经合成处理的 ERI 和 SSZ-13 沸石用铜改性后用作 NH3-SCR-DeNOx 催化剂

Catalysts Pub Date : 2024-07-16 DOI:10.3390/catal14070457
Alejandro Mollá Robles, Gabriele Deplano, K. Góra-Marek, M. Rotko, A. Wach, Muhammad Fernadi Lukman, Marko Bertmer, M. Signorile, Silvia Bordiga, A. Pöppl, Roger Gläser, Magdalena Jabłońska
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摘要

ERI和SSZ-13经过后合成处理(取决于沸石的拓扑结构),形成了微孔/多孔材料。NH3-SCR-DeNOx方面的结果表明,所采用的处理方法提高了以含铜ERI为基础的材料的催化活性;然而,用NaOH或NaOH/HNO3处理的不同材料的NO转化率并无不同。对于微孔/多孔含铜 SSZ-13,在 NH3-SCR-DeNOx 中观察到较低的 NO 转化率。因此,我们的研究结果对微孔/介孔催化剂在 NH3-SCR-DeNOx 中活性增强的现有模式提出了挑战。对支撑物的改性导致 ERI 和 SSZ-13 样品中存在不同数量和种类的铜物种(尤其是孤立的 Cu2+ 和聚集的铜物种)。铜物种的存在进一步区分了反应中间产物的形成。我们的研究表明,在这些催化体系中,除了 μ-η2,η2- 过氧化二铜(II)配合物(通过原位 DR 紫外可见光谱验证)之外,硝酸铜(通过原位傅立叶变换红外光谱证明)也是反应中间体。
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Post-Synthetically Treated ERI and SSZ-13 Zeolites Modified with Copper as Catalysts for NH3-SCR-DeNOx
ERI and SSZ-13 were subjected to post-synthetic treatments (depending on the zeolite topology) to create micro-/mesoporous materials. The results in terms of NH3-SCR-DeNOx show that the applied treatments improved the catalytic activity of the Cu-containing ERI-based materials; however, the NO conversion did not vary for the different materials treated with NaOH or NaOH/HNO3. For the micro-/mesoporous Cu-containing SSZ-13, a lower NO conversion in NH3-SCR-DeNOx was observed. Thus, our findings challenge the current paradigm of enhanced activity of micro-/mesoporous catalysts in NH3-SCR-DeNOx. The modification of the supports results in the presence of different amounts and kinds of copper species (especially isolated Cu2+ and aggregated Cu species) in the case of ERI- and SSZ-13-based samples. The present copper species further differentiate the formation of reactive reaction intermediates. Our studies show that besides the μ-η2,η2-peroxo dicopper(II) complexes (verified by in situ DR UV-Vis spectroscopy), copper nitrates (evidenced by in situ FT-IR spectroscopy) also act as reactive intermediates in these catalytic systems.
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