Colloidal Synthesis of Palladium Nanocluster-Decorated Cs3Sb2Cl9 Perovskite Heterostructural Nanorods for Enhanced CO2 Photoreduction

Abstract

Developing efficient and sustainable photocatalysts for CO2 reduction remains a significant challenge, particularly with environmentally benign materials. Here, we report the first one-step synthesis of metal–lead-free perovskite heterostructural nanocrystals by decorating Cs3Sb2Cl9 perovskite nanorods with size-controlled Pd nanoclusters via a one-step hot-injection method. The resulting Pd-Cs3Sb2Cl9 heteronanorods (HNRs) exhibit strong interfacial electronic coupling, enhanced charge separation, and excellent colloidal stability. Transient absorption spectroscopy and DFT calculations reveal a built-in electric field that drives directional electron transfer from the perovskite host to the Pd domains. Under UV irradiation, the Pd-Cs3Sb2Cl9 HNRs demonstrate excellent CO2 photoreduction activity with high CH4 selectivity, achieving a record apparent quantum yield (AQY) of 2.62% among halide perovskite nanocrystal-based systems with a large electronic yield of 689.3 ± 12.2 µmol·gcat−1. In situ spectroscopic monitoring and Gibbs free energy analysis further unveil a Pd-facilitated reaction pathway involving stabilization of key intermediates. This work introduces a new class of lead-free perovskite-based heterostructures through a facile one-step synthesis strategy and offers a new design principle for next-generation photocatalysts for solar fuel production.

Xiaohang Jia

Chemistry

Brenda Rubenstein

Krieble Professor of Chemistry, Professor of Physics, and Director of Data Science