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Metal-Free Chemoselective Reduction of Nitroarenes Catalyzed by Covalent Triazine Frameworks: The Role of Embedded Heteroatoms.

Chemoselective reduction of nitroarenes to arylamines is a core technology for the synthesis of numerous chemicals. The technology, however, relies on applying precious noble metal catalysts. We present our findings on the development of robust nanoporous covalent triazine frameworks (CTFs) as metal-free catalysts for the green chemoselective reduction of nitroarenes. The turnover frequency is found to be 43.03 h-1, exceeding activities of the heteroatom-doped carbon nanomaterials by a factor of 30. The X-ray photoelectron spectroscopy and control experiments provide further insights into the nature of active species for prompt catalysis. This report confirms the importance of quaternary 'N' and 'F' atom functionalities to create active hydrogen species via charge delocalization as a critical step in improving the catalytic activity.