Construction of continuous flow catalytic reactor-HPLC system with ultrahigh catalytic activity using 2D nanoflower MOF-derived Cu2O/Cu/PDA/CF catalyst

Abstract

Currently, metal-organic frameworks (MOFs) derived materials have been widely concerned for the reduction of 4-nitrophenol (4-NP). However, complex recovery of powder catalysts and low utilization ratio of active sites make their application challenging. Herein, a novel Cu2O/Cu/PDA/CF catalyst has been developed for the rapid reduction of 4-NP to 4-aminophenol (4-AP). The catalyst was constructed by compositing a two-dimensional nanoflower MOF-derived nanoporous Cu2O/Cu network on a polydopamine (PDA)-modified porous copper foam by a mild and controllable in-situ reduction synthesis. Notably, an enhanced catalytic performance of Cu2O/Cu/PDA/CF was obtained for 4-NP reduction with a rate constant (k) of 0.8001 min−1, outperforming Cu/PDA/CF-X (X = 400, 500 and 600 ℃ pyrolysis temperature) catalysts (2.3–6.4 folds), and even many reported catalysts (2.3–46.5 folds). The ultrafast degradation of 4-NP was completed in 70 s. Moreover, an ingenious online continuous flow catalytic reactor (CFCR)-high performance liquid chromatography (HPLC) system was constructed for automatic and real-time monitoring of the reduction reaction. System stability experiments over 300 min revealed a surprisingly high reaction k value of 76.68 min−1 at low NaBH4 usage, significant increasing by 2–3 orders of magnitude compared with Cu2O/Cu/PDA/CF batch catalysis, due to the high aspect ratio of 2D nanoflower MOF and convection-accelerated mass transfer. This work offers new insights for the rational design of catalytic reactor and its potential application in wastewater treatment.