Boosting the Hydroformylation Activity of a Rh/CeO2 Single-Atom Catalyst by Tuning Surface Deficiencies,ACS Catalysis

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Boosting the Hydroformylation Activity of a Rh/CeO2 Single-Atom Catalyst by Tuning Surface Deficiencies
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-15 , DOI: 10.1021/acscatal.3c00810
Ying Zheng _{1,

2,

3} , Qiang Wang ₂ , Qi Yang ₂ , Sikai Wang _{1,

3} , Max Joshua Hülsey ₃ , Shipeng Ding ₃ , Shinya Furukawa ₄ , Maoshuai Li _{1,

2} , Ning Yan _{1,

3} , Xinbin Ma _{1,

2}

Affiliation

Controlling the interactions between atomically dispersed metal atoms and the support plays significant roles in determining the activity and selectivity of single-atom catalysts. In this report, we tuned the local coordination environment of Rh single atoms on CeO₂ via calcination to construct a highly active hydroformylation catalyst. Single-atom Rh/CeO₂ calcined at a high temperature exhibits more oxygen vacancies, which lead to the formation of a large amount of low-coordination Rh active species that are more active for hydroformylation. Under the optimum conditions, the best Rh/CeO₂ catalyst achieved a TOF at approximately 5000 h^–1 with 100% aldehyde selectivity in propylene hydroformylation to butanal. In situ FTIR spectroscopy and in situ XPS characterizations provide strong evidence that Rh on 800 °C-calcined CeO₂ is easily activated to form surface HRh(CO)₂ active species, favoring propylene adsorption and CO insertion. This work highlights the significance of engineering metal–support interactions in tuning the hydroformylation performance of single-atom catalysts and contributes to mechanistic insights into single-atom Rh-catalyzed hydroformylation reactions.

中文翻译：

通过调节表面缺陷提高 Rh/CeO2 单原子催化剂的加氢甲酰化活性

控制原子分散的金属原子与载体之间的相互作用在决定单原子催化剂的活性和选择性方面起着重要作用。_{在本报告中，我们通过煅烧调整 Rh 单原子在 CeO 2}上的局域配位环境，构建了一种高活性加氢甲酰化催化剂。高温煅烧的单原子Rh/CeO _{2氧空位较多，导致形成大量低配位的Rh活性种，对加氢甲酰化反应更具活性。}在最佳条件下，最好的 Rh/CeO _{2催化剂在大约 5000 h}^–1时实现了 TOF在丙烯加氢甲酰化成丁醛中具有 100% 的醛选择性。原位 FTIR 光谱和原位 XPS 表征提供了强有力的证据，证明 800 °C 煅烧的 CeO ₂上的 Rh很容易被激活形成表面 HRh(CO) ₂活性物质，有利于丙烯吸附和 CO 插入。这项工作强调了工程金属-载体相互作用在调节单原子催化剂的加氢甲酰化性能方面的重要性，并有助于深入了解单原子 Rh 催化的加氢甲酰化反应的机理。

更新日期：2023-05-15

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