Radical Polymerization by Heterogeneous Ceria Nanocatalysts

Yifan Sun; Zongyu Wang; Jihua Chen; Zhennan Huang; Hanxin Fu; Miaofang Chi; Mark A. Arnould; Sheng Dai

doi:10.1002/smll.202502142

Radical Polymerization by Heterogeneous Ceria Nanocatalysts

Yifan Sun, Zongyu Wang, Jihua Chen, Zhennan Huang, Hanxin Fu, Miaofang Chi, Mark A. Arnould, Sheng Dai

Research output: Contribution to journal › Article › peer-review

Abstract

Heterogeneous catalysts for radical polymerization are desired due to advantageous recyclability, which facilitates further purification and various applications. Herein, colloidal ceria (CeO₂) nanocrystals function as an efficient heterogeneous catalyst driving radical polymerization of methyl methacrylate (MMA). Enrichment of Ce³⁺ is observed on the CeO₂ surface upon polymerization, revealing a surface-mediated redox mechanism underpinned by the reversible formation of oxygen defects. The heterogeneous polymerization pathway is further extended to the preparation of SiO₂-grafted-PMMA particle brushes, which demonstrates the potential to access polymeric composite materials. The study provides an effective heterogeneous route to catalyzing radical polymerization that has been routinely realized with homogeneous catalysis. A wider scope of reducible metal oxides is anticipated to be explored, where compelling recyclability and tunable reactivities can be attained.

Original language	English
Article number	2502142
Journal	Small
Volume	21
Issue number	22
DOIs	https://doi.org/10.1002/smll.202502142
State	Published - Jun 5 2025

Funding

Y.S. and Z.W. contributed equally to this work. Y.S. acknowledges support from the National Natural Science Foundation of China (22205135), Shanghai Sailing Program under Grant 22YF1419600, Shanghai Pilot Program for Basic Research—Shanghai Jiao Tong University (21TQ1400219), Fundamental Research Funds for the Central Universities (23X010301599, 24X010301678), and start-up funds from Shanghai Jiao Tong University. Z.W. and S.D. acknowledge support from the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Y.S. and Z.W. contributed equally to this work. Y.S. acknowledges support from the National Natural Science Foundation of China (22205135), Shanghai Sailing Program under Grant 22YF1419600, Shanghai Pilot Program for Basic Research—Shanghai Jiao Tong University (21TQ1400219), Fundamental Research Funds for the Central Universities (23X010301599, 24X010301678), and start‐up funds from Shanghai Jiao Tong University. Z.W. and S.D. acknowledge support from the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Keywords

CeO nanocrystals
heterogeneous catalyst
radical polymerization

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10.1002/smll.202502142

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title = "Radical Polymerization by Heterogeneous Ceria Nanocatalysts",

abstract = "Heterogeneous catalysts for radical polymerization are desired due to advantageous recyclability, which facilitates further purification and various applications. Herein, colloidal ceria (CeO2) nanocrystals function as an efficient heterogeneous catalyst driving radical polymerization of methyl methacrylate (MMA). Enrichment of Ce3+ is observed on the CeO2 surface upon polymerization, revealing a surface-mediated redox mechanism underpinned by the reversible formation of oxygen defects. The heterogeneous polymerization pathway is further extended to the preparation of SiO2-grafted-PMMA particle brushes, which demonstrates the potential to access polymeric composite materials. The study provides an effective heterogeneous route to catalyzing radical polymerization that has been routinely realized with homogeneous catalysis. A wider scope of reducible metal oxides is anticipated to be explored, where compelling recyclability and tunable reactivities can be attained.",

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AU - Sun, Yifan

AU - Wang, Zongyu

AU - Chen, Jihua

AU - Huang, Zhennan

AU - Fu, Hanxin

AU - Chi, Miaofang

AU - Arnould, Mark A.

AU - Dai, Sheng

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Y1 - 2025/6/5

N2 - Heterogeneous catalysts for radical polymerization are desired due to advantageous recyclability, which facilitates further purification and various applications. Herein, colloidal ceria (CeO2) nanocrystals function as an efficient heterogeneous catalyst driving radical polymerization of methyl methacrylate (MMA). Enrichment of Ce3+ is observed on the CeO2 surface upon polymerization, revealing a surface-mediated redox mechanism underpinned by the reversible formation of oxygen defects. The heterogeneous polymerization pathway is further extended to the preparation of SiO2-grafted-PMMA particle brushes, which demonstrates the potential to access polymeric composite materials. The study provides an effective heterogeneous route to catalyzing radical polymerization that has been routinely realized with homogeneous catalysis. A wider scope of reducible metal oxides is anticipated to be explored, where compelling recyclability and tunable reactivities can be attained.

AB - Heterogeneous catalysts for radical polymerization are desired due to advantageous recyclability, which facilitates further purification and various applications. Herein, colloidal ceria (CeO2) nanocrystals function as an efficient heterogeneous catalyst driving radical polymerization of methyl methacrylate (MMA). Enrichment of Ce3+ is observed on the CeO2 surface upon polymerization, revealing a surface-mediated redox mechanism underpinned by the reversible formation of oxygen defects. The heterogeneous polymerization pathway is further extended to the preparation of SiO2-grafted-PMMA particle brushes, which demonstrates the potential to access polymeric composite materials. The study provides an effective heterogeneous route to catalyzing radical polymerization that has been routinely realized with homogeneous catalysis. A wider scope of reducible metal oxides is anticipated to be explored, where compelling recyclability and tunable reactivities can be attained.

KW - CeO nanocrystals

KW - heterogeneous catalyst

KW - radical polymerization

UR - https://www.scopus.com/pages/publications/105003807622

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VL - 21

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Radical Polymerization by Heterogeneous Ceria Nanocatalysts

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