Lattice Oxygen Insertion Mechanism in CeO2-Catalyzed Reactions in Water: Nitrile Hydration Reaction

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Takaaki Endo, Tatsushi Ikeda, Koki Muraoka, Yusuke Kita, Masazumi Tamura, Akira Nakayama
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Abstract

Cerium oxide (CeO2) exhibits prominent catalytic activity in various organic reactions owing to its unique acid-base and redox properties. One of the most interesting applications of pure CeO2-catalyzed organic reactions is the hydration of nitriles in water. The experimental results showed that the hydration of 2-cyanopyridine to picolinamide in water using CeO2 catalysts proceeds readily at low temperatures (30−100 °C) in high yields and that this reaction occurs exclusively on CeO2 among various metal-oxide catalysts. To elucidate the unique catalytic activity of CeO2, the reaction mechanism is dissected using the density functional theory-based molecular dynamics (DFT-MD) simulations. Based on the free energy analysis, it is demonstrated that the reaction proceeds with the involvement of the surface lattice oxygen, where the lattice oxygen atom is inserted into picolinamide. The involvement of the surface lattice oxygen is notably uncommon given the low temperatures of the reaction, and this computational prediction is verified by the two experiments using H218O solvent and 18O-exchanged CeO2 catalyst, where the introduction of surface lattice oxygen into picolinamide is confirmed. The inherent flexibility of the surface lattice oxygen and the unique acid-base properties of CeO2, which can favorably bind and activate both nitrile and water molecules, are key factors in the high reactivity for various organic reactions, which characterizes the outstanding catalytic activity of CeO2.
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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