Synergistic effect of metal-organic framework-derived boron and nitrogen heteroatom-doped three-dimensional porous carbons for precious-metal-free catalytic reduction of nitroarenes

We report a scalable and controllable synthesis of metal-organic framework (MOF)-derived three-dimensional boron and nitrogen heteroatom-doped porous carbons (3D-BNPCs) and their synergistic effect for metal-free catalytic 4-nitrophenol (4-NP) reduction. The substitution of boron atoms into zeolitic imidazole framework-8 (ZIF-8)-derived nitrogen-doped porous carbon (B-NPC-1200) significantly improves the electrical conductivity and the catalytic 4-NP reduction. We propose the heteroatom-doping of boron, nitrogen and oxygen in the 3D- B-N PC catalysts creates synergistic effect on 4-NP reduction by creating more catalytically active sites. High-Resolution X-ray Photoelectron Spectroscopy (HR-XPS) and Density Functional Theory (DFT) calculations were carried out to confirm and investigate the role of active sites on adsorption of 4-NP molecules in B-NPC-1200. We find that the strongly active sites can only be created based on the synergistic effect between nitrogen, boron and oxygen atoms, and the increased density of the active sites are responsible for the lowering of the apparent activation energy in B-NPC-1200 structure. As synthesized B-NPC-1200 exhibits superior catalytic activities for 4-NP reduction with a low apparent activation energy of 27.0 kJ/mol and a high reaction rate constant of 2.3*10(boolean AND-3) (s(-1)). The catalyst can run five times without decreasing significant catalytic activity. The reduction reactions of various nitroarene compounds have been further tested using the B-N PC-1200 material as the precious-metal-free catalyst.