Metal-acid bifunctional catalysts based on porous aromatic frameworks for tandem alkylation-hydrogenation of phenolics with furanics

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED Microporous and Mesoporous Materials Pub Date : 2025-03-13 DOI:10.1016/j.micromeso.2025.113594

Andrei Dubiniak , Leonid Kulikov , Sergey Egazar'yants , Anton Maximov , Eduard Karakhanov

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Abstract

Noble metal catalysts based on porous aromatic frameworks modified with sulfo groups were studied in tandem alkylation-hydrogenation reaction between lignocellulose-derived furanic (furfural, furfuryl alcohol and 5-hydroxymethylfurfural) and phenolic compounds (phenol, m-cresol, guaiacol) to produce high-density fuel precursors. Platinum catalysts were synthesized based on PAF-30-SO₃H-3 and PAF-30-SO₃H-5 supports with 3 and 5 % of sulfur, respectively, and both with 0.8 % of platinum. Hydroalkylation of mixtures of two substrates was performed. The reaction of guaiacol with furfuryl alcohol is characterized by the highest yields of long-chain products. The influence of substrates ratio, H₂ pressure, reaction temperature and time on selectivity and activity of the catalysts was studied. The highest yield (77 %) of long-chain oxygenates among all experiments was achieved under the following reaction conditions: 2 MPa H₂, 4 h, 130 °C and 1:8 mol/mol furfuryl alcohol-guaiacol ratio. Catalysts Pd-PAF-30-SO₃H-3 (with 1.1 % of palladium) and Ru-PAF-30-SO₃H-3 (with 0.3 % of ruthenium) were tested in the tandem process to evaluate the impact of metal on reaction. To our knowledge, tandem alkylation-hydrogenation between biomass-derived furanics and phenolics over bifunctional catalysts based on organic polymers is reported for the first time. Moreover, some products of hydroalkylation (e.g., tricyclic oxygenates) haven't yet been described.

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.