Engineering Lewis Acidity in Zeolite Catalysts by Electrochemical Release of Heteroatoms during Synthesis

Chem Mater. 2023 Jun 1;35(13):5049-5058. doi: 10.1021/acs.chemmater.3c00552. eCollection 2023 Jul 11.

Abstract

The creation of heteroatom nodes in zeolite frameworks is a challenging but rewarding pathway to superior materials for numerous catalytic applications. Here, we present a novel method for precise control over heteroatom incorporation by in situ anodic release of a desired metal during hydrothermal zeolite synthesis. The generic character of the technique and the applicability of the new synthesis reactor are shown across 3 zeolite structures crystallized and 4 electrode metals in two pH zones and by offering access to a new mixed-metal zeolite. The timed and voltage-controlled metal release offers a minimized interference between the metal precursor state and critical events in the zeolite's crystallization. A mechanistic study for Sn-MFI revealed the key importance of controlled release: while keeping its concentration lower than in batch, a lot more Sn can be incorporated into the framework. The method grants access to 10× increased framework Lewis acid site densities (vs batch controls) for the most relevant stannosilicates. As a proof, the electro-made materials demonstrate higher productivity than their classic counterparts in lactate catalysis. This innovative approach effectively expands the synthesis space of zeolites.