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Epoxidation of Propylene by Hydrogen Peroxide Catalyzed by the Silanol-Functionalized Polyoxometalates-Supported Ferrate: Electronic Structure, Bonding Feature, and Reaction Mechanism
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  • Yun-Jie Chu,
  • Gang Sun,
  • Xue-Mei Chen,
  • Chun-Guang Liu
Yun-Jie Chu
Northeast Electric Power University
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Gang Sun
Beihua University
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Xue-Mei Chen
Northeast Electric Power University
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Chun-Guang Liu
Beihua University
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Hydrogen peroxide (H2O2), as clean oxidant, has long suffered from low efficiency and selectivity for the oxidation of olefins. In the present paper, the redox important ferrate anion (FeO42-) has been anchored into a silanol-decorated polyoxometalates (POM) to form single–site supported Fe-POM catalyst. And possible reaction mechanism for the epoxidation of propylene with hydrogen peroxide (H2O2) catalyzed by the Fe-POM catalyst have been investigated based on density functional theory with M06L functional. The study of molecular geometry, electronic structure, and bonding feature shows that the Fe-POM complex can be viewed as a high-valent Fe-oxo (Fe=O) species. The propylene molecule was activated by the Fe-POM catalyst via an effective electron transfer from propylene to the Fe-POM catalyst to form a cation propylene radical. Due to the high reactivity of radical species, the calculated activation energy barrier is only 4.50 kcal mol-1 for epoxidation of propylene to epoxypropane catalyzed by the Fe-POM catalyst. Subsequently, the calculated free energy profiles show that H2O2 was decomposed into a H2O molecule and a surface O species over the Fe-POM catalyst, and the remaining O atom attaches to the exposed the Fe center, resulting in the replenishing of Fe-POM catalyst via a two-state reaction pathway. The calculated activation energy barrier for this process is 23.42 kcal mol–1, and thus decomposition of H2O2 is the rate-determining step for the whole reaction. The Fe center serves as an electron acceptor, accepting electrons from the binding propylene molecule to form radical species in the first half of the reaction, and acts as the role of electron donor in the rest reaction steps to eliminate the radical feature, reduce the reactivity, and stop the reaction at the stage of the desired epoxypropane product.

Peer review status:ACCEPTED

19 Jun 2020Submitted to International Journal of Quantum Chemistry
19 Jun 2020Submission Checks Completed
19 Jun 2020Assigned to Editor
10 Jul 2020Reviewer(s) Assigned
28 Jul 2020Review(s) Completed, Editorial Evaluation Pending
29 Jul 2020Editorial Decision: Revise Minor
09 Aug 20201st Revision Received
10 Aug 2020Submission Checks Completed
10 Aug 2020Assigned to Editor
10 Aug 2020Reviewer(s) Assigned
11 Aug 2020Review(s) Completed, Editorial Evaluation Pending
14 Aug 2020Editorial Decision: Accept