XRD

XPS
 Conversion of guaiacol over MoWC, Mo2C, WC and Mo2C + WC catalysts at different temperatures.
Benzene was not formed over the WC-700 catalyst. P = 400 psig; WHSV = 1.8 h−1; TOS = 2–4 h (solid
line: guaiacol conversion; dashed line: benzene selectivity). B) Arrhenius plot for guaiacol conversion
over monometallic and bimetallic carbides.

The intrinsic reaction rate calculated by normalizing the reaction rate to the exposed
surface metals (Mo and/or W) derived from the XPS analysis 44 (Table S3 and in Fig.
S6†) also indicates the highest activity of MoWC among the catalysts studied.

In addition, these results are consistent with reports demonstrating similar deoxygenation
activity over molybdenum-based carbide catalysts (i.e. 90% benzene selectivity from
anisole over Mo2C and >80% non-oxygen-containing product selectivity from guaiacol
over Ni/Mo2C and Pt/Mo2C.14,18

the synergistic effect between Mo and W, which is confirmed via the catalyst
characterization, increases significantly the density of H2-activating sites. The hydrogen
availability plays a crucial role in both hydrogenolysis of surface-bound intermediates and
removal of surface oxygen to regenerate the active sites. Therefore, the bimetallic
catalyst (Mo–W) displayed a superior HDO activity. On the other hand, the addition of W
significantly decreases the acidic site density of molybdenum carbide in favor of DDO to
yield benzene as the major product.