Effective Hydrogenolysis of Glycerol to 1,3‐Propanediol over Metal‐Acid Concerted Pt/WOx/Al2O3 Catalysts.

Selective cleavage of secondary C−O bond is an important yet challenging strategy in glycerol valorization, and the product 1,3‐propanediol (1,3‐PDO) is of great value in polyester industry. Herein, we report a series of Pt/WOx/Al2O3 catalysts for selective hydrogenolysis of glycerol in a fixed‐bed reactor and obtain the highest space‐time yield of 1,3‐PDO (191.7*10−3 g1,3‐PDO h−1 g−1cat.) to date. Both Pt and W have substantial effects on the 1,3‐PDO yield with the optimum Pt/W atomic ratio of 1/2∼1/4. Spectroscopy characterizations as well as chemisorption experiments reveal that at the medium domain size of WOx, hydrogen spillover can take place to the greatest extent due to the improved dispersion of Pt and the suitable reducibility of WOx. Dehydration/dehydrogenation tests of 2‐butanol suggest that strong Brønsted acid sites are created via hydrogen dissociation at the Pt−WOx interface and spillover to the neighboring oxygen atom. Such in situ formed protons are critical to the selective cleavage of secondary C−O bonds of polyols. [ABSTRACT FROM AUTHOR]