Study on Adsorption Characteristics and Sensing Performance of Zr-MOF-808@GO for SF6 Discharge Decomposition Gas

doi:10.21203/rs.3.rs-8226201/v1

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Study on Adsorption Characteristics and Sensing Performance of Zr-MOF-808@GO for SF6 Discharge Decomposition Gas

https://doi.org/10.21203/rs.3.rs-8226201/v1

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Sulfur hexafluoride (SF₆) gas-insulated switchgear (GIS) is widely used in electrical power engineering. The decomposition products of SF₆ have attracted significant attention as key indicators for assessing the operational safety of GIS. Consequently, developing sensing materials capable of detecting SF₆ decomposition products at or near room temperature has become a significant research objective in this field. Resistive chemical sensors are commonly employed as research tools in gas detection studies and have been applied to the development of such sensing materials. Zr-MOF-808, a metal–organic framework known for its excellent gas adsorption properties, is widely used in gas storage applications. However, its practical application in chemical sensing is limited by its high initial electrical resistance and excessive gas response sensitivity. In this study, a Zr-MOF-808@GO composite was synthesized by coating Zr-MOF-808 with graphene oxide (GO). The introduction of GO, which possesses a large specific surface area and excellent electrical conductivity, serves three main purposes: (1) it mitigates the adverse effect of the high intrinsic resistivity of Zr-MOF-808 on the detection accuracy of resistive sensors; (2) it partially blocks the porous structure of Zr-MOF-808, reducing effective gas–material contact; and (3) it occupies active adsorption sites through electron pair interactions between oxygen atoms in GO and zirconium in the MOF, thereby attenuating the adsorption capacity. This synergistic interaction passivates the gas adsorption effect of the MOF, bringing the resistive response into a more readily measurable range.Furthermore, due to differences in adsorption energy and electron transfer between Zr-MOF-808@GO and various gas molecules, the composite exhibits distinct rates of resistance increase, enabling the discriminative detection of SF6 decomposition gases. By adjusting the mass ratio of Zr-MOF-808 to GO, the sensing responses to major SF6 decomposition products were systematically investigated. The resistance response trends indicate that a mass ratio of 1:2 provides optimal differentiation among the four target gases (CF₄ < SO₂F₂ < H₂S < SO₂). In addition, density functional theory (DFT) calculations were employed to elucidate the underlying adsorption mechanisms, revealing principles for selective gas detection.

Zr-MOF-808

SF6

gas sensing

Metal-organic frameworks (MOFs)^1–5 have been extensively studied over the past two decades as a new type of inorganic-organic hybrid crystal material and have become a classic platform for various advanced functional materials and applications⁶. Due to the design flexibility, structural diversity, and plasticity^7–12 of MOFs, these materials exhibit unique structural features and physicochemical properties. Li et al. reported the synthesis of monocarboxylate-based MOFs, whose surface area and pore volume are superior to those of traditional porous crystalline zeolites²⁰. The porous structure and high specific surface area make MOFs and their derivatives ideal candidate materials for gas adsorption/separation and electrochemical energy storage systems^13–19. Chen et al. prepared MOF-14, which can reversibly adsorb large amounts of gases and organic solvents²¹.

Modification of MOFs materials, such as the development of MOF-based composite systems, can enhance their functional properties by utilizing the synergistic effect between composite components, thereby expanding their application range^22–24. Thornton et al. found that using magnesium-modified Mg(10)C(60) fullerene-impregnated MOF structures (denoted as Mg-C(60)@MOF) promoted the close interaction between the gas and the MOF, improving the methane absorption capacity²⁵. In addition, the modification of MOFs can improve their conductivity. Chen et al. synthesized graphene oxide-doped carbon-supported Eu₂O₃ modified Fe₃O₄ catalysts (Fe₃O₄/Eu₂O₃@NCG) using layered Fe-Eu-MOF/GO precursors. The resulting carbon-metal-carbon structure is rich in oxygen vacancies and variable metal active sites, exhibiting excellent conductivity²⁶.

Due to the excellent adsorption properties of MOF composites for gases, they have great potential in the detection of gases from the discharge decomposition of SF₆. Resistive sensors, as a classic gas sensing method, are widely used in the detection research of the aforementioned gases²⁷. This paper also uses a resistive sensor to study the gas sensing characteristics of Zr-MOF-808 composites.

The experimental study of the response of intrinsic Zr-MOF-808 to four SF₆ mixtures containing 10 ppm SO₂ or H₂S or SO₂F₂ or CF₄ (Figure S1) shows that: (1) the material adsorbs a large amount of gas in a short time, leading to a rapid increase in the material's resistivity; (2) the initial resistance of the material is high, and after adsorbing the gas, it reaches the upper limit of the resistive sensor's detection range in a short time.

