Location of Cu2+ in CHA zeolite investigated by X-ray diffraction using the Rietveld/maximum entropy method

• Published in: IUCrJ Vol. 1; no. 6; pp. 382 - 386
• Main Authors: Andersen, Casper Welzel, Bremholm, Martin, Vennestrøm, Peter Nicolai Ravnborg, Blichfeld, Anders Bank, Lundegaard, Lars Fahl, Iversen, Bo Brummerstedt
• Format: Journal Article
• Language: English
• Published: Chester International Union of Crystallography 01.11.2014
• Subjects: Aluminum; Catalysis; Catalysts; catalytic activity; CHA zeolites; Copper; Diffraction; location of Cu2; Maximum entropy method; Research Letters; Rietveld/maximum entropy method; synchrotron powder X-ray diffraction; X-rays; Zeolites
• ISSN: 2052-2525; 2052-2525
• DOI: 10.1107/S2052252514020181

Accurate structural models of reaction centres in zeolite catalysts are a prerequisite for mechanistic studies and further improvements to the catalytic performance. The Rietveld/maximum entropy method is applied to synchrotron powder X-ray diffraction data on fully dehydrated CHA-type zeolites with and without loading of catalytically active Cu2+ for the selective catalytic reduction of NOx with NH3 . The method identifies the known Cu2+ sites in the six-membered ring and a not previously observed site in the eight-membered ring. The sum of the refined Cu occupancies for these two sites matches the chemical analysis and thus all the Cu is accounted for. It is furthermore shown that approximately 80% of the Cu2+ is located in the new 8-ring site for an industrially relevant CHA zeolite with Si/Al = 15.5 and Cu/Al = 0.45. Density functional theory calculations are used to corroborate the positions and identity of the two Cu sites, leading to the most complete structural description of dehydrated silicoaluminate CHA loaded with catalytically active Cu2+ cations.