# Black Phosphorus/Palladium Nanohybrid: Unraveling the Nature of P-Pd Interaction and Application in Selective Hydrogenation

## TL;DR

This study develops a novel black phosphorus/palladium nanohybrid catalyst with unique Pd-P covalent bonds, demonstrating enhanced stability and superior selectivity in hydrogenation reactions of chloronitroarenes.

## Contribution

It uncovers the covalent Pd-P interaction in bP-supported Pd nanoparticles and demonstrates improved catalytic performance and stability in hydrogenation.

## Key findings

- Discovery of covalent Pd-P bonds with 2.26 Å distance.
- bP acts as a polydentate ligand, stabilizing Pd nanoparticles.
- Enhanced chemoselectivity in hydrogenation of chloronitroarenes.

## Abstract

The burgeoning interest in 2D black phosphorus (bP) contributes to expand its applications in countless fields. In the present study, 2D bP is used as a support for homogeneously dispersed palladium nanoparticles directly grown on it by a wet chemical process. EELS-STEM analysis evidences a strong interaction between palladium and P atoms of bP nanosheets. A quantitative evaluation of this interaction comes from XAS measurements that find out a very short Pd-P distance of 2.26 {\AA} proving for the first time the existence of an unprecedented Pd-P coordination bond of covalent nature. Additionally, the average Pd-P coordination number of about 1.7 reveals that bP acts as a polydentate phosphine ligand towards the surface Pd atoms of the nanoparticles, thus preventing their agglomeration and inferring structural stability. These unique properties result in a superior performance in the catalytic hydrogenation of chloronitroarenes to chloroaniline, where a higher chemoselectivity in comparison to other heterogeneous catalyst based on palladium has been observed.

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Source: https://tomesphere.com/paper/1903.02363