▎ 摘　　要

Graphene oxide (GO) is highly attractive for catalysis because of its large specific surface area and rich chemical structures. However, it has generally been used as a catalyst carrier. Here, we designed a three-dimensional monolith of neat GO aerogel as a fixed bed carbocatalyst used in the reaction of S -> O acetyl migration for the synthesis of thiol compounds, showing the merits of ultrafast catalytic speed (5-8 h), high selectivity (100%), high yields (near 100%), easy isolation of products, and long -life recyclability (>18 times). Particularly, we achieved for the first time thiol compounds containing functional groups of halogen and hydroxyl, which cannot be synthesized using other currently reported catalysts Control experiments demonstrated that the efficient catalysis mechanism is mainly attributed to the protonic functional groups, ultralarge size, and unpaired electrons of GO, as well as the "cage effect" at nanoscale confined spaces of aerogel cells