Nitrogen and sulfur doped ZnAl layered double hydroxide/reduced graphene oxide as an efficient nanoelectrocatalyst for oxygen reduction reactions

Abstract

In this work, to synthesize an efficient and low-cost electrocatalysts for Oxygen Reduction Reaction (ORR), the combination of N,S-rGO and ZnAl-LDH with several concentrations is studied for the first time. For this purpose, six electrocatalysts including Graphene Oxide (GO), functionalized reduced graphene oxide with nitrogen and sulfur atoms (N,S–rGO), Zinc–Aluminum layered double hydroxides (ZnAl-LDH), and ZnAl-LDH/N,S–rGO hybrids in three weight ratios of 1:1, 1:3, and 1:5 (the weight ratio of N,S-rGO is 1) are synthesized by the hydrothermal method. The physical properties, morphology, and structure of the synthesized electrocatalysts are determined by using X-Ray Diffraction (XRD) analysis, Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Analysis (EDX), the Fourier Transform Infrared Spectroscopy (FTIR) and Raman analysis. Electrochemical measurements are implemented by using Cyclic Voltammetry (CV), Linear Scanning Voltammetry (LSV), and chronoamperometric. Also, the electron transfer number is calculated by K-L plot. The obtained results for all samples are compared with the %20 Pt/C commercial catalyst. Based on the results of the physical tests, in addition to the uniform distribution and the correct deposition of the synthesized electrocatalysts, the particle size also reached the nanometer range. According to the electrochemical results, among the synthesized electrocatalysts, the ZnAl-LDH/N,S–rGO with 1:1 wt ratio has the best electrochemical activity. This result indicates a well synergistic and interaction effect between N,S–rGO and ZnAl-LDH for the ORR. The onset potential is obtained to be −0.01 V vs Ag/AgCl. The average of electron transfer number by this electrocatalyst is 3.60, which indicates that it is close to the 4e pathway for the ORR. The electrocatalytic stability was favorable in the alkaline medium. It can be concluded that the Layered Double Hydroxides (LDHs) improve the electrical conductivity, the electrocatalytic activity, the active surface area, and the stability for the oxygen reduction reaction after the combination with carbon bases. To be clear, the combination of N,S-rGO and ZnAl-LDH with several concentrations has been investigated for the first time on the ORR applications. The sensitivity analysis is implemented to determine the optimal concentration. This study proposes a new approach for using N, S-rGO composite to improve the low electron conductivity of LDHs.