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

• Published in: ACS applied materials & interfaces Vol. 11; no. 27; pp. 24140 - 24153
• Main Authors: Shit, Subhash Chandra, Koley, Paramita, Joseph, Boby, Marini, Carlo, Nakka, Lingaiah, Tardio, James, Mondal, John
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.07.2019
• Subjects: activation energy; adsorption; biofuels; biomass; catalysts; catalytic activity; cations; cobalt; cobalt oxide; lignocellulose; nanohybrids; nanoparticles; nanosheets; phosphides; polymers; refining; spectroscopy; structure-activity relationships; vanillin; cobalt phosphide; porous organic polymer; hydrodeoxygenation (HDO); biofuel; vanillin; ATR-IR
• ISSN: 1944-8244; 1944-8252; 1944-8252
• DOI: 10.1021/acsami.9b06789

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 Co x P@POP, where substoichiometric Co x P nanoparticles are distributed in a porous organic polymer (POP) via solid-state phosphidation of the Co3O4@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 Co x P@POP exhibited superior catalytic activity and selectivity toward desired product with improved stability compared to the Co3O4@POP. Based on advanced sample characterization results, the extraordinary selectivity of Co x P@POP is attributed to the strong interaction of the cation of the Co x P 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 Co3O4@POP compared to Co x P@POP catalyst could be attributed to the stronger adsorption of vanillin over the Co3O4@POP catalyst. Also from kinetic investigation, it is clearly demonstrated that the Co3O4@POP has higher activation energy barrier than the Co x P@POP, which also reflects to the reduction of the overall efficiency of the Co3O4@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.