Recent Progress in Spinel Ferrite (MFe2O4) Chemiresistive Based Gas Sensors

Abstract

Gas-sensing technology has gained significant attention in recent years due to the increasing concern for environmental safety and human health caused by reactive gases. In particular, spinel ferrite (MFe₂O₄), a metal oxide semiconductor with a spinel structure, has emerged as a promising material for gas-sensing applications. This review article aims to provide an overview of the latest developments in spinel-ferrite-based gas sensors. It begins by discussing the gas-sensing mechanism of spinel ferrite sensors, which involves the interaction between the target gas molecules and the surface of the sensor material. The unique properties of spinel ferrite, such as its high surface area, tunable bandgap, and excellent stability, contribute to its gas-sensing capabilities. The article then delves into recent advancements in gas sensors based on spinel ferrite, focusing on various aspects such as microstructures, element doping, and heterostructure materials. The microstructure of spinel ferrite can be tailored to enhance the gas-sensing performance by controlling factors such as the grain size, porosity, and surface area. Element doping, such as incorporating transition metal ions, can further enhance the gas-sensing properties by modifying the electronic structure and surface chemistry of the sensor material. Additionally, the integration of spinel ferrite with other semiconductors in heterostructure configurations has shown potential for improving the selectivity and overall sensing performance. Furthermore, the article suggests that the combination of spinel ferrite and semiconductors can enhance the selectivity, stability, and sensing performance of gas sensors at room or low temperatures. This is particularly important for practical applications where real-time and accurate gas detection is crucial. In conclusion, this review highlights the potential of spinel-ferrite-based gas sensors and provides insights into the latest advancements in this field. The combination of spinel ferrite with other materials and the optimization of sensor parameters offer opportunities for the development of highly efficient and reliable gas-sensing devices for early detection and warning systems.

Keywords: chemiresistive gas sensor; doping; heterostructure; metal oxide semiconductor; nanostructure; spinel ferrite.

Figure 1

The crystal structure of ZnFe₂O₄, with Zn²⁺ in the tetrahedron gap and Fe³⁺ in the octahedron gap.

Figure 2

(a) The effect of operating temperature of the CdFe₂O₄ sensor on the various gas responses. (b) Response of the sensors to 100 ppm ethanol at different operating temperatures. (c) XRD pattern of (Co, Cu, Ni, and Zn) ferrite thin films. (d) Response value of (Co, Cu, Ni, and Zn) ferrite thin films to 5 ppm LPG at different operating temperatures. (e) Size of CoFe₂O₄ nanoparticles dependent on response value (%) with varying temperatures for 200 ppm ethanol. (f) The sensitivity of individual CoFe₂O₄ sensors to 100 ppm methanol across varying temperature conditions. (a) Reproduced with permission [43], copyright 1998, Elsevier B.V. (b) Reproduced with permission [35], copyright 2022, Elsevier B.V. (c,d) Reproduced with permission [51], copyright 2015, Elsevier B.V. (e) Reproduced with permission [52], copyright 2015, IEEE Xplore. (f) Reproduced with permission [54], copyright 2020, IEEE Xplore.

Figure 3

(a) XRD of the synthesized MgFe₂O₄ samples. (b)Variation in the response of MgFe₂O₄ samples at 300 °C. (c) HRTEM image showing cubic NiFe₂O₄. (d) H₂S sensitivity of NiFe₂O₄ with various milled times at operating temperatures. (e) Responses of sensors to 500 ppm acetone at various temperatures. (f) TEM images of the synthesized ZnFe₂O₄ nanoparticles. (a,b) Reproduced with permission [69], copyright 2018, Elsevier B.V. (c,d) Reproduced with permission [78], copyright 2015, Elsevier B.V. (e,f) Reproduced with permission [92], copyright 2015, Elsevier B.V.

Figure 4

(a) The sensitivity–temperature characteristics of various MFe₂O₄ sensors in detecting formaldehyde. (b) The sensitivity-temperature characteristics of various MFe₂O₄ sensors in detecting formaldehyde ethanol: (a) Fe₃O₄, (b) CoFe₂O₄, (c) NiFe₂O₄, (d) MgFe₂O₄, (e) CdFe₂O₄, (f) ZnFe₂O₄. (c) TEM image of the ZnFe₂O₄ nanoparticles. (d) Comparative analysis of the NO₂ response among sensors based on ZFO-300, ZFO-500, and ZFO-700 materials when exposed to 10 ppm NO₂ at varying operating temperatures. (e) The TEM image of ZnFe₂O₄ nanoparticles at low magnification. (f) The response values of sensors based on ZnFe₂O₄ nanoparticles to 5 ppm H₂S gas at different working temperatures. (g) Cross-sectional FESEM image of the ZnFe₂O₄ film. (h) Total density of states (TDOS) of the ZnFe₂O₄. (a,b) Reproduced with permission [93], copyright 2016, Elsevier B.V. (c,d) Reproduced with permission [99], copyright 2019, Royal Society of Chemistry. (e,f) Reproduced with permission [110], copyright 2018, Elsevier B.V. (g,h) Reproduced with permission [102], copyright 2022, IEEE Xplore.

