ZIF-67 derived hollow carbon with embedded Co nanoparticles for highly selective hydrogenation of HMF to 2,5-dihydroxymethylfuran

Metals embedded nitrogen-doped carbon (M/NC) materials have garnered substantial attention due to the catalytic active centers provided by their transition metals. Here, the ZIF-67 derived Co/NC hollow structure catalyst (Co/NHC-4) exhibited remarkable performance in the hydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to valuable 2,5-dihydroxymethylfuran (DHMF). Under mild conditions of 60 °C and 2 MPa H 2 , the conversion of HMF reached nearly 100 %, with DHMF selectivity >99 %. Through the integration of advanced characterization techniques, such as TEM, XPS, XAFS, Raman spectroscopy, vapor adsorption curve, H 2 -TPD and in situ FTIR spectroscopy, it was demonstrated that the superior hydrogenation performance of hollow-structured catalysts primarily stems from unique morphology. Specifically, the hollow morphology facilitates the adsorption and diffusion of HMF on Co surface, which substantially enhances the hydrogenation efficiency. DFT calculation reveals the preferential parallel adsorption geometry of HMF and the energetically favorable hydrogenation pathway.