Issue 8, 2024

Cation substitution effects (Mn, Ni, and Zn) on ZIF-67 derived spinel modified with 3DGO for the detection of NO2 gas with high sensitivity and selectivity

Abstract

The need to improve the sensitivity, selectivity and stability of NO2-based gas sensors that are capable of monitoring toxic gases in the environment has sparked research attention among scientists. In this direction, herein, we propose three different cation-substituted MOF-derived spinels (MCo2O4, M = Zn, Ni, and Mn) using ZIF-67 as a template for potential NO2-based gas sensors. Among the three spinel-based sensors, the ZnCo2O4 spinel showed enhanced sensitivity. Our results showed that the sensing performances of MCo2O4 having a slightly distorted dodecahedron shaped structure varied when different cations (M2+ = Zn, Ni, and Mn) were substituted into the MCo2O4 spinels. In comparison to the other two spinels, such as NiCo2O4 and MnCo2O4, the perfect dodecahedron-shaped ZnCo2O4 nanostructures allowed more open pores for better gas diffusion and provided more active sites for gas adsorption, while maintaining good electrical conductivity. This p-type sensor also exhibited an ultralow detection limit of up to 5 ppm towards NO2 detection with fast response and recovery, as well as adequate selectivity. The pristine ZnCo2O4 showed higher responses (S% = 7.6%) with low response time (10 s) and recovery time (13 s) at higher temperature (150 °C). Later on, to enhance its performance, ZnCo2O4 was supported on 3D-graphene oxide (3DGO) to develop an efficient composite sensor for sensing at room temperature. The composite (3DGO-ZnCo2O4) showed p-type responses and formed a n–p heterojunction at their interface with an enhanced sensing performance of about 17.6% and lowest response–recovery time (7 s and 9 s, respectively) at room temperature. Our study demonstrated the advantages of combining the effects of higher electrical conductivity and larger specific surface of 3DGO with enhanced surface defects in MOF-derived ZnCo2O4 for the adsorption of greater number of NO2 gas molecules.

Graphical abstract: Cation substitution effects (Mn, Ni, and Zn) on ZIF-67 derived spinel modified with 3DGO for the detection of NO2 gas with high sensitivity and selectivity

Supplementary files

Article information

Article type
Paper
Submitted
02 Apr 2023
Accepted
27 Jun 2023
First published
28 Jun 2023

Environ. Sci.: Nano, 2024,11, 3637-3656

Cation substitution effects (Mn, Ni, and Zn) on ZIF-67 derived spinel modified with 3DGO for the detection of NO2 gas with high sensitivity and selectivity

B. Maji, A. Das, B. Barik and P. Dash, Environ. Sci.: Nano, 2024, 11, 3637 DOI: 10.1039/D3EN00205E

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