<br>通过 N-CNT 支持的 RhP 亚纳米团簇和用于烯烃加氢甲酰化的限域 Co 纳米颗粒的协同催化降低动力学屏障,ACS Catalysis

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通过 N-CNT 支持的 RhP 亚纳米团簇和用于烯烃加氢甲酰化的限域 Co 纳米颗粒的协同催化降低动力学屏障
ACS Catalysis ( IF 11.3 ) Pub Date : 2025-01-09 , DOI: 10.1021/acscatal.4c06822
Jiamei Wei ₁ , Peng Gao ₁ , Shen Wang ₁ , Yue Ma ₁ , Dong Cao ₁ , Daojian Cheng ₁

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为多步基本反应开发协同位点很重要，但具有挑战性。在此，限制在碳纳米管内部的 Co 纳米颗粒和负载在碳纳米管外部的 RhP 亚纳米团簇（Co@N-CNTs|RhP）是通过缺陷辅助浸渍策略合成的。值得注意的是，Co 纳米颗粒和 RhP 亚纳米团簇的协同工程距离为 0.66 nm。Co@N-CNT 的周转频率|RhP 催化剂在二异丁烯加氢甲酰化过程中可以达到 82603 h^–1，比商用 Rh 均相催化剂高 15 倍。更重要的是，获得的 Co@N-CNTs|RhP 实现了 25 个催化循环。动力学实验表明，限制 Co 纳米颗粒和 RhP 亚纳米团簇的协同工程是促进二异丁烯加氢甲酰化的关键，使活化能降低到 64.6 kJ/mol。进一步的原位漂移光谱和理论计算表明，经 RhP 亚纳米团簇改性的局限 Co 纳米颗粒有利于 H₂、CO 和二异丁烯的吸附，而 RhP 亚纳米团簇负责醛的形成。这项工作为构建用于长链烯烃转化反应的高效多位点非均相催化剂提供了深刻的见解。

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Lowering the Kinetic Barrier via the Synergistic Catalysis of N-CNTs Supported RhP Subnanoclusters and Confined Co Nanoparticles for Olefins Hydroformylation

Developing synergistic sites for a multistep elementary reaction is important, but challenging. Herein, the coexistence of Co nanoparticles confined inside the carbon nanotubes and RhP subnanoclusters loaded on the outside of carbon nanotube (Co@N-CNTs|RhP) is synthesized by a defect-assisted impregnation strategy. Notably, Co nanoparticles and RhP subnanoclusters have a synergistic engineering distance of 0.66 nm. The turnover frequency over Co@N-CNTs|RhP catalyst could reach 82603 h^–1 during the diisobutylene hydroformylation, 15 times higher than that of the commercial Rh homogeneous catalysts. More importantly, the obtained Co@N-CNTs|RhP achieved 25 catalytic cycles. Kinetic experiments show that the synergistic engineering of confined Co nanoparticles and RhP subnanoclusters is the key to promote the hydroformylation of diisobutylene, which reduces the activation energy to 64.6 kJ/mol. Further in situ DRIFT spectra and theoretical calculations reveal the confined Co nanoparticles modified by RhP subnanoclusters are conducive to the adsorption of H₂, CO, and diisobutylene, while the RhP subnanoclusters are responsible for the formation of aldehydes. This work provides profound insight for the construction of efficient multisite heterogeneous catalyst for long-chain olefin conversion reactions.

更新日期：2025-01-09

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