Synthesis of Layered Lead-Free Perovskite Nanocrystals with Precise Size and Shape Control and Their Photocatalytic Activity

Haoxin Mai; Xuying Li; Junlin Lu; Xiaoming Wen; Tu C Le; Salvy P Russo; Dehong Chen; Rachel A Caruso

doi:10.1021/jacs.3c04890

Synthesis of Layered Lead-Free Perovskite Nanocrystals with Precise Size and Shape Control and Their Photocatalytic Activity

J Am Chem Soc. 2023 Aug 9;145(31):17337-17350. doi: 10.1021/jacs.3c04890. Epub 2023 Jul 31.

Authors

Haoxin Mai¹, Xuying Li¹, Junlin Lu², Xiaoming Wen^{1

2}, Tu C Le³, Salvy P Russo⁴, Dehong Chen¹, Rachel A Caruso¹

Affiliations

¹ Applied Chemistry and Environmental Science, School of Science, STEM College, RMIT University, Melbourne, Victoria 3001, Australia.
² School of Science, Computing and Engineering Technologies, Swinburne University of Technology, Hawthorn, Victoria 3122, Australia.
³ School of Engineering, STEM College, RMIT University, Melbourne, Victoria 3001, Australia.
⁴ ARC Centre of Excellence in Exciton Science, School of Science, RMIT University, Melbourne, Victoria 3000, Australia.

PMID: 37523781
DOI: 10.1021/jacs.3c04890

Abstract

Halide perovskites have attracted enormous attention due to their potential applications in optoelectronics and photocatalysis. However, concerns over their instability, toxicity, and unsatisfactory efficiency have necessitated the development of lead-free all-inorganic halide perovskites. A major challenge in designing efficient halide perovskites for practical applications is the lack of effective methods for producing nanocrystals with precise size and shape control. In this work, a layered perovskite, Cs₄ZnSb₂Cl₁₂ (CZS), is found from calculations to exhibit size- and facet-dependent optoelectronic properties in the nanoscale, and thus, a colloidal method is used to synthesize the CZS nanoparticles with size-tunable morphologies: zero- (nanodots), one- (nanowires and nanorods), two- (nanoplates), and three-dimensional (nanopolyhedra). The growth kinetics of the CZS nanostructures, along with the effects of surface ligands, reaction temperature, and time were investigated. The optoelectronic properties of the nanocrystals varied with size due to quantum confinement effects and with shape due to anisotropy within the crystals and the exposure of specific facets. These properties could be modulated to enhance the visible-light photocatalytic performance for toluene oxidation. In particular, the 9.7 nm CZS nanoplates displayed a toluene to benzaldehyde conversion rate of 1893 μmol g^-1 h^-1 (95% selectivity), 500 times higher than the bulk synthesized CZS, and comparable with the reported photocatalysts. This study demonstrates the integration of theoretical calculations and synthesis, revealing an approach to the design and fabrication of novel, high-performance colloidal perovskite nanocrystals for optoelectronic and photocatalytic applications.