Increasing Al-Pair Abundance in SSZ-13 Zeolite via Zeolite Synthesis in the Presence of Alkaline Earth Metal Hydroxide Produces Hydro-Thermally Stable Cobalt and Pd-SSZ-13 Materials for Pollutant Abatement Applications

We show that replacing alkaline (NaOH) for alkaline-earth metal (Sr(OH)2 as an example) in the synthesis of SSZ-13 zeolite with Si/Al~10 produces SSZ-13 zeolite material with novel, advantageous properties. Its NH4-form ion-exchanges higher amount of Co(II) ions than the conventional one: this is the consequence of increased number of Al pairs in the structure induced by the +2 charge of Sr(II) cations in the synthesis gel that force two charge-compensating AlO4- motives to be closer together. We characterize the +2 state of Co(II) ions in these materials with infra-red spectroscopy and XANES measurements. They can be used for NOx pollutant adsorption from ambient air: the ones derived from SSZ-13 with higher Al pair content contain more cobalt(II) and thus, perform better as ambient-air NOx adsorbers before reaching full saturation capacity. Notably, Co(II)/SSZ-13 material with increased number of Al pairs is significantly more hydrothermally stable than its NaOH-derived analogue. Loading 1.7 wt% Pd into Co-SSZ-13 synthesized in the presence of Sr(II) produces a passive NOx adsorber (PNA) material that can be used for NOx adsorption from simulated diesel engine exhaust. The critical issue for these applications is hydrothermal stability of Pd-zeolites. Pd/SSZ-13 synthesized in NaOH media loses most of its PNA capacity after ~800 ⁰C hydrothermal aging in the flow of air and steam (10 hours in 10% H2O/air flow). The 1.7 wt% Pd/Co/SSZ-13 material with Si/Al ~10 does not lose its PNA capacity after extremely harsh aging at 850 and 900 ⁰C (10 hours in 10% H2O/Air flow) and loses only ~55% capacity after hydrothermal aging at 930 ⁰C. It shows considerably enhanced stability compared with previous record for Pd/FER, Pd/SSZ-39 and Pd/BEA materials that could survive hydrothermal aging no higher than 820 ⁰C. We herein reveal a new, simple, and scalable strategy for making remarkably (hydro)thermally stable metal-zeolite materials/catalysts with a number of useful applications.