Selective hydrogenation of substituted nitroaromatic compounds is an extremely important and challenging reaction. Supported metal catalysts attract much attention in this reaction because the properties of metal nanoparticles (NPs) can be modified by the nature of the support. Herein, the support morphology on the catalytic performance of selective hydrogenation of 3‐nitrostyrene to 3‐vinylaniline was investigated. Pt NPs supported on octadecahedral α‐Fe2O3 supports with a truncated hexagonal bipyramid shape (Pt/α‐Fe2O3‐O) and rod‐shaped α‐Fe2O3 supports (Pt/α‐Fe2O3‐R) were prepared by glycol reduction method. Detailed characterizations reveal that the electronic structure and dispersion of Pt NPs can be modified by the supports. The Pt/α‐Fe2O3‐O catalyst exhibited superior catalytic performance for hydrogenation of 3‐nitrostyrene because of its low coordinated Pt sites and the small Pt NPs size, which is benefit from the high‐index exposed surfaces of truncated hexagonal bipyramid‐shaped α‐Fe2O3 support. The structural evolution during the catalytic reaction was investigated in detail by identical location transmission electron microscopy (IL‐TEM) method, which found that the high cycling activity of Pt/α‐Fe2O3‐O catalyst during the cycle experiment results from the stability of Pt NPs.
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