title: Modelling a Linker Mix-and-Match Approach for Controlling the Optical Excitation Gaps and Band Alignment of Zeolitic Imidazolate Frameworks.
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 CO2reduction 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.
authors.affiliation: Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK.
authors.forename: Ricardo
authors.identifier: 0000-0001-8845-1719
authors.initials: R
authors.lastname: Grau-Crespo
authors.affiliation: Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK.
authors.forename: Alex
authors.initials: A
authors.lastname: Aziz
authors.affiliation: Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK.
authors.forename: Angus W
authors.initials: AW
authors.lastname: Collins
authors.affiliation: School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS, UK.
authors.forename: Rachel
authors.initials: R
authors.lastname: Crespo-Otero
authors.affiliation: Department of Applied Physics I, Escuela Técnica Superior de Ingeniería Informática, Ave. Reina Mercedes, Universidad de Sevilla, 41012, Sevilla, Spain.
authors.forename: Norge C
authors.initials: NC
authors.lastname: Hernández
authors.affiliation: Department of Inorganic Chemistry, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain.
authors.forename: L Marleny
authors.initials: LM
authors.lastname: Rodriguez-Albelo
authors.affiliation: Department of Physical, Chemical and Natural Systems, Univ. Pablo de Olavide, Ctra. de Utrera km. 1, 41013, Seville, Spain.
authors.forename: A Rabdel
authors.initials: AR
authors.lastname: Ruiz-Salvador
authors.affiliation: Department of Physical, Chemical and Natural Systems, Univ. Pablo de Olavide, Ctra. de Utrera km. 1, 41013, Seville, Spain.
authors.forename: Sofia
authors.initials: S
authors.lastname: Calero
authors.affiliation: Department of Physical, Chemical and Natural Systems, Univ. Pablo de Olavide, Ctra. de Utrera km. 1, 41013, Seville, Spain.
authors.forename: Said
authors.initials: S
authors.lastname: Hamad
keywords: band gaps; computational chemistry; metal-organic frameworks; photocatalysis; zeolitic imidazolate frameworks