Establishment of Integrated Analysis Method for Probing and Reconstructing Hydrogenation Mechanism of a Model Reaction

The hydrogenation of 4-nitrophenol (4-NP) has attracted much attention, since it is typically used as a model reaction for evaluating newly developed catalysts, but its mechanism is still debated. Herein, Co(OH)2-modified CuO catalyst (Co(OH)2/CuO) was used for the reduction of 4-NP to 4-aminophenol (4-AP) in an aqueous sodium borohydride (NaBH4) solution. The reaction mechanism was investigated by UV-Vis spectroscopy (UV-Vis), high-performance liquid chromatography (HPLC), HPLC-Q-orbitrap high-resolution mass spectrometry (LC-MS/MS), and1HNMR spectroscopy (1HNMR) as an integrated technology at different concentrations of NaBH4. Samples were taken at specified time intervals and monitored using UV-Vis, HPLC, LC-MS/MS, and1HNMR. With the help of comprehensive analysis, eight intermediates, including azo and azoxy compounds, were effectively captured, and the variation tendency of each intermediate was determined, revealing that the hydrogenation of 4-NP proceeds via a coexistence of the direct and condensation routes. The integrated analysis methods were powerful technical supports for the study of the catalysis mechanism.Keywords:4-nitrophenol hydrogenation;intermediates;mechanism;Co(OH)2/CuO bimetallic nanocatalyst;integrated analysis method