Dataset of Supported Uranyl Photocatalyst on Hafnium-Metal-organic Layers for Alkylation of Cyclic Alcohols

Visible-light excitation of uranyl cations produces highly oxidizing excited states capable of activating inert chemical bonds. The process utilizes 238U-depleted uranium, a fission fuel byproduct enriched in 238U, which has significantly lower radioactivity and is safe for practical use. However, homogeneous uranyl photocatalysis suffers from limited recyclability and potential uranium contamination concerns even with low radioactivity. Therefore, immobilization of depleted uranyl onto suitable supports is critical. To address these limitations, we implemented two distinct post-synthetic modification strategies targeting the secondary building units (SBUs) and organic linkers separately, enabling effective immobilization of uranyl ions on hafnium-based metal-organic layers (BTB/TPY-Hf-MOLs). Characterization revealed that BTB-Hf-MOL-U forms surface-bound uranyl species predominantly in the form of uranium oxide (UO3) nanoparticles, while TPY-Hf-MOL-U generates a single-site heterogeneous catalyst through ligand chelation. Under blue LED irradiation, BTB-Hf-MOL-U demonstrates noteworthy catalytic efficiency and diastereoselectivity, whereas TPY-Hf-MOL-U exhibited superior cycling stability.铀酰阳离子（uranyl cations）在可见光激发下可生成具有强氧化活性的激发态，能够活化惰性化学键。该工艺采用贫化铀（238U-depleted uranium）——一种富含238U的裂变燃料副产物，其放射性水平显著更低，可安全用于实际场景。然而，即便放射性较低，均相铀酰光催化仍存在可回收性有限以及潜在铀污染的隐患。因此，将贫化铀酰固定于合适载体上具有关键意义。为解决上述局限，我们开发了两种差异化的后合成修饰策略，分别靶向次级结构单元（secondary building units, SBUs）与有机配体，实现了铀酰离子在铪基金属有机层（BTB/TPY-Hf-MOLs）上的高效固定。表征结果表明，BTB-Hf-MOL-U主要以三氧化铀（UO3）纳米颗粒的形式形成表面结合型铀酰物种，而TPY-Hf-MOL-U则通过配体螯合构建出单中心多相催化剂。在蓝光LED辐照下，BTB-Hf-MOL-U展现出优异的催化效率与非对映选择性，而TPY-Hf-MOL-U则具备更出色的循环稳定性。