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Issue 2, 2015
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Transition metal inclusion in RhoZMOF materials

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Abstract

Porous RhoZMOF is a negatively charged zeolite-like MOF material susceptible to post-synthesis modification by an ion-exchange process replacing as-synthesized organic cations with transition metals. This material exhibiting open transition metal sites is a very attractive candidate for industrial applications related to clean energy technologies, like electrochemistry and gas storage. In the present work, partial or total Co2+, Ni2+ and Cu2+ inclusions have been successfully carried out in the RhoZMOF structure by ion-exchange treatment. Particularly, complete exchange of HDMA+ with Co2+ could be reached at room temperature after 12 h of contact time. For Cu2+ exchange, a rapid transformation of the RhoZMOF structure into a new Cu-rich, crystalline and practically non-porous phase was observed at room temperature; its appearance can be avoided and the desired structure can be preserved when ion-exchange treatment is carried out at −20 °C for 6 h, reaching a partial ion-exchange degree of 30%. Moreover, for Ni2+ ion-exchange treatment at 25 and 0 °C, a covering of an amorphous Ni-rich organometallic phase over the crystals was detected by SEM analysis; its appearance can be prevented by reducing the amount of HDMA+ in the media by developing the ion-exchange process in two steps: exchanging HDMA+ with Na+ and Na+ with Ni2+. The results provide a post-synthesis modification route for obtaining porous MOF materials containing open transition metal sites accessible for redox catalysis and selective gas adsorption.

Graphical abstract: Transition metal inclusion in RhoZMOF materials

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Publication details

The article was received on 07 Jul 2014, accepted on 22 Sep 2014 and first published on 22 Sep 2014


Article type: Paper
DOI: 10.1039/C4CE01401D
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Citation: CrystEngComm, 2015,17, 338-343

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    Transition metal inclusion in RhoZMOF materials

    G. Calleja, C. Martos, G. Orcajo, J. A. Botas and J. A. Villajos, CrystEngComm, 2015, 17, 338
    DOI: 10.1039/C4CE01401D

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