Highly efficient catalytic transfer hydrogenation for the conversion of nitrobenzene to aniline over PdO/TiO2: The key role of in situ switching from PdO to Pd

The reduction of nitrobenzene to aniline is very important for both pollution control and chemical synthesis. Nevertheless, difficulties still remain in developing a catalytic system having high efficiency and selectivity for the production of aniline. Herein, it was found that PdO nanoparticles highly dispersed on TiO2 support (PdO/TiO2) functioned as a highly efficient catalyst for the reduction of nitrobenzene in the presence of NaBH4. Under favorable conditions, 95% of the added nitrobenzene (1 mmol/L) was reduced within 1 min with an ultra-low apparent activation energy of 10.8 kJ/mol by using 0.5%PdO/TiO2 as catalysts and 2 mmol/L of NaBH4 as reductants, and the selectivity to aniline even reached up to 98%. The active hydrogen species were perceived as dominant species during the hydrogenation of nitrobenzene by the results of isotope labeling experiments and ESR spectroscopic. A mechanism was proposed as follows: PdO activates the nitro groups and leads to in-situ generation of Pd, and the generated Pd acts as the reduction sites to produce active hydrogen species. In this catalytic system, nitrobenzene prefers to be adsorbed on the PdO nanoparticles of the PdO/TiO2 composite. Subsequently, the addition of NaBH4 results in-situ generation of a Pd/PdO/TiO2 composite from the PdO/TiO2 composite, and the Pd nanoclusters would activate NaBH4 to generate active hydrogen species to attack the adsorbed nitro groups. This work will open up a new approach for the catalytic transfer hydrogenation of nitrobenzene to aniline in green chemistry.