Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole

Abstract

Hydrodeoxygenation (HDO) is one of the promising catalytic routes for converting biomass derived molecules to high value products. A key step of HDO is the cleavage of an aromatic C–O bond to accomplish the deoxygenation step, however, which is energetically unfavorable. Herein, we report a series of palladium (Pd)-incorporated α-phase of molybdenum carbide (α-MoC) mesoporous composites for enhanced HDO activity of a biomass model molecule, anisole. The catalysts, x%Pd/α-MoC (x% is the molar ratio of Pd/Mo), were investigated by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption (TPD), Brunauer–Emmett–Teller (BET), Raman, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques. Pd is highly dispersed on α-MoC when x% ≤ 1%, but aggregate to form nanoparticles when x% = 5%. The x%Pd/α-MoC catalysts (x% ≤ 1%) show enhanced HDO activity in terms of turnover frequency (TOF) and apparent activation energy barrier (Ea) compared with α-MoC and β-Mo2C catalysts. The TOF of 1%Pd/α-MoC catalyst at 160 °C is 0.115 h−1 and the Ea is 48.2 kJ/mol. Moreover, the direct cleavage of aromatic C–O bond is preferred on 1%Pd/α-MoC catalyst. The enhanced HDO activity is attributed to superior H2 dissociation ability by the highly dispersed Pd sites on carbide. This work brings new insights for rational design of the catalyst for selective C–O bond activation.

Keywords

• hydrodeoxygenation
• carbide
• palladium
• anisole
• biomass
• C–O bond cleavage