10.1021/acs.jpcc.5b12079.s001

Electronic Structure of Zn<sup>+</sup>‑Modified Zeolite: A Density Functional Theory Study of Ferrierite

Abstract

Density functional theory (DFT) calculations were used to study the monovalent Zn<sup>+</sup> cation exchanged in an extra-framework position of zeolite ferrierite. A single Zn<sup>+</sup> was found to be paramagnetic. Two Zn<sup>+</sup> cations combined to form a subnano-sized dimeric species [Zn–Zn]<sup>2+</sup> which fits into the eight- or ten-membered rings (8MR or 10MR, respectively) of ferrierite. Within the [Zn–Zn]<sup>2+</sup> pair, two cations were bound via a covalent s–s bond. Upon the pair forming, a huge stabilization was observed, linked with a decrease in potential energy by 235–296 kJ/mol, depending on the location of Zn<sup>+</sup> in the framework. The [Zn–Zn]<sup>2+</sup> species is an electron paramagnetic resonance (EPR) silent insulator with a band gap of 4.82 eV. Because 8MR and 10MR are present in a majority of zeolite structures, we predict that the Zn-modified electron-rich materials can be fabricated from almost any stable aluminum-rich zeolite. Because of the strong tendency for the conversion of Zn<sup>+</sup> to Zn<sup>2+</sup>, the Zn<sup>+</sup>-modified zeolites are strong solid Lewis bases with promising catalytic properties

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oai:figshare.com:article/3116650Last time updated on 2/12/2018

This paper was published in FigShare.

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