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Niobium oxide prepared through a novel supercritical-CO2-assisted method as a highly active heterogeneous catalyst for the synthesis of azoxybenzene from aniline

Tao, Y., Singh, B., Jindal, V., Tang, Z. & Pescarmona, P. P., 2019, In : Green Chemistry. 21, 21, p. 5852-5864 13 p.

Research output: Contribution to journalArticleAcademicpeer-review

High-surface area Nb2O5 nanoparticles were synthesised by a novel supercritical-CO2-assisted method (Nb2O5-scCO2) and were applied for the first time as a heterogeneous catalyst in the oxidative coupling of aniline to azoxybenzene using the environmentally friendly H2O2 as the oxidant. The application of scCO2 in the synthesis of Nb2O5-scCO2 catalyst resulted in a significantly enhanced catalytic activity compared to a reference catalyst prepared without scCO2 (Nb2O5-Ref) or to commercial Nb2O5. Importantly, the Nb2O5-scCO2 catalyst achieved an aniline conversion of 86% (stoichiometric maximum of 93% with the employed aniline-to-H2O2 ratio of 1 : 1.4) with an azoxybenzene selectivity of 92% and with 95% efficiency in H2O2 utilisation in 45 min without requiring external heating (the reaction is exothermic) and with an extremely low catalyst loading (weight ratio between the catalyst and substrate, Rc/s = 0.005). This performance largely surpasses that of any other heterogeneous catalyst previously reported for this reaction. Additionally, the Nb2O5 catalyst displayed high activity also for substituted anilines (e.g. methyl or ethyl-anilines and para-anisidine) and was reused in consecutive runs without any loss of activity. Characterisation by means of N2-physisorption, XRD, FTIR and TEM allowed the correlation of the remarkable catalytic performance of Nb2O5-scCO2 to its higher surface area and discrete nanoparticle morphology compared to the aggregated larger particles constituting the material prepared without scCO2. A catalytic test in the presence of a radical scavenger proved that the reaction follows a radical pathway.
Original languageEnglish
Pages (from-to)5852-5864
Number of pages13
JournalGreen Chemistry
Volume21
Issue number21
Early online date11-Sep-2019
Publication statusPublished - 2019

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