| Abstract: | Platinum nanoparticles encapsulated into zeolite Y (Pt@Y catalyst) exhibit excellent catalytic selectivity in the hydrogenation of substituted nitroarenes to form the corresponding aromatic amines, even after complete conversion. With the hydrogenation of p‐chloronitrobenzene as a model, the role of zeolite encapsulation toward perfect selectivity can be attributed to constraint of the substrate adsorbed on the platinum surface in an end‐on conformation. This conformation results in the activation of only one adsorbed group, with little influence on the other one in the molecule. Owing to a much lower apparent activation energy of Pt@Y for the hydrogenation of a separately adsorbed nitro group than that of the adsorbed chloro group, the Pt@Y catalyst can prevent hydrodechlorination of p‐chloronitrobenzene under mild conditions. Moreover, such a conformation results in a reduced adsorption energy of target p‐chloroaniline on the platinum surface; thus suppressing the reactivity of hydrodechlorination of p‐chloroaniline to circumvent further C−Cl bond breakage. |
