Hybrid Halide Perovskite Materials for Photocatalytic Carbon-Carbon Bond Formation

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Natural photosynthesis in plants stores the energy of sunlight in new carbon-carbon bonds formed from carbon dioxide. One of the grand challenges of the 21st century is to figure out how to accomplish similar chemical reactions with man-made materials known as photocatalysts. Efficient photocatalysts use low cost and abundant molecules like carbon dioxide and methane for the light-driven production of valuable organic chemicals. Scientists have been trying to develop photocatalysts using metals such as iridium or ruthenium. However, these and many of the other materials currently under examination perform poorly as photocatalysts, are expensive, are not abundant on Earth, and/or are difficult to recycle. Dr. Yong Yan of the New Jersey Institute of Technology is developing easy-to-process photocatalysts from the lead halide perovskites that are composed entirely of low cost and abundant elements. This project focuses on demonstrating that small particles of perovskite photocatalysts can help to efficiently form new carbon-carbon bonds. Professor Yan engages in outreach to students from economically disadvantaged areas, to under-represented minorities, and women. High school student interns synthesize some of the perovskite nanoparticles used for this project.With funding support from the Chemical Catalysis Program of the Chemistry Division, Dr. Yong Yan of the New Jersey Institute of Technology is developing a novel photocatalytic approach for carbon-carbon bond formation reactions using inexpensive lead halide perovskite nanoparticles. APbX3 perovskite, where A is either methylammonium or cesium and X is a halide, has displayed the potential to be an efficient and cost-effective photovoltaic material. These perovskites also show promise for photocatalytic organic synthesis due to their simple synthesis, post-reaction processability, composition from earth-abundant elements, exceptional photophysical properties, readily tunable conduction and valence bands, and high catalytic turnover numbers. Although the instability of these perovskites towards moisture hinders their application as photovoltaics, moisture sensitivity is less of a hindrance for chemical catalysis with suitable organic solvents. This project examines the stability of perovskite nanoparticles in various organic solvents and their suitability for several carbon-carbon bond formation reactions. Band edge-tuning of perovskites is used to adjust their excited-state redox potential to optimize photocatalytic organic synthesis. High school student interns synthesize some of the perovskite nanoparticles used for this project.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.