Integrated Experimental and Theoretical Approach for Efficient Design and Synthesis of Gold-Based Double Halide Perovskites

Applied cutting-edge electronic structure and phonon simulations provide a reliable knowledge about the stability of perovskite structures and their electronic properties, which are crucial for design of effective nanomaterials. Gold is one of the exceptional elements, which can exist both as a monovalent and a trivalent ion in the B site of a double perovskite such as A2BIBIIIX6. However, until now, electronic properties of Cs2AuIAuIIIX6 have not been sufficiently explored and this material was never synthesized using Au1+ and Au3+ precursors in the preparation route. Here, computational simulations combined with an experimental study provide new insight into the properties and synthesis route of Cs2AuIAuIIIX6 (X = Cl, Br, and I) perovskites. First-principles calculations reveal that tetragonal Cs2AuIAuIIIX6 (X = I, Br, Cl) molecules present a band gap of 1.10, 1.15, and 1.40 eV, respectively. Application of novel approaches in the simulations of the VB-XPS for Cs2AuIAuIIICl6 allows replication of the observed spectrum and provides strong evidence of the reliability of the obtained results for the other perovskites Cs2AuIAuIIIX6, X = Br, I. Following theoretical findings, a one-step preparation route of the Cs2AuIAuIIICl6 is developed using a combination of monovalent and trivalent gold precursors at a relatively low temperature. It should be emphasized that this is the first synthesis of this material at low temperatures, allowing for obtaining highly crystalline Cs2Au2Cl6 particles with controlled morphology and without gold impurities. The band gap of synthesized Cs2AuIAuIIICl6 is extended into the NIR spectral range, where most other double perovskites are limited to higher energies, limiting their usage in single junction solar cells or in photocatalysis. The as-synthesized Cs2AuIAuIIICl6 exhibits high efficiency in a photocatalytic toluene degradation reaction under visible light irradiation. The developed approach provides information necessary for structure manipulation at the early stage of its synthesis and offers a new and useful guidance for design of novel improved lead-free inorganic halide perovskite with interesting optical and photocatalytic properties.