Selective Glucose Isomerization to Fructose via a Nitrogen-doped Solid Base Catalyst Derived from Spent Coffee Grounds

In this work, glucose isomerization to fructose was conducted via a solid base biochar catalyst derived from spent coffee grounds and melamine. The X-ray photoelectron spectroscopy spectra identified the majority of pyridinic nitrogen on the biochar surface, which imparted the strong base character of the catalyst. Activity of the catalyst was evidenced by fast conversion of glucose (12%) and high selectivity to fructose (84%) in 20 min at a moderate temperature (120 °C) compared to recently reported immobilized tertiary amines at comparable N concentrations (10-15 mol % relative to glucose). By increasing the reaction temperature to 160 °C, fructose yield achieved 14% in 5 min. The base biochar catalyst showed superior selectivity (>80%) to commonly used homogeneous base catalysts, such as aqueous hydroxides and amines (50-80%) and comparable catalytic activity (∼20 mol % conversion within 20 min). Moreover, cosolvent of acetone in the reaction system may increase the overall basicity by stabilizing protonated water clusters via hydrogen bonding, which led to faster conversion and higher fructose selectivity than those in water. Approximately 19% fructose was obtained at 160 °C, and the basic sites on the biochar catalyst were stable in hydrothermal environment, as indicated by an acid-base titration test. Therefore, nitrogen-doped engineered biochar can potentially serve as a green solid base catalyst for biorefinery processes.