Physics

Electron

Organic chemistry

Covalent bond

Palladium

Atom (system on chip)

Crystallography

Vacancy defect

Density functional theory

Catalysis

Valence (chemistry)

Electronegativity

Computational chemistry

Embedded system

Inorganic chemistry

Chemistry

Materials science

Phenylacetylene

Valence electron

Computer science

Quantum mechanics

Advanced Materials

Single‐atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero‐valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi‐hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent‐like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero‐valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero‐valent SACs on BP for organic transformations.

Zero‐Valent Palladium Single‐Atoms Catalysts Confined in Black Phosphorus for Efficient Semi‐Hydrogenation