Tungsten Carbide: A Remarkably Efficient Catalyst for the Selective Cleavage of Lignin C−O Bonds

Graphical Breaking up : Tungsten carbide shows remarkable activity in selective C−O bond cleavage of typical β-O-4 model compounds and deconstruction of lignin feedstocks. High yields of C−O cleavage products from model compounds (up to 96.8 %) and from lignin feedstock (up to 70.7 %) are obtained without destroying the aromatic rings. A remarkably effective method for the chemoselective cleavage of the C−O bonds of typical β-O-4 model compounds and the deconstruction of lignin feedstock was developed by using tungsten carbide as the catalyst. High yields of C−O cleavage products (up to 96.8 %) from model compounds and liquid oils (up to 70.7 %) from lignin feedstock were obtained under low hydrogen pressure (0.69 MPa) in methanol. The conversion efficiency was determined to a large extent by solvent effects and was also affected by both the electronic and steric effects of the lignin model compounds. In situ W 2 C/activated carbon (AC)-catalyzed hydrogen transfer from methanol to the substrate was proposed to be responsible for the high performance in methanol solvent. The conversion of 2-(2-methoxyphenoxy)-1-phenylethanol showed that the catalyst could be reused five times without a significant loss in activity for C−O bond cleavage, whereas the selectivity to value-added styrene increased markedly owing to partial oxidation of the W 2 C phase according to X-ray diffraction, Raman spectroscopy, and transmission electron microscopy characterization. 2 D-HSQC-NMR spectroscopy analysis showed that W 2 C/AC exhibited high activity not only for β-O-4 cleavage but also for the deconstruction of more resistant α-O-4 and β-β linkages, so that a high yield of liquid oil was obtained from lignin. Corn stalk lignin was more liable to be depolymerized than birch lignin owing to its loosened structure (scanning electron microscopy results), larger surface area (BET results), and lower molecular weight (gel-permeation chromatography results), whereas its liquid oil composition was more complicated than that of birch wood lignin in that the former lignin contained more p -hydroxyphenyl units and the former contained noncanonical units.