Function of Brønsted and Lewis acid sites in xylose conversion into furfural

In this work, the xylose conversion and the selectivity to furfural were assessed over mesoporous sulfonic silica SBA-15-(X)SO₃H catalysts doped with metal ions (X = Al(iii), Ti(iv) or Zr(iv)). The type and amount of acid sites were analyzed by adsorption of pivalonitrile. The SBA-15-(X)SO₃H materials show Lewis acid sites (LAS) and two types of Brønsted acid sites (BAS) with different strengths. Type I (BAS I) belongs to terminal silanol groups, type II (BAS II) is ascribed to hydroxyl groups bonded to sulfur or transition metal, and the LAS is related to M-O bonds. Optimal reaction conditions for the most active catalyst (SBA-15-(Zr)SO₃H) were 120 minutes of reaction at 160 °C, 20 wt% of catalyst, and 2.5% of xylose/solvent. Additionally, a kinetic study was carried out to calculate the rate constants, the activation energy, and the pre-exponential factor for the xylose dehydration reaction. It was found that the selectivity to furfural in sulfonic silica SBA-15-(X)SO₃H catalysts was directly related to the BAS II fraction. While LAS negatively impacts the selectivity to furfural leading to the undesired reaction between furfural and xylose obtaining humins as secondary products.