UraniumIV and uranyle salts, efficient and reusable catalysts for acylation of aromatic compounds

Barbier‐Baudry, D.; Bouazza, Abdellah; Desmurs, Jean‐Roger; Dormond, A.; Richard, Stéphanie

doi:10.1016/s1381-1169(00)00410-6

Cited by 12 publications

(4 citation statements)

References 13 publications

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“…The strongest Lewis acids, the uranyl salts, produce the best yields, and these also possess the advantage of aqueous solubility, key for an increased ease of extraction from the organic products. 402 Taking advantage of the Lewis acidic properties of the uranium, uranium triiodide has been found to be an efficient catalyst for Diels-Alder reactions requiring only short reaction times and 1 mol % amounts of catalyst. 403 Stepping away from catalytic applications, waste remediation has also been of import in driving research in uranium chemistry.…”

Section: Uranium and Uranyl Coordination Chemistrymentioning

confidence: 99%

“…When protected from water, the catalytic reaction is highly specific, and both the mono- or bisacylation products are obtained in high yield, free of uranium. The strongest Lewis acids, the uranyl salts, produce the best yields, and these also possess the advantage of aqueous solubility, key for an increased ease of extraction from the organic products . Taking advantage of the Lewis acidic properties of the uranium, uranium triiodide has been found to be an efficient catalyst for Diels−Alder reactions requiring only short reaction times and 1 mol % amounts of catalyst …”

Section: Uranyl Ion-sequestering Agentsmentioning

confidence: 99%

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Rational Design of Sequestering Agents for Plutonium and Other Actinides

et al. 2003

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Section: Uranium and Uranyl Coordination Chemistrymentioning

confidence: 99%

Section: Uranyl Ion-sequestering Agentsmentioning

confidence: 99%

Rational Design of Sequestering Agents for Plutonium and Other Actinides

et al. 2003

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“…The application of uranium-containing compounds in heterogeneous catalysis was reviewed by Taylor et al in 2009 and by Ismagilov et al in 2013; however, a large body of data has become available since then and some of the highlights are summarized in the following account. Whereas Taylor et al focused on uranium oxides and their applications in oxidation, − reduction, and steam forming reactions, Ismagilov reviewed solid-supported, uranium oxide composites and uranium-containing compounds for catalytic reactions in organic synthesis, − syngas production, , Fischer–Tropsch and hydrocracking processes, hydrodesulfurization, and oxidation and reduction reactions . Because of the thermal stability and resistance to catalytic poisons, such as sulfur, water, and chlorine, the application of uranium oxides for purification of waste gases polluting the environment was examined heavily in the past decades. , As the present Review mainly focuses on recent developments in small molecule activation using actinide containing compounds, several interesting publications and break-through observations on catalytic reactions such as the reduction of 4-nitrophenol using urania-palladium-graphene nanohybrids, the oxidation of chlorobenzene and benzyl alcohols, ,,,,− the degradation of Rhodamine B, or Suzuki–Miyaura cross-coupling reactions of aryl halides will not be reviewed herein.…”

Section: Heterogeneous Catalysis: Small-molecule Activation Using Ura...mentioning

confidence: 99%

Chemistry of Actinide Centers in Heterogeneous Catalytic Transformations of Small Molecules

et al. 2019

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The chemistry of actinide molecules and materials has shown remarkable conceptual advancements in the past decade illustrating their unique reactivity profiles, when compared with lanthanides and transition elements, but there are still some challenging questions on the intriguing stability of low valent states and the significant role of 5f orbitals in bonding and reactivity of actinides. The distinctive electronic flexibility of actinide centers makes them potential catalysts for heterogeneous molecular transformations because of the kinetic lability of their coordination states and facile switching among oxidaton states. Actinide-enabled chemical transformations such as the six-electron reduction of dinitrogen into two reactive ammonia molecules or four-electron oxidation of water into oxygen under mild conditions are promising pathways in the quest of high-efficiency heterogeneous catalysts. This Review provides a comprehensive account on actinide-mediated catalytic transformation of small molecules such as CO, CO2, N2, O2, H2O, CH4, HCl, and NH3. The emphasis is placed on the emerging phenomena in actinide-based solid catalysts and controlled synthesis of nanostructured actinide materials as pristine and substrate-grown phases. The mechanistic investigations highlight the influence of the 5f electrons in multielectron transfer reactions and the propensity of actinide centers to achieve higher oxidation states that defines the surface termination in actinide oxides. Finally, the status and perspectives of actinide-containing materials beyond the nuclear fuel applications is discussed, underlining their exciting chemistry and unexplored potential toward alternative catalytic energy production processes.

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“…Actinide-containing materials have been used in catalytic applications ( Jackson and Hargreaves, 2008 ; Ismagilov and Lazareva, 2013 ; Falcone et al, 2017 ; Leduc et al, 2019 ). Uranium-containing compounds are efficient catalysts in organic syntheses ( Barbier-Baudry et al, 2000 ) and in the activation of small molecules such as CO, H 2 O, CH 4 , and HCl ( Leduc et al, 2019 ). This is because of the large ionic radii of actinides and the active participation of 5 f electrons in the valence space that can lead to unique reactivity patterns and product distributions not accessible to transition metal complexes ( Leduc et al, 2019 ).…”

Section: Introductionmentioning

confidence: 99%

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

2023

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Ammonia (NH3) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber−Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N2 activation barrier and make NH3 synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N2-to-NH3 conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N2 and H2 molecules. Herein, we report single-component heterogeneous catalysts based on 5f actinide dioxide surfaces (ThO2 and UO2) with oxygen vacancies for N2-to-NH3 conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N2 and H2 can be activated at different vacancy sites on the same surface; NH3 is subsequently formed by H− migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH3, making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5f actinide dioxide surfaces for N2 activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH3 conversion.

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UraniumIV and uranyle salts, efficient and reusable catalysts for acylation of aromatic compounds

Cited by 12 publications

References 13 publications

Rational Design of Sequestering Agents for Plutonium and Other Actinides

Rational Design of Sequestering Agents for Plutonium and Other Actinides

Chemistry of Actinide Centers in Heterogeneous Catalytic Transformations of Small Molecules

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

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