Blurring the boundary between homogenous and heterogeneous catalysis using palladium nanoclusters with dynamic surfaces.
Blurring the boundary between homogenous and heterogeneous catalysis using palladium nanoclusters with dynamic surfaces.
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使用具有动态表面的钯纳米簇模糊了同质和异质催化之间的边界。
DOI：
10.1038/s41467-021-25263-6
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发表时间：
2021-08-17
影响因子：
16.6
通讯作者：
Alves Fernandes J
中科院分区：
文献类型：
--
作者：
Cano I;Weilhard A;Martin C;Pinto J;Lodge RW;Santos AR;Rance GA;Åhlgren EH;Jónsson E;Yuan J;Li ZY;Licence P;Khlobystov AN;Alves Fernandes J
使用磁控溅射方法可以控制纳米团簇的形成，我们创建了结合了非均相和均相催化剂特征的钯纳米团簇。在这里，我们报告了离子液体中不同形成阶段的一系列金属纳米团簇的原子结构和电子环境，从而发现了核心为 ca 的 Pd 纳米团簇。 2 nm 被 [C4C1Im][NTf2] 中原子的扩散动态壳层包围。钯纳米团簇在烯烃环丙烷化中的催化活性的比较表明，原子动态表面至关重要，可以将活性提高约 1 倍。 2 与相似尺寸的紧凑纳米团簇相比。使用汞和二苯并[a,e]环辛烯进行的催化剂中毒测试表明，动态Pd纳米团簇保持了其催化活性，这证明了它们在同一材料中具有均相和非均相催化剂的综合特征。此外，由动态 Pd 纳米团簇介导的烯烃环丙烷化的动力学研究揭示了观察到的催化剂级数为 1，支撑了动态 Pd 纳米团簇的伪均质特征。建立纳米团簇的结构-性能关系以及与其催化性能的联系仍然具有挑战性。在这里，作者展示了具有 2 nm 核心、被 Pd 原子扩散动态壳包围的钯纳米团簇，同时表现出非均相和均相催化剂的特征。
Using a magnetron sputtering approach that allows size-controlled formation of nanoclusters, we have created palladium nanoclusters that combine the features of both heterogeneous and homogeneous catalysts. Here we report the atomic structures and electronic environments of a series of metal nanoclusters in ionic liquids at different stages of formation, leading to the discovery of Pd nanoclusters with a core of ca. 2 nm surrounded by a diffuse dynamic shell of atoms in [C4C1Im][NTf2]. Comparison of the catalytic activity of Pd nanoclusters in alkene cyclopropanation reveals that the atomically dynamic surface is critically important, increasing the activity by a factor of ca. 2 when compared to compact nanoclusters of similar size. Catalyst poisoning tests using mercury and dibenzo[a,e]cyclooctene show that dynamic Pd nanoclusters maintain their catalytic activity, which demonstrate their combined features of homogeneous and heterogeneous catalysts within the same material. Additionally, kinetic studies of cyclopropanation of alkenes mediated by the dynamic Pd nanoclusters reveal an observed catalyst order of 1, underpinning the pseudo-homogeneous character of the dynamic Pd nanoclusters. Establishing a structure-property relationship for nanoclusters and the link with their catalytic performance remain challenging. Here the authors show palladium nanocluster with a core of 2 nm surrounded by a diffuse dynamic shell of Pd atoms exhibit features of heterogeneous and homogenous catalyst at the same time.
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DOI：
10.1002/anie.201508983
发表时间：
2016-02-05
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Burés J
通讯作者：
Burés J
影响因子：
16.6
作者：
Imaoka T;Akanuma Y;Haruta N;Tsuchiya S;Ishihara K;Okayasu T;Chun WJ;Takahashi M;Yamamoto K
通讯作者：
Yamamoto K
影响因子：
5.7
作者：
Kuwabata, Susumu;Tsuda, Tetsuya;Torimoto, Tsukasa
通讯作者：
Torimoto, Tsukasa
影响因子：
16.6
作者：
Bures, Jordi
通讯作者：
Bures, Jordi
影响因子：
16.6
作者：
Gaertner, Dominik;Welther, Alice;Jacobi von Wangelin, Axel
通讯作者：
Jacobi von Wangelin, Axel