Work

In-situ and operando FT-IR investigation of Pd speciation in Pd/SSZ-13: The pivotal role of CO and NO adsorption with and without H₂O

Year: 2025

Type: article

Abstract: In-situ and operando FT-IR spectroscopy was employed to give fundamental insights on CO and NO adsorption and effects on Pd/SSZ-13 investigated for potential passive NO x adsorber applications. Emphasis is placed on understanding the effects of key exhaust components, particularly H 2 O and O 2 , under conditions relevant to low-temperature NO x emission control. In-situ CO adsorption experiments at room temperature revealed the coexistence of Pd species with varying local environments and oxidation states. Notably, nearly all Pd²⁺ ions are reduced to Pd⁺/Pd⁰ through the combined action of CO and adsorbed water. Operando studies at 50 °C confirmed that Pd²⁺ reduction occurs even in the presence of trace amounts of water, while oxygen has minimal influence on Pd speciation in terms of oxidation state or coordination geometry. In-situ NO adsorption at room temperature further demonstrated that the nitrosyl bands near 1860 and 1810 cm⁻¹, well documented in literature, are both constituted by contributions from both Pd²⁺ and Pd⁺ species. Additionally, NO and water together significantly promote Pd²⁺ reduction, as evidenced by post-NO CO adsorption at room temperature with the formation of mixed Pd n ⁺(CO)(NO) complexes, mainly related to Pd + . Under operando conditions performed at 120 and 150 °C, hydrated Pd⁺(NO)(H₂O) x species form readily, but full Pd²⁺ reduction is unlikely due to potential re-oxidation by oxygen. Importantly, Pd⁺(CO)(NO) species is not significantly formed under realistic PNA conditions (80–150 °C, presence of H 2 O and O 2 ). These findings offer critical new insights into Pd redox behavior and speciation in Pd/SSZ-13, with emphasis on IR band assignments. • CO and NO adsorption on anhydrous and hydrated Pd/SSZ-13 passive NO x adsorber. • Combined in situ and operando FT-IR measurements outline evolution of Pd speciation. • Detailed IR band assignments to carbonyl and nitrosyl species of Pd 2+ and Pd + . • Both CO and NO reduce Pd 2+ into Pd + only in the presence of water. • Formation of mixed palladium carbonyl-nitrosyl complexes mainly related to Pd + sites.

Source: Applied Catalysis A General

DOI: 10.1016/j.apcata.2025.120592

Authors: Sara Morandi, Lidia Castoldi, Roberto Matarrese

Institutions: National Interuniversity Consortium of Materials Science and Technology, University of Turin, Politecnico di Milano

Language: English

Topic: Catalytic Processes in Materials Science

Subfield: Materials Chemistry

Field: Materials Science

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $3,760

Funders: European Commission, Ministero dell’Istruzione, dell’Università e della Ricerca, Ministero dell'Università e della Ricerca