Figure 5

(a) SEM image and (b) TEM image of as-prepared NiFe₂O₄ nanorods. (c) The dynamic response−recovery characteristics of NiFe₂O₄ nanorods to n-propanol at different concentrations. Insert: response and recovery curve of the sensor to 100 ppm n-propanol. (d) TEM image of NiFe₂O₄ nanorods. (e) SEM images of ZnFe₂O₄ nanofiber. (f) SEM images of porous ZnFe₂O₄ nanorods. (g) SEM images of ZnFe₂O₄ nanosheets. (h) The response values of the sensors to 1 ppm H₂S at various operating temperatures. (a–c) Reproduced with permission [115], copyright 2018, Wiley-VCH. (d) Reproduced with permission [116], copyright 2007, Elsevier B.V. (e) Reproduced with permission [123], copyright 2018, Elsevier B.V. (f) Reproduced with permission [122], copyright 2017, Elsevier B.V. (g,h) Reproduced with permission [129], copyright 2017, Elsevier B.V.

Figure 6

(a) SEM and TEM images of the NiFe₂O₄ polyhedron. (b) The response comparison of sensors to 50 ppm TEA at various temperatures. (c) SEM image and TEM image (inset) of the ZnFe₂O₄ sphere. (d) Comparative analysis of the 30 ppm acetone response of porous ZnFe₂O₄ nanospheres and the 100 ppm acetone response of ZnFe₂O₄ nanoparticles at varying operating temperatures. (e) XRD patterns of ZnFe₂O₄ double-shell, yolk–shell, and solid microspheres. (f) The sensitivity–temperature characteristics of the ZnFe₂O₄ double-shell, yolk–shell, and solid microsphere-based sensors in detecting 20 ppm acetone. (g) SEM image and TEM image (inset) of the hierarchical ZnFe₂O₄ microspheres. (h) Dynamic curve of the gas sensor to acetone with different concentrations at 215 °C. (a,b) Reproduced with permission [142], copyright 2020, Royal Society of Chemistry. (c,d) Reproduced with permission [147], copyright 2015, Elsevier B.V. (e,f) Reproduced with permission [153], copyright 2018, Elsevier B.V. (g,h) Reproduced with permission [149], copyright 2015, American Chemical Society.

Figure 7

(a) FESEM image of embedded Mg₀.₅Zn₀.₅Fe₂O₄ nanotubes. (b) Resistance transients of embedded Mg₀.₅Zn₀.₅Fe₂O₄ nanotubes towards H₂ (∼1660 ppm). (c) Dynamic curve of the resistance embedded Mg0.₅Zn₀.₅Fe₂O₄ nanotube sensors to the 10–1660 ppm range of H₂ at ∼350 °C. (d) Variations of the lattice constant with Ni content of NiZnFe₂O₄ system. (e) SEM image of the isolated Mg₀.₅Zn₀.₅Fe₂O₄ nanotubes. (f) Resistance transient of isolated Mg₀.₅Zn₀.₅Fe₂O₄ nanotubes to 1660 ppm H₂. (g) Dynamic curve of the resistance isolated Mg0.₅Zn₀.₅Fe₂O₄ nanotube sensors to the 10–1660 ppm range of H₂ at 350 °C. (h) Response of sensors based on Ni_xZn_1−xFe₂O₄ (x = 0, 0.6, 1.0) to LPG gas at different operating temperatures. (i) The TEM images and SAED pattern of Ni₀._7−xMn_xZn₀.₃Fe₂O₄. (j) Small-range XRD patterns of the pure ZFNPs and Cu-ZFNPs with different Cu concentrations. (k) The variation in sensitivity with operating temperatures of pure ZFNPs and Cu-ZFNPs for 5 ppm H₂S. (l) The response−concentration plots of Ni₀.₄Mn₀.₃Zn₀.₃Fe₂O₄ towards different test gases. (a–c,e–g) Reproduced with permission [155], copyright 2013, Elsevier B.V. (d,h) Reproduced with permission [90], copyright 2015, Springer Nature. (i,l) Reproduced with permission [199], copyright 2022, Elsevier B.V. (j,k) Reproduced with permission [187], copyright 2019, Elsevier B.V.

Figure 8

(a) HRTEM images of MgCe₀.₂Fe₁.₈O₄. (b) The XRD patterns of MgCe_xFe_2−xO₄. (c) Responses of MgCe_xFe_2−xO₄ nanoferrites (x = 0, 0.05, 0.1, and 0.2) to various gas with 100 ppm. (d) TEM image of CZLF ferrite with x = 0.1. (e) XRD pattern of La³⁺-CZLF powders. (f) The resistance plot of a sensor based on Co₀.₇Zn₀.₃La₀.₁Fe₁.₉O₄. (a–c) Reproduced with permission [207], copyright 2020, Elsevier B.V. (d–f) Reproduced with permission [214], copyright 2022, Elsevier B.V.

