An Ab Initio Study of Clusters as Building Blocks for Crystals: From Prussian Blue Analogs to Hybrid Perovskites

Abstract

Cluster‐based crystals containing the (Nb6Cl12)2+ or (Ta6Cl12)2+ clusters, including the well‐known Nb6Cl14, K4Nb6Cl18, and the Prussian blue analog (Me4N)2 [MnNb6Cl12(CN)6], have been investigated by density functional theory. The electronic structure of the cluster is the same for all compounds, with a semiconducting gap of around 1 eV between occupied and empty states, in the range of interest for solar energy applications. Calculations suggest that these clusters could be used as cations in hybrid organic–inorganic perovskites, as a substitute for toxic Pb2+. Moreover, bandgaps, band alignment, and hydrogen adsorption calculations show that the designed cluster‐based hybrid perovskites have potential as intermediate band materials for photovoltaics, and as photocatalysts for the hydrogen evolution reaction.

A review on functional nanoarchitectonics nanocomposites based on octahedral metal atom clusters (Nb 6 , Mo 6 , Ta 6 , W 6 , Re 6 ): inorganic 0D and 2D powders and films

“…Indeed, band gaps, band alignment, and hydrogen adsorption calculations show that the designed cluster-based hybrid perovskites have potential as intermediate-band materials for photovoltaics, and as photocatalysts for the hydrogen evolution reaction. [268] Another possibility is to use these transition metal atom clusters as precursors for the discovery of new compounds and nanocomposites like nitrides, carbides, borides, sulfides or alloys. [269][270][271][272][273] The field of possibilities is open to everyone and the adventure of the nanocomposites based on metal atom clusters has only just begun.…”