Chemistry of Actinide Centers in Heterogeneous Catalytic Transformations of Small Molecules,ACS Catalysis

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Chemistry of Actinide Centers in Heterogeneous Catalytic Transformations of Small Molecules
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-04-10 00:00:00 , DOI: 10.1021/acscatal.8b04924
Jennifer Leduc ₁ , Michael Frank ₁ , Lasse Jürgensen ₁ , David Graf ₁ , Aida Raauf ₁ , Sanjay Mathur ₁

Affiliation

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.

中文翻译：

小分子非均相催化转化中Act系中心的化学反应

act系元素分子和材料的化学性质在过去十年中已显示出显着的概念进步，表明它们与镧系元素和过渡元素相比具有独特的反应性，但对于低价态的耐人寻味的稳定性以及其低价态的重要作用仍存在一些挑战性的问题。 f系元素的键合和反应性中的5f轨道。act系元素中心独特的电子柔韧性使其成为异质分子转化的潜在催化剂，因为它们的配位态具有动力学上的不稳定性，并且在氧化态之间容易切换。mild系元素活化的化学转化，例如在温和的条件下将六价氮还原成两个反应性氨分子或将四价水氧化成氧气，是寻求高效多相催化剂的有前途的途径。这篇综述全面综述了act系元素介导的小分子如CO，CO的催化转化₂，N ₂，O ₂，H ₂ O，CH ₄，HCl和NH ₃。重点放在基于act系元素的固体催化剂中的新兴现象以及作为原始相和底物生长相的纳米结构act系材料的受控合成。机理研究突显了5f电子在多电子转移反应中的影响以及act系元素中心达到更高氧化态的倾向，这些更高的氧化态定义了act系氧化物的表面终止作用。最后，讨论了含act系元素材料在核燃料应用领域之外的现状和前景，强调了其令人兴奋的化学性质和在替代催化能源生产过程中的未开发潜力。

更新日期：2019-04-10

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