Signorile Matteo, Borfecchia Elisa, Bordiga Silvia, Berlier Gloria
Department of Chemistry and NIS Centre, Università di Torino Via P. Giuria 7 Torino 10125 Italy
Chem Sci. 2022 Aug 19;13(35):10238-10250. doi: 10.1039/d2sc03565k. eCollection 2022 Sep 14.
This contribution aims at analysing the current understanding about the influence of Al distribution, zeolite topology, ligands/reagents and oxidation state on ions mobility in Cu-zeolites, and its relevance toward reactivity of the metal sites. The concept of Cu mobilization has been originally observed in the presence of ammonia, favouring the activation of oxygen by formation of NH oxo-bridged complexes in zeolites and opening a new perspective about the chemistry in single-site zeolite-based catalysts, in particular in the context of the NH-mediated Selective Catalytic Reduction of NO (NH-SCR) processes. A different mobility of bare Cu/Cu ions has been documented too, showing for Cu a better mobilization than for Cu also in absence of ligands. These concepts can have important consequences for the formation of Cu-oxo species, active and selective in other relevant reactions, such as the direct conversion of methane to methanol. Here, assessing the structure, the formation pathways and reactivity of Cu-oxo mono- or multimeric moieties still represents a challenging playground for chemical scientists. Translating the knowledge about Cu ions mobility and redox properties acquired in the context of NH-SCR reaction into the field of direct conversion of methane to methanol can have important implications for a better understanding of transition metal ions redox properties in zeolites and for an improved design of catalysts and catalytic processes.
本论文旨在分析当前对于铝分布、沸石拓扑结构、配体/试剂以及氧化态对铜沸石中离子迁移率的影响的理解,及其与金属位点反应性的相关性。铜迁移的概念最初是在氨存在的情况下观察到的,氨有利于在沸石中形成NH氧桥络合物从而活化氧,并为基于单中心沸石的催化剂中的化学过程开辟了新的视角,特别是在NH介导的选择性催化还原NO(NH-SCR)过程的背景下。也有文献记载了裸铜/铜离子的不同迁移率,表明即使在没有配体的情况下,铜的迁移性也比铜更好。这些概念对于形成在其他相关反应(如甲烷直接转化为甲醇)中具有活性和选择性的铜氧物种可能具有重要影响。在这里,评估铜氧单聚体或多聚体部分的结构、形成途径和反应性仍然是化学科学家面临的一个具有挑战性的领域。将在NH-SCR反应背景下获得的关于铜离子迁移率和氧化还原性质的知识转化到甲烷直接转化为甲醇的领域,对于更好地理解沸石中过渡金属离子的氧化还原性质以及改进催化剂和催化过程的设计可能具有重要意义。