Atomically Dispersed Dual Metal Sites Boost the Efficiency of Olefins Epoxidation in Tandem with CO2 Cycloaddition

Yinming Wang; Ziqi Tian; Qihao Yang; Kaicheng Tong; Xuan Tang; Nian Zhang; Jing Zhou; Linjuan Zhang; Qiuju Zhang; Sheng Dai; Yichao Lin; Zhiyi Lu; Liang Chen

doi:10.1021/acs.nanolett.2c03087

Atomically Dispersed Dual Metal Sites Boost the Efficiency of Olefins Epoxidation in Tandem with CO₂ Cycloaddition

Nano Lett. 2022 Oct 26;22(20):8381-8388. doi: 10.1021/acs.nanolett.2c03087. Epub 2022 Sep 20.

Authors

Yinming Wang^{1

2}, Ziqi Tian^{1

2}, Qihao Yang^{1

2}, Kaicheng Tong^{1

2}, Xuan Tang³, Nian Zhang⁴, Jing Zhou⁵, Linjuan Zhang⁵, Qiuju Zhang^{1

2}, Sheng Dai³, Yichao Lin^{1

2}, Zhiyi Lu^{1

2}, Liang Chen^{1

2}

Affiliations

¹ Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology and Engineering, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, People's Republic of China.
² University of Chinese Academy of Sciences, 100049 Beijing, People's Republic of China.
³ Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, People's Republic of China.
⁴ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, People's Republic of China.
⁵ Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, People's Republic of China.

PMID: 36125371
DOI: 10.1021/acs.nanolett.2c03087

Abstract

Tandem catalysis provides an economical and energy-efficient process for the production of fine chemicals. In this work, we demonstrate that a rationally synthesized carbon-based catalyst with atomically dispersed dual Fe-Al sites (ADD-Fe-Al) achieves superior catalytic activity for the one-pot oxidative carboxylation of olefins (conversion ∼97%, selectivity ∼91%), where the yield of target product over ADD-Fe-Al is at least 62% higher than that of monometallic counterparts. The kinetic results reveal that the excellent catalytic performance arises from the synergistic effect between Fe (oxidation site) and Al sites (cycloaddition site), where the efficient CO₂ cycloaddition with epoxides in the presence of Al sites (3.91 wt %) positively shifts the oxidation equilibrium to olefin epoxidation over Fe sites (0.89 wt %). This work not only offers an advanced catalyst for oxidative carboxylation of olefins but also opens up an avenue for the rational design of multifunctional catalysts for tandem catalytic reactions in the future.

Keywords: CO2 utilization; atomically dispersed dual metal sites; carbon-based catalyst; olefin epoxidation; tandem catalysis.