Synergy of carbon defect and transition metal on tungsten carbides for boosting the selective cleavage of aryl ether C[sbnd]O bond.

• The inert tungsten carbides are activated by C-etching in the presence of Pt. • Pt–WC with C-defects shows efficient activity for cleavage of aryl ether C O bond. • The catalytic promotion is ascribed to the synergy effects of Pt species and C-defects. • Pt–WC displays a different reaction pathway compared with WC and Pt alone. • The synergy effects of other transition metals and C-defects are also manifested. Transition-metal carbides are attractive heterogeneous catalysts for the transformation of lignin-derived compounds. However, the effects of the surface carbon defect (C-defect) remain unclear due to coke deposition and exposed C terminations. Herein, we transform inert tungsten carbides (WC) into active catalysts via surficial C-etching using transition metals in the presence of H 2. An optimized 1% Pt–WC catalyst with synergy of Pt and C-defects can perform a 78.6% conversion in the selective hydrogenolysis of guaiacol to phenol with 89.0% selectivity at 300 °C, while the intact WC only gives a 7.1% guaiacol conversion with 51.0% phenol selectivity under the same conditions. As a result, the 1% Pt–WC catalyst exhibits 19-fold higher reaction rate and 12.6-fold higher turnover frequency than those of WC. Moreover, no substantial loss of catalytic performance has been observed with 1% Pt–WC for 50 h on stream. A rational reaction pathway is accordingly proposed through in-depth characterizations. [ABSTRACT FROM AUTHOR]