Interfacial Engineering of Supported M-WO_x Catalysts for Selective Glycerol Hydrogenolysis to 1,3-Propanediol: A Systematic Review

Glycerol hydrogenolysis is a promising pathway for converting abundant biodiesel-derived glycerol into value-added products, particularly 1,3-propanediol (1,3-PDO), a high-value chemical and key monomer for polytrimethylene terephthalate production. However, selective production of 1,3-PDO remains challenging due to the difficulty of selectively cleaving the secondary C-O bond in the presence of competitive primary C-O bond or C-C bond cleavage pathways. Supported M-WO_x catalyst systems have attracted significant attention due to their ability to generate metal-oxide interfacial sites that facilitate selective glycerol hydrogenolysis.

A systematic review was conducted following the PRISMA 2020 framework through Scopus and Web of Science databases from 2016 to 2026 using keywords related to "glycerol" "hydrogenolysis" "1,3-propanediol" and "WO_x". From 861 identified records, 47 studies were screened by title, after removing 23 duplicated records, 24 studies were finally included for analysis. Selection criteria included reporting quantitative glycerol conversion and product selectivity, reaction conditions, catalyst preparation methods, and characterization data for supported M-WO_x catalysts.

The analysis revealed that glycerol conversion and 1,3-PDO selectivity are primarily governed by the metal-oxide interface, rather than isolated metal or WO_x sites. Among the catalyst systems reviewed, Pt-WO_x-based catalysts demonstrated the highest reported performance, achieving 67.3% selectivity and 94.9% conversion over Pt/WO_x/Nb₂O₅ but required high hydrogen pressures (8MPa H₂) and expensive noble metals. Moderate WO_x loadings provided an optimal balance of Brönsted acidity and WO_x dispersion, whereas excessive WO_x loadings promoted WO₃ crystallization and reduced catalytic performance. In contrast, non-noble metal systems, particularly, Cu-WO_x and Ni-WO_x catalysts, remain less developed despite their economic advantages.

This review identifies the M-WO_x interface as a key factor controlling glycerol hydrogenolysis performance. Significant opportunities remain in understanding and engineering non-noble metal interfaces, particularly Ni-based systems, for glycerol valorization. Future research should focus on rational interfacial engineering strategies to develop cost-effective, scalable, and sustainable catalysts for selective 1,3-PDO production.