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• Functional boron clusters modified GO to anchor ultrafine and highly dispersed Pd nanoparticles. • Pd/BGO can efficiently catalyze the hydrogenation of nitroaromatics to realize value-added. • Pd/BGO-catalyzed hydrogenation reaction of nitroarenes exhibits ultrafast reaction kinetics. • Pd/BGO exhibits durable stability in catalytic hydrogenation of nitroaromatic hydrocarbons. The reduction of nitroaromatics to aminoaromatics is essential for fine chemical production and effective sewage treatment. However, the activity of an external catalyst is essential for the reaction. In this study, Pd nanocrystals were anchored in situ on two-dimensional graphene oxide (GO), which acted as a catalyst support with high specific surface area. The oxygen-containing groups on the surface of GO bonded to the functionally rich boron clusters through hydrogen bonding interactions. A mildly reducible closed-dodecahydrododecaboric acid anion cluster (closo‑ [B 12 H 12 ]2–) was employed as the target site. The mild reducibility of closo‑ [B 12 H 12 ]2– resulted in a wide dispersion of ultrafine Pd nanocrystals on GO. Under ambient conditions, Pd/BGO rapidly hydrogenated nitroaromatics, such as 4-nitrophenol, to aminoaromatics with approximately 100% efficiency. Moreover, Pd/BGO retained its high catalytic activity for the hydrogenation/reduction of 4-nitrophenol after five catalytic cycles. Therefore, Pd/BGO could be a promising and economically viable candidate for various practical applications. The proposed innovative preparation strategy and highly efficient catalytic activity suggested the effective performance of closo‑ [B 12 H 12 ]2– as nanometal nucleation target sites. In addition to providing an alternate route for preparing supported nanometals, this study presents a stable and efficient catalyst for the hydrogenation of nitroaromatics. [Display omitted] [ABSTRACT FROM AUTHOR]

• Functional boron clusters modified GO to anchor ultrafine and highly dispersed Pd nanoparticles. • Pd/BGO can efficiently catalyze the hydrogenation of nitroaromatics to realize value-added. • Pd/BGO-catalyzed hydrogenation reaction of nitroarenes exhibits ultrafast reaction kinetics. • Pd/BGO exhibits durable stability in catalytic hydrogenation of nitroaromatic hydrocarbons. The reduction of nitroaromatics to aminoaromatics is essential for fine chemical production and effective sewage treatment. However, the activity of an external catalyst is essential for the reaction. In this study, Pd nanocrystals were anchored in situ on two-dimensional graphene oxide (GO), which acted as a catalyst support with high specific surface area. The oxygen-containing groups on the surface of GO bonded to the functionally rich boron clusters through hydrogen bonding interactions. A mildly reducible closed-dodecahydrododecaboric acid anion cluster (closo‑ [B 12 H 12 ]2–) was employed as the target site. The mild reducibility of closo‑ [B 12 H 12 ]2– resulted in a wide dispersion of ultrafine Pd nanocrystals on GO. Under ambient conditions, Pd/BGO rapidly hydrogenated nitroaromatics, such as 4-nitrophenol, to aminoaromatics with approximately 100% efficiency. Moreover, Pd/BGO retained its high catalytic activity for the hydrogenation/reduction of 4-nitrophenol after five catalytic cycles. Therefore, Pd/BGO could be a promising and economically viable candidate for various practical applications. The proposed innovative preparation strategy and highly efficient catalytic activity suggested the effective performance of closo‑ [B 12 H 12 ]2– as nanometal nucleation target sites. In addition to providing an alternate route for preparing supported nanometals, this study presents a stable and efficient catalyst for the hydrogenation of nitroaromatics. [Display omitted] [ABSTRACT FROM AUTHOR]