Molybdenum doped carbon aerogels with catalytic potential

• Published in: Carbon (New York) 2014-01, Vol.66, p.210-218
• Main Authors: Nagy, Balázs, Ábrahám, Dániel, Dobos, Gábor, Madarász, János, Onyestyák, György, Sáfrán, György, Geissler, Erik, László, Krisztina
• Format: Article
• Language: English
• Subjects: Acetic acid; Aerogels; Carbon; Catalysis; Catalysts; Chemical Physics; Chemistry; Colloidal state and disperse state; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Fullerenes and related materials; diamonds, graphite; General and physical chemistry; Materials science; Molybdenum; Physics; Polymerization; Porosity; Porous materials; Solvents; Specific materials; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0008-6223; 1873-3891
• DOI: 10.1016/j.carbon.2013.08.060

Mo-doped carbon aerogels were obtained in the polycondensation reaction of aqueous resorcinol and formaldehyde by adding Mo-salt at two different stages of the synthesis: (i) to the initial sol; (ii) by incipient wetting impregnation of the supercritically dried polymer gel. Molybdenum added during the polymerization yielded a more compact gel structure with practically no mesoporosity. With post-impregnation, by contrast, mesopores of diameter 3–15nm were generated. Carbonization appreciably enhanced the microporous character of both samples, but in the mesopore range their pore size distribution was conserved. The Mo-content of the samples was also different: Mo was lost during the solvent exchange before the supercritical drying (i.e., the Mo failed to bind chemically to the polymer matrix). The residual Mo congregated into 25–60nm bulk clusters of α-Mo2C. In the other carbon aerogel, finely dispersed α-Mo2C and η-Mo3C2 crystals formed, of size 8–20nm. On the surface of both carbons the Mo formed oxides. In the model test reaction (acetic acid hydroconversion) the catalytic activity of both carbon aerogels was enhanced by molybdenum. The more open pore structure, higher concentration and finer Mo distribution, as well as its chemical form, may all be responsible for the greater conversion and higher value products obtained with the post-impregnated sample.