Elucidating the Effect of Ion Exchange Protocol on the Copper Exchange Efficacy, Copper Siting, and SCR Activity in Cu-SSZ-13.

The front cover artwork is provided by Professor Jean-Sabin McEwen at Washington State University. The image shows how ion exchanges prepared with different copper precursors influence how the copper ultimately sites relative to the zeolite framework, which ultimately impacts its catalytic reactivity for the selective catalytic reduction (SCR) of NOx in Cu-SSZ-13. Read the full text of the Research Article at 10.1002/cphc.202300271.

Elucidating the Effect of Ion Exchange Protocol on the Copper Exchange Efficacy, Copper Siting, and SCR activity in Cu-SSZ-13.

The influence of the copper ion exchange protocol on SCR activity of SSZ-13 is quantified. Using the same parent SSZ-13 zeolite, four exchange protocols are used to assess how exchange protocol impacts metal uptake and SCR activity. Large differences in the SCR activity, nearly 30 percentage points at 160 °C at constant copper content, are observed for different exchange protocols implying that different exchange protocols lead to different copper species. Hydrogen temperature programmed reduction on selected samples and infrared spectroscopy of CO binding corroborates this conclusion as the reactivity at 160 °C correlates with the intensity of the IR band at 2162 cm-1 . DFT-based calculations show that such an IR assignment is consistent with CO adsorbed on a Cu(I) cation within an eight-membered ring. This work shows that SCR activity can be influenced by the ion exchange process even when different protocols lead to the same metal loading. Perhaps most interesting, a protocol used to generate Cu-MOR for methane to methanol studies led to the most active catalyst both on a unit mass or unit mole copper basis. This points to a yet not recognized means to tailor catalyst activity as the open literature is silent on this issue.

Understanding Enantioselective Interactions by Pulling Apart Molecular Rotor Complexes.

Enantioselective interactions underpin many important phenomena from biological mechanisms to chemical catalysis. In this regard, there is great interest in understanding these effects at the molecular level. Surfaces provide a platform for these studies and aid in the long-term goal of designing heterogeneous enantiospecific interfaces. Herein we report a model system consisting of molecular rotors, one intrinsically chiral (propylene oxide) and one that becomes chiral when adsorbed on a surface (propene). Scanning tunneling microscopy (STM) measurements enable the chirality of each individual molecule to be directly visualized, and density functional theory based calculations are performed to rationalize the chiral time-averaged appearance of the molecular rotors. While there are no attractive intermolecular interactions between the molecular species themselves, when mixed together there is a strong preference for the formation of 1:1 heteromolecular pairs. We demonstrate that STM tip-induced molecular manipulations can be used to assemble these complexes, examine the chirality of each species, and thereby interrogate if their interactions are enantioselective. A statistical analysis of this data reveals that intrinsically chiral propylene oxide preferentially binds one of the enantiomers of propene with a 3:2 ratio, thereby demonstrating that the surface chirality of small nonchiral molecules can be directed with a chiral modifier. As such, this investigation sheds light onto previously reported ensemble studies in which chirally seeded layers of molecules that are achiral in the gas phase can lead to an amplification of enantioselective adsorption.