Modulating free radical types in ZnSn(OH)6 through orbital rehybridization by interstitial C-doping for deep oxidation of toluene

doi:10.1016/j.jmst.2025.01.079

J. Mater. Sci. Technol. ›› 2026, Vol. 246: 247-255.DOI: 10.1016/j.jmst.2025.01.079

• Research Article • Previous Articles Next Articles

Modulating free radical types in ZnSn(OH)₆ through orbital rehybridization by interstitial C-doping for deep oxidation of toluene

Wenji Pu^a,1, Yunqiao Zhou^b,1, Xinyuan Song^a, Zeyong Meng^a, Jiawei Niu^c, Yuhan Li^a,*, Youyu Duan^d,e,*, Sónia A.C. Carabineiro^f, Wanjun Wang^g, Fan Dong^h

^aEngineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Key Laboratory of Catalysis and New Environmental Materials, Chongqing Technology and Business University, Chongqing 400067, China;
^bBeijing Key Laboratory of Farmland Soil Pollution Prevention and Remediation, College of Resources and Environmental Science, China Agricultural University, Beijing 100193, China;
^cChongqing College of the University of the Chinese Academy of Sciences, Chongqing University, Chongqing 400044, China;
^dSchool of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, China;
^eChongqing Institute of New Energy Storage Materials and Equipment, Chongqing 401120, China;
^fLAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, Universidade NOVA de Lisboa, Caparica 2829-516, Portugal;
^gCollege of environmental science and engineering, Guangdong University of Technology, Guangdong 510006, China;
^hResearch Center for Environmental and Energy Catalysis, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China

Received:2024-12-21 Revised:2025-01-09 Accepted:2025-01-29 Published:2026-03-01 Online:2025-04-08
Contact: *E-mail addresses: lyhctbu@126.com (Y. Li), youyuduan@cqjtu.edu.cn (Y. Duan).
About author:¹These authors contributed equally to this work.

Abstract

Abstract: Toluene (C₇H₈) has a stable benzene ring structure and inert C(sp³)-H bonds, making its deep mineralization a significant challenge. Here, we prepared a C-doping zinc hydroxystannate photocatalyst (ZHS-C5) by a simple microwave method, showing excellent performance (degradation rate of 91.25%) in the mineralization of C₇H₈ into CO₂. A series of characterization experiments reveal the unique molecular structure of ZHS-C5, with C being doped into the gaps of the ZHS crystal, forming C=O bonds with surface lattice oxygen, and generating oxygen vacancies (OVs), leading to a redistribution of electrons. Experimental and theoretical results elucidate the reason for the improved photocatalytic activity, as the interstitial C-doping can effectively transfer electrons to O₂ through p-orbital hybridization, enhancing O₂ adsorption and activation to form ·O₂^-. Additionally, OVs can efficiently adsorb C₇H₈, and using activated ·O₂^- from adjacent C sites, mineralize it into CO₂ and H₂O. This avoids quenching due to long-distance radical transfer, improving the efficiency of radical utilization. Finally, the detection of oxidation products using in situ infrared technology proposes a possible oxidation pathway for C₇H₈. This work may shed light on the design of efficient photocatalysts for C₇H₈ mineralization.

Key words: ZnSn(OH)₆, Interstitial doping, Orbital hybridization, Mineralization, C₇H₈

Wenji Pu, Yunqiao Zhou, Xinyuan Song, Zeyong Meng, Jiawei Niu, Yuhan Li, Youyu Duan, Sónia A.C. Carabineiro, Wanjun Wang, Fan Dong. Modulating free radical types in ZnSn(OH)₆ through orbital rehybridization by interstitial C-doping for deep oxidation of toluene[J]. J. Mater. Sci. Technol., 2026, 246: 247-255.

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Modulating free radical types in ZnSn(OH)₆ through orbital rehybridization by interstitial C-doping for deep oxidation of toluene

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