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

Abstract

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 Co 3 O 4 @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 Co 3 O 4 @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 Co 3 O 4 @POP compared to Co x P@POP catalyst could be attributed to the stronger adsorption of vanillin over the Co 3 O 4 @POP catalyst. Also from kinetic investigation, it is clearly demonstrated that the Co 3 O 4 @POP has higher activation energy barrier than the Co x P@POP, which also reflects to the reduction of the overall efficiency of the Co 3 O 4 @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.

Fabrication of Ir-CoOx@mesoporous SiO2 Nanoreactors for Selective Hydrogenation of Substituted Nitroaromatics

“…The peaks at 780.7 and 797.0 eV are ascribed, respectively, to the Co 2p 3/2 and Co 2p 1/2 of Co 6+ species, while the binding energies of 785.5 and 803.2 eV are indexed to the Co 2p 3/2 satellite and Co 2p 1/2 satellite of Co 2+ , respectively. It was difficult to identify the type of cobalt oxide. − Based on the position and shape of satellites, it was likely dominated by CoO [pure Co­(II)]; yet, we could not rule out the coexistence of Co 3 O 4 [CoIICoIII 2 O 4 ]. Evidently, the surface Ir and Co atoms on IrCo NPs are oxidized when exposed to air, and the ratios of Ir 0+ /Ir 4+ and Co 0+ /Co 6+ are 90.9:9.1 and 11.4:88.6, respectively (Table ).…”

Navigating Copper-Atom-Pair Structural Effect inside a Porous Organic Polymer Cavity for Selective Hydrogenation of Biomass-Derived 5-Hydroxymethylfurfural

“…The limited stock of fossil fuels and growing concern about global climate change played a crucial role behind the wisdom to discover the alternative energy sources, such as biomass derived carbohydrates. 1,2,3 Bio-refinery is a widely advanced concept to transform the biomass derived oxygenates to generate biofuel. 4,5,6 5-hydroxymethylfurfural (5-HMF) is a platform chemical of lignocelluloses valorization.…”

“…The limited stock of fossil fuels and growing concern about global climate change played a crucial role behind the wisdom to discover alternative energy sources, such as biomass-derived carbohydrates. − Bio-refinery is a widely advanced concept to transform biomass-derived oxygenates to generate biofuel. − 5-Hydroxymethylfurfural (5-HMF) is a platform chemical of lignocellulose valorization. Among the hydrogenated products including 2,5-dihydroxymethylfuran (DHMF), 2,5-dihydroxymethyltetrahydrofuran (DHMTHF), 2,5-dimethylfuran (DMF), 2,5-dimethyltetrahydrofuran (DMTHF), and so forth, DHMF has attracted significant attention due to tremendous application in the production of resin, ethers, and artificial fibers and as an important intermediate in drug synthesis .…”

Effects of metal promoters in bimetallic catalysts in hydrogenolysis of lignin derivatives into value‐added chemicals

“…have demonstrated that the modification of Cu−Pd interfaces by electronic effects was contributed to the enhanced catalytic activity over the Cu 3 Pd 1 @BBA‐1 (N‐rich porous organic polymer) bimetallic catalyst. Besides, the introduction of the metal promoters can modify the electronic structure of active sites through the ligand effect, which can alter the metal electron density and facilitate Hydrogen activation [48] . For example, Zhou et al [49] .…”