Regulating the electronic state of MFI zeolite encapsulated Pt nanoparticles to boost the atom efficiency in reductive amination of biomass-derived furfural

Furfural is an abundant biomass-derived building block that can be converted into furan-based N-containing compounds through direct reductive amination by using dihydrogen (H₂). Nonetheless, the synthesis of furan-based tertiary amines is highly limited via this route. Herein, we reported the straightforward synthesis of MFI zeolite encapsulated Pt nanoparticles and finely modulated the surface electronic state by facilely controlling the reduction process. The constructed catalyst Pt@Z5 effectively catalyzed the amination of furfural with diethylamine for the synthesis of N-ethyl-N-(furan-2-ylmethyl)ethanamine, affording the high yield (>95 %), large turnover number (TON) of 2058, turnover frequency (TOF) of 1029 h⁻¹, and stable recyclability. Systematic investigations comprising in-situ Fourier transform infrared spectroscopy (FTIR) spectra and kinetic isotope effect (KIE) unraveled that the mild reduction condition allowed the catalyst with a superior affinity towards H atom and beneficial furfural adsorption behavior, accelerating the H₂ activation in the rate-determining step for the conversion of furfural into furan-based amine.