To facilitate the detection of SF₆ discharge decomposition component gases by Zr-MOF-808, two modification objectives were set: (1) reducing the amount of gas adsorbed or the adsorption efficiency to make the results easier to observe; and (2) reducing the initial resistance value so that a complete adsorption characteristic curve could be observed in the experiment. This paper uses oligolayer graphene oxide (GO), which has good conductivity, to synthesize a composite material with Zr-MOF-808 to achieve the above-mentioned material modification objectives. Petit et al. elucidated that in the MOF/GO composite system, GO enhances the dispersion interaction, while the MOF component promotes the expansion of the pore space, thus facilitating the containment of the adsorbent²⁸. Their results further show that the structural diversity of MOF can provide active sites for reactive adsorption or heterogeneous catalysis, while the introduction of GO significantly improves the conductivity of the composite material. Experimental results of Zr-MOF-808@GO show that the introduction of GO reduces the resistivity of the system and modulates the adsorption characteristics in the following two ways: 1) it partially passivates the unsaturated Zr coordination sites through the interaction of oxygen-containing groups, reducing the number of unsaturated Zr ions; 2) it covers the pores, reducing the effective surface area for gas adsorption and weakening the diffusion of gas molecules into the porous framework.

2.1. Materials

The Zr-MOF-808 nanoparticles, measuring the size of ~ 200 nm, were supplied from Shanghai McLean Biochemical Technology Co., Ltd. The graphene oxide (GO) dispersion, with the concentration of 10 mg/mL, was obtained from Nanjing XFNANO Materials Technology Co., Ltd. All reagents had a purity exceeding 99.0% and were directly utilized without further purification treatment. Deionized water (DI) was homemade with a conductivity of 10 µs/cm.

2.2. Experimental method

Zr-MOF-808 was dispersed in 10 mL of DI water and then added to a GO dispersion. The mixture was vigorously stirred for 6 h to form a homogeneous Zr-MOF-808/GO dispersion. After that, the dispersion was subsequently subjected to a stepwise vacuum impregnation process in a vacuum drying oven upon the following conditions: first at 80°C and 0.7 Bar for 1 h, then at 80°C and 0.3 Bar for 1 h, and finally at 80°C and 0.01 Bar for 4 h. After drying, the Zr-MOF@GO composite material was obtained. The preparation process is schematically illustrated in Fig. 1. The incorporation of GO aims to further reduce the unsaturated metal coordination sites in the MOFs through chelation between the oxygen-containing functional groups of GO and the metal ions in the MOF structure, thereby enhancing electrical conductivity and reducing the gas sensing response. To investigate the optimal configuration of the Zr-MOF@GO composite for detecting SF₆ decomposition products, a series of Zr-MOF@GO composites were prepared by varying the mass ratio of Zr-MOF-808 to GO. These materials are denoted as Zr-MOF@GO-n (where n = 1, 0.5, 0.3), with n representing the mass ratio of Zr-MOF-808 to GO.

2.3. Calculation method

The molecular models are first constructed using Gauss View software. Subsequently, geometry optimization and single point energy calculations are performed with the Gaussian 16 software. The PBE0 hybrid functional is selected to treat electron exchange-correlation functional, following simulation parameters established in our previous studies^{27, 34}. To balance computational efficiency and accuracy, the def2-svp basis set is utilized for geometry optimization, while the more precise def2-tzvp basis set is utilized for single-point energy calculations^{31, 32}. Dispersion corrections are incorporated using the GD3BJ empirical scheme for van der Waals interactions, with system charge and spin multiplicity maintained at 0 and 1, respectively.

2.4. Characterizations

The morphology of the Zr-MOF@GO composite was characterized by Scanning electron microscope (SEM, TESCAN MIRA LMS) and transmission electron microscopy (TEM, FEI Tecnai G2 F20), with energy dispersive spectroscopy (EDS) employed to analyze the elemental distribution. The crystal structure was determined using X-ray diffraction (XRD, Rigaku Ultima IV), while the chemical composition was investigated by X-ray photoelectron spectroscopy (XPS, Thermo Scientific K-Alpha). Furthermore, the interaction between Zr-MOF-808 and GO was examined using a Raman spectrometer (Horiba LabRAM HR Evolution).

The gas sensing platform consisted of a gas reservoir, a dynamic gas mixing system, a resistive chemical sensor module, and an exhaust gas collection device, as demonstrated in Fig. 2. To simulate the decomposition of SF₆ following a discharge fault in GIS, