气中具有催化活性。据推测,在所研究的催化剂存在下氨氧化按照内选择性催化还原机理(i-SCR)进行,因此聚集氧化铜物种和单体铜阳离子之间的合适比例对于获得用于NH-SCO过程的活性和选择性催化剂是必要的。Cu/Al-ITQ-6表现出最佳的催化性能,这可能是由于这些铜物种的比例最优化。