4.8 Article

Influence of ion mobility on the redox and catalytic properties of Cu ions in zeolites

Journal

CHEMICAL SCIENCE
Volume 13, Issue 35, Pages 10238-10250

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc03565k

Keywords

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Funding

  1. European Union's Horizon 2020 Excellence Science ERC-Synergy program 2019-CUBE: Unravelling the secrets of Cu-based catalysts for C-H activation [856446]
  2. European Union's Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [955839]
  3. Italian ministry of University and Research [2017KKP5ZR]
  4. Marie Curie Actions (MSCA) [955839] Funding Source: Marie Curie Actions (MSCA)
  5. European Research Council (ERC) [856446] Funding Source: European Research Council (ERC)

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This paper analyzes the influence of Al distribution, zeolite topology, ligands/reagents, and oxidation state on ions mobility in Cu-zeolites, and its impact on the reactivity of metal sites. The mobility of Cu ions has been observed in the presence of ammonia, enabling the activation of oxygen and providing a new perspective on the chemistry of zeolite-based catalysts. The different mobility of Cu+/Cu2+ ions, even in the absence of ligands, has important implications for the formation of Cu-oxo species and their activity in relevant reactions.
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 NH3 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 NH3-mediated Selective Catalytic Reduction of NOx (NH3-SCR) processes. A different mobility of bare Cu+/Cu2+ ions has been documented too, showing for Cu+ a better mobilization than for Cu2+ 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 NH3-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.

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