Template-free construction of hollow mesoporous carbon spheres from a covalent triazine framework for enhanced oxygen electroreduction

Yong Zheng; Shan Chen; Kai A I Zhang; Jingyu Guan; Xiaohui Yu; Wei Peng; Hui Song; Jixin Zhu; Jingsan Xu; Xiaoshan Fan; Chao Zhang; Tianxi Liu

doi:10.1016/j.jcis.2021.11.048

Template-free construction of hollow mesoporous carbon spheres from a covalent triazine framework for enhanced oxygen electroreduction

J Colloid Interface Sci. 2022 Feb 15;608(Pt 3):3168-3177. doi: 10.1016/j.jcis.2021.11.048. Epub 2021 Nov 15.

Authors

Yong Zheng¹, Shan Chen¹, Kai A I Zhang², Jingyu Guan³, Xiaohui Yu¹, Wei Peng¹, Hui Song¹, Jixin Zhu⁴, Jingsan Xu⁵, Xiaoshan Fan⁶, Chao Zhang⁷, Tianxi Liu⁸

Affiliations

¹ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, PR China.
² Department of Materials Science, Fudan University, Shanghai 200433, PR China. Electronic address: kai_zhang@fudan.edu.cn.
³ State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, PR China.
⁴ Shaanxi Institute of Flexible Electronics (SIFE), Northwestern Polytechnical University (NPU), 127 West Youyi Road, Xi'an 710072, PR China.
⁵ School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, QLD 4001, Australia.
⁶ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, PR China. Electronic address: xsfan@dhu.edu.cn.
⁷ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, PR China. Electronic address: czhang@dhu.edu.cn.
⁸ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, PR China; Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China.

PMID: 34809992
DOI: 10.1016/j.jcis.2021.11.048

Abstract

The construction of hollow mesoporous carbon nanospheres (HMCS) avoiding the use of traditional soft/hard templates is highly desired for nanoscience yet challenging. Herein, we report a simple and straightforward template-free strategy for preparing nitrogen, sulfur dual-doped HMCSs (N/S-HMCSs) as oxygen reduction reaction (ORR) electrocatalysts. The unique hollow spherical and mesoporous structure was in-situ formed via a thermally initiated hollowing pathway from an elaborately engineered covalent triazine framework. Regulation of pyrolysis temperatures contributed to precisely tailoring of the shell thickness of HMCSs. The resulting N/S-HMCS₉₀₀ (pyrolyzed at 900 °C) possessed high N and S contents, large specific surface areas, rich and uniform mesopores distribution. Consequently, as a metal-free ORR electrocatalyst, N/S-HMCS₉₀₀ exhibits a high half-wave potential, excellent methanol tolerance and great long-term durability. Additionally, density functional theory calculations demonstrate that N, S-dual dopant can create extra active sites with higher catalytic activity than the isolated N-dopant. This strategy provides new insights into the construction of hollow and mesoporous multi-heteroatom-doped carbon materials with tunable nanoarchitecture for various electrochemical applications.

Keywords: Covalent triazine framework; Hollow mesoporous carbon nanospheres; N; Oxygen reduction reaction; S-dual doping; Template-free.