Abstract
Tuning the electronic structure of metal–organic frameworks is the key to extending their functionality to the photocatalytic conversion of absorbed gases. Herein we discuss how the band edge positions in zeolitic imidazolate frameworks (ZIFs) can be tuned by mixing different imidazole‐based linkers within the same structure. We present the band alignment for a number of known and hypothetical Zn‐based ZIFs with respect to the vacuum level. Structures with a single type of linker exhibit relatively wide band gaps; however, by mixing linkers of a low‐lying conduction edge with linkers of a high‐lying valence edge, we can predict materials with ideal band positions for visible‐light water splitting and CO2 reduction photocatalysis. By introducing copper in the tetrahedral position of the mixed‐linker ZIFs, it would be possible to increase both photo‐absorption and the electron–hole recombination times.
Highlights
The attractive pore structure of metal–organic frameworks (MOFs) has led to their huge success in gas adsorption and separation applications.[1]
Some success has been achieved on MOF-based photocatalysis in the last few years, typically involving MOFs with metal nanoparticles or complexes incorporated inside their pores, or introduced via postsynthetic ligand modification.[3]
Gascon et al reported the use of the IRMOF family of MOFs, with band gaps tuned via linker functionalization, in photocatalytic propylene epoxidation,[4] while Gomes-Silva et al have shown the potential of UiO-66 and related MOFs for photocatalytic hydrogen generation.[5]
Summary
(2016) Modelling a linker mixand-match approach for controlling the optical excitation gaps and band alignment of zeolitic imidazolate frameworks. It is advisable to refer to the publisher’s version if you intend to cite from the work. All outputs in CentAUR are protected by Intellectual Property Rights law, including copyright law. Copyright and IPR is retained by the creators or other copyright holders. Terms and conditions for use of this material are defined in the End User Agreement
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