Porous Organic Polymer-Driven Evolution of High-Performance Cobalt Phosphide Hybrid Nanosheets as Vanillin Hydrodeoxygenation Catalyst.

Hydrodeoxygenation (HDO) is a promising route for the upgrading of bio-oils to eco-friendly biofuel produced from lignocellulose. Herein, we report the sequential synthesis of a hybrid nanocatalyst CoP@POP, where substoichiometric CoP nanoparticles are distributed in a porous organic polymer (POP) via solid-state phosphidation of the CoO@POP nanohybrid system. We also explored the catalytic activity of the above two nanohybrids toward the HDO of vanillin, a typical compound of lignin-derived bio-oil to 2-methoxy-4-methylphenol, which is a promising future biofuel. The CoP@POP exhibited superior catalytic activity and selectivity toward desired product with improved stability compared to the CoO@POP. Based on advanced sample characterization results, the extraordinary selectivity of CoP@POP is attributed to the strong interaction of the cation of the CoP nanoparticle with the POP matrix and the consequent modifications of the electronic states. Through attenuated total reflectance-infrared spectroscopy, we have also observed different interaction strengths between vanillin and the two catalysts. The decreased catalytic activity of CoO@POP compared to CoP@POP catalyst could be attributed to the stronger adsorption of vanillin over the CoO@POP catalyst. Also from kinetic investigation, it is clearly demonstrated that the CoO@POP has higher activation energy barrier than the CoP@POP, which also reflects to the reduction of the overall efficiency of the CoO@POP catalyst. To the best of our knowledge, this is the first approach in POP-encapsulated cobalt phosphide catalyst synthesis and comprehensive study in establishing the structure-activity relationship in significant step-forwarding in promoting biomass refining.