The hydrodeoxygenation (HDO) reaction is crucial to the upgrading of biomass-derived furfural to produce a promising fuel additive, 2-methylfuran. In order to enhance the stability of the molybdenum carbide (Mo₂C) catalyst, this work utilizes cobalt (Co) modification to tune the oxygen and furfural binding energies on Mo₂C. Density functional theory (DFT) calculations of the adsorption configuration of furfural on Mo₂C(0001) and cobalt-modified molybdenum carbide (Co/Mo₂C(0001)) reveal that the CO bond of furfural is elongated, facilitating the selective CO scission to produce 2-methylfuran. The reduced oxygen and furfural binding energies on Co/Mo₂C(0001) allow the facile removal of surface oxygen and furfural to improve the stability of the catalyst. Temperature-programmed desorption (TPD) experiments on model surfaces confirm the enhanced stability and overall HDO performance of Co/Mo₂C/Mo(110). Based on the results from high-resolution electron energy loss spectroscopy (HREELS), 2-methylfuran-like intermediates are observed on both Mo₂C/Mo(110) and Co/Mo₂C/Mo(110). Parallel reactor evaluations over the corresponding powder catalysts further demonstrate the enhanced stability of Co/Mo₂C over Mo₂C at ambient pressure. This work illustrates the important roles of oxygen and furfural binding energies in the furfural HDO reaction on both model surfaces and powder catalysts, which in turn provides insights into designing selective and stable carbide-based catalysts for HDO reactions.

加氢脱氧（HDO）反应对于将生物质衍生的糠醛进行提质以生产出有前途的燃料添加剂2-甲基呋喃至关重要。为了提高碳化钼（Mo ₂ C）催化剂的稳定性，该工作利用钴（Co）改性来调节Mo ₂ C上的氧和糠醛结合能。 Mo ₂ C（0001）和钴改性的碳化钼（Co / Mo ₂ C（0001））上的糠醛显示糠醛的C O键是延长的，有利于选择性的C O分裂以生成2-甲基呋喃。Co / Mo ₂上的氧和糠醛结合能降低C（0001）允许容易地除去表面氧和糠醛以改善催化剂的稳定性。在模型表面进行温度编程的脱附（TPD）实验证实了Co / Mo ₂ C / Mo（110）的增强的稳定性和整体HDO性能。基于高分辨率电子能量损失谱（HREELS）的结果，在Mo ₂ C / Mo（110）和Co / Mo ₂ C / Mo（110）上均观察到了2-甲基呋喃样中间体。在相应的粉末催化剂并联反应器评价进一步证明的Co / Mo的增强的稳定性₂下经沫₂C在环境压力下。这项工作说明了氧气和糠醛结合能在模型表面和粉末催化剂上的糠醛HDO反应中的重要作用，从而为设计选择性和稳定的基于碳化物的HDO反应提供了见识。