N, S-codoped CNTs supported Co4S3 nanoparticles prepared by using CdS nanorods as sulfur sources and hard templates: An efficient catalyst for reversible oxygen electrocatalysis

Dengke Zhao; Zhenghua Tang; Wei Xu; Zexing Wu; Li-Jun Ma; Zhiming Cui; Chenghao Yang; Ligui Li

doi:10.1016/j.jcis.2019.10.069

N, S-codoped CNTs supported Co₄S₃ nanoparticles prepared by using CdS nanorods as sulfur sources and hard templates: An efficient catalyst for reversible oxygen electrocatalysis

J Colloid Interface Sci. 2020 Feb 15:560:186-197. doi: 10.1016/j.jcis.2019.10.069. Epub 2019 Oct 18.

Authors

Dengke Zhao¹, Zhenghua Tang², Wei Xu², Zexing Wu³, Li-Jun Ma⁴, Zhiming Cui⁵, Chenghao Yang², Ligui Li⁶

Affiliations

¹ Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China; Guangdong Provincial Key Laboratory of Petrochemical Pollution Process and Control, Guangdong University of Petrochemical Technology, Maoming 525000, China.
² Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China.
³ State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, No. 53 Zhengzhou Road, 266042 Qingdao, China.
⁴ Key Laboratory of Theoretical Chemistry of Environment Ministry of Education, School of Chemistry and Environment, South China Normal University, Shipai, Guangzhou 510631, China.
⁵ Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China.
⁶ Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China; Guangdong Provincial Key Laboratory of Petrochemical Pollution Process and Control, Guangdong University of Petrochemical Technology, Maoming 525000, China; State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, South China University of Technology, Guangzhou 510641, China. Electronic address: [email protected].

PMID: 31670016
DOI: 10.1016/j.jcis.2019.10.069

Abstract

Non-precious efficient bifunctional catalysts towards oxygen reduction/evolution reactions (ORR/OER) are highly desired to enable the widespread application of rechargeable Zn-air batteries (r-ZABs). Herein, Prussian blue analogues (PBA) anchored on CdS nanorods (CdS NRs) pre-coated with polydopamine (PDA) are utilized as precursors to prepare ultrafine Co₄S₃ nanoparticles supported on N, S-codoped CNTs (Co₄S₃@N,S-CNT), where CdS NRs are served as sulfur sources and hard templates. After pyrolysis, the resulting Co₄S₃@N,S-CNT-800 shows a high specific surface area of 142.4 m² g^-1, together with merely 0.780 V difference between the OER potential at 10 mA cm^-2 and the ORR potential at 3 mA cm^-2. The Co₄S₃@N,S-CNT-800 based air cathode displays a higher discharge capacity of 787 mAh g_Zn^-1 at 10 mA cm^-2, a higher output power density of 154 mW cm^-2, better working stability, as well as a lower charge-discharge voltage gap than the Pt/C + RuO₂ based air electrode at various working current density. The remarkable oxygen reversible catalytic activities are mainly attributed to the presence of a thin layer of mesoporous carbon on partial sections of the open-end N,S-CNTs, which not only shortens the mass diffusion length but also prevents N,S-CNTs from excessively bundling to maximize the exposure of Co₄S₃ nanocrystallites and graphitized carbon skeletons with N or S heteroatoms.

Keywords: CdS nanorod; Oxygen evolution reaction; Oxygen reduction reaction; Prussian blue analogue; Rechargeable Zn-air battery.