Hierarchical N-doped CNTs grafted onto MOF-derived porous carbon nanomaterials for efficient oxygen reduction

Yuanyuan Guo; Anrui Dong; Qi Huang; Qipeng Li; Yue Hu; Jinjie Qian; Shaoming Huang

doi:10.1016/j.jcis.2021.08.180

Hierarchical N-doped CNTs grafted onto MOF-derived porous carbon nanomaterials for efficient oxygen reduction

J Colloid Interface Sci. 2022 Jan 15;606(Pt 2):1833-1841. doi: 10.1016/j.jcis.2021.08.180. Epub 2021 Aug 28.

Authors

Yuanyuan Guo¹, Anrui Dong¹, Qi Huang¹, Qipeng Li², Yue Hu¹, Jinjie Qian³, Shaoming Huang⁴

Affiliations

¹ Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, PR China.
² College of Chemistry and Chemical Engineering, Zhaotong University, Zhaotong, PR China.
³ Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, PR China; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, PR China. Electronic address: jinjieqian@wzu.edu.cn.
⁴ School of Materials and Energy, Guangdong University of Technology, Guangzhou, PR China.

PMID: 34507174
DOI: 10.1016/j.jcis.2021.08.180

Abstract

The rational design and preparation of nonprecious metal-based oxygen reduction reaction (ORR) catalysts to facilitate electron and mass transport are of great significance in oxygen-involved energy applications. Herein, a stepwise approach to synthesize a type of hierarchically porous N-doped carbon nanotubes (CNTs) grafted onto zinc-based coordination polymer derived carbon nanomaterials (M-NCNT, M = Fe/Co/Ni) is proposed. At first, an isostructural zinc-based metal-organic framework (MOF) to HKUST-1(Cu) (ZnHKUST-1) is solvothermally prepared, and then under pyrolysis to obtain MOF-derived porous carbon. After the secondary calcination, the in-situ formed N-doped CNTs are efficiently catalyzed by iron group metal-based nanoparticles (Fe/Co/Ni), which are thermally reduced by porous carbon together with additional urea. The synergistic effect between ultrahigh porosity, large surface area, suitable N-doping, high graphitization degree, and ultrafine metal particles prompts M-NCNT series to exhibit satisfactory electrocatalysis in oxygen reduction. Among them, Fe-NCNT owns the optimal ORR activity with high positive onset potential (0.987 V), half-wave potential (0.860 V) and large diffusion-limited current density (4.893 mA cm^-2). Meanwhile, it shows a high current retention of 90.7% after the 24-hour stability, and the obtained Zn-air battery by Fe-NCNT with open-circuit voltage of 1.44 V owns moderate capacity and satisfying stability. The demonstrated method to prepare hierarchically porous N-doped carbon nanomaterials stemmed from MOF precursors unfolds a new route for the facile construction of efficient nanocatalysts for advanced energy applications.

Keywords: Carbon nanotube; Metal-organic framework; Oxygen reduction reaction; Porous carbon; Zn-air battery.