In Situ Implantation of Bi 2 S 3 Nanorods into Porous Quasi-Bi-MOF Architectures: Enabling Synergistic Dissociation of Borohydride for an Efficient and Fast Catalytic Reduction of 4-Nitrophenol.

Catalytic hydrogenation reduction based on sodium borohydride (NaBH 4 ) has gained attention as an appealing "one-stone-two-birds" approach for the simultaneous elimination of nitroaromatic pollutants and the production of high-value aminoaromatics under mild conditions. However, the slow kinetics of NaBH 4 dissociation on the surface of catalysts restrict the catalytic hydrogenation reduction efficiency. Herein, we report an intelligent localized sulfidation strategy for an in situ implantation of Bi 2 S 3 nanorods within quasi-Bi-MOF architectures (Bi 2 S 3 @quasi-Bi-MOF) by fine-tuning the pyrolysis temperature. In this novel Bi 2 S 3 @quasi-Bi-MOF, the porous quasi-Bi-MOF enables efficient adsorption of BH 4 - and 4-nitrophenol (4-NP), while Bi 2 S 3 facilitates the BH 4 - dissociation to form H ads * species adsorbed on the catalyst surface. Benefiting from the synergistic structure, Bi 2 S 3 @quasi-Bi-MOF exhibits excellent performance for the catalytic reduction of 4-NP, delivering a high turnover frequency (TOF) of 1.67 × 10 -4 mmol mg -1 min -1 and an extremely high normalized rate constant ( k nor ) of 435298 s -1 g -1 . The kinetic analysis and electrochemical tests indicate that this catalytic hydrogenation reduction follows the Langmuir-Hinshelwood mechanism. This study enriches the synthetic strategy of MOF-based derivatives and offers a new catalytic platform for hydrogenation reduction reactions.