Issue 38, 2024

Exclusive catalytic hydrogenation of nitrobenzene toward p-aminophenol over atomically precise Au36(SR)24 clusters

Abstract

Despite the advances in devising green methodologies for selective hydrogenation of nitrobenzene toward p-aminophenol, it is still difficult to realize p-aminophenol as the exclusive product in heterogeneous metal catalysis, as the excessive hydrogenation of nitrobenzene usually results in the aniline byproduct. Herein we report that a metal cluster containing 36 gold atoms capped by 24 thiolate ligands provides a unique pathway for nitrobenzene hydrogenation to achieve a p-aminophenol selectivity of ∼100%. The gold cluster can efficiently suppress the over-hydrogenation of amino groups via hydroxyl rearrangement with the aid of water and sequentially the proton transfer promoted by acid toward p-aminophenol. More notably, remarkable catalytic performances can be extended to clusters with similar structures such as Au28(SR)20 and Au44(SR)28, where only an atomic layer change of 2.1 Å thickness in the Au36(SR)24 cluster can tailor the proton affinity for the amino group of the key intermediate phenylhydroxylamine, thereby altering the activity while the p-aminophenol selectivity remained.

Graphical abstract: Exclusive catalytic hydrogenation of nitrobenzene toward p-aminophenol over atomically precise Au36(SR)24 clusters

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Article information

Article type
Edge Article
Submitted
27 Jul 2024
Accepted
30 Aug 2024
First published
10 Sep 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 15617-15624

Exclusive catalytic hydrogenation of nitrobenzene toward p-aminophenol over atomically precise Au36(SR)24 clusters

J. Lu, K. Tang, G. Qi, C. Juan, J. Xu, Z. Cai, D. Li, X. Cai, X. Liu, M. Chen, W. Ding and Y. Zhu, Chem. Sci., 2024, 15, 15617 DOI: 10.1039/D4SC05018E

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