Figure 9

(a) HRTEM images of the Au nanoparticles/ZFO yolk–shell spheres and the inset is the size distribution of Au nanoparticles (marked with red circle). (b) Dynamic curve of the gas sensor based on the ZFO and Au/ZFO sphere to CB with different concentrations at 150 °C. (c) TEM images of 0.25 wt.% Ag/ZnFe₂O₄. (d) The effect of operating temperatures of the Ag/ZnFe₂O₄-sensor on the various gas responses of the sensors to 100 ppm acetone vapor at 125–200 °C. (e) SEM and (f) TEM images of ZnO/ZnFe₂O₄/Au ternary heterostructure. (g) Responses–temperature characteristics of the ZnO/ZnFe₂O₄/Au sensors to 100 ppm acetone. (h) The responses of sensors to ZnFe₂O₄ thick films vs. the content of V doping. (a,b) Reproduced with permission [220], copyright 2019, American Chemical Society. (c,d) Reproduced with permission [224], copyright 2018, Elsevier B.V. (e–g) Reproduced with permission [219], copyright 2019, Elsevier B.V. (h) Reproduced with permission [233], copyright 2006, Elsevier B.V.

Figure 10

(a) SEM and (b) TEM images of NiO/NiFe₂O₄. (c) Dynamic curve of the NiO/NiFe₂O₄-sensor to formaldehyde with different concentrations at 240 °C. (d) SEM image of Fe₂O₃/ZnFe₂O₄. (e) Comparative analysis of the 100 ppm TEA response among sensors based on Fe₂O₃ spindles and Fe₂O₃/ZnFe₂O₄ at varying operating temperatures. (f) SEM images of CuO/CuFe₂O₄. (g) Comparative analysis of the 100 ppm TEA response among sensors based on CuO microspheres, CuFe₂O₄ nanoparticles, and CuO/CuFe₂O₄ heterostructure at varying operating temperatures. (h) TEM images of Fe₂O₃/CuFe₂O₄ composite. (i) Gas-sensing performances of hollow Fe₂O₃ and CuFe₂O₄/Fe₂O₃-2-composite-based sensors under various concentrations of acetone ranging from 5 to 500 ppm. (a–c) Reproduced with permission [258], copyright 2020, Elsevier B.V. (d,e) Reproduced with permission [254], copyright 2020, Elsevier B.V. (f,g) Reproduced with permission [248], copyright 2018, Elsevier B.V. (h,i) Reproduced with permission [29], copyright 2018, Elsevier B.V.

Figure 11

(a) SEM images of hollow ZnO/ZnFe₂O₄ microspheres. (b) Response value towards acetone with 0.1–5 ppm. (c) N₂ adsorption−desorption isotherms for ZnO/ZnFe₂O₄ nanocages (inset is the pore size distribution). (d,e) SEM images of the coral-like ZnO/ZnFe₂O₄ with different magnifications. (f) Dynamic response/recover curves of the coral-like ZnO/ZnFe₂O₄ to different TEA concentrations at 240 °C. (g) Dynamic continuous response of ZnO/ZnFe₂O₄ hollow nanocages to 100 ppm acetone at 290 °C. (a,b) Reproduced with permission [287], copyright 2017, Elsevier B.V. (c,g) Reproduced with permission [278], copyright 2017, Elsevier B.V. (d–f) Reproduced with permission [41], copyright 2019, Elsevier B.V.

Figure 12

(a) TEM image of g-C₃N₄. (b) SEM image of MgFe₂O₄/g-C₃N₄ composites. (c) TEM images of ZnFe₂O₄/GQDs. (d) The dynamic response/recover curves of the sensor based on the sample S-15 composite to various concentrations of acetone at RT. (e) SEM image of 9WO₃-ZnFe₂O₄. (f) SEM micrographs of the 0.8 wt.% rGO/9WO₃/ZnFe₂O₄ composite. (g) SEM images of PANI/CuFe₂O₄. (h) The sensitivity–temperature characteristics of the sensors based on MgFe₂O₄/g-C₃N₄ composites to 500 ppm acetone. (i) Dynamic responses curve of the different ratio of rGO/WO₃/ZnFe₂O₄ composites; (j) Response of the sensors toward NH₃ at 20 °C. (k) Response and recovery curves of the sensors toward 5 ppm NH₃ at 20 °C. (a,b,h) Reproduced with permission [290], copyright 2018, MDPI. (c,d) Reproduced with permission [291], copyright 2019, Elsevier B.V. (e,f,i) Reproduced with permission [298], copyright 2021, Elsevier B.V. (g,j,k) Reproduced with permission [307], copyright 2020, Elsevier B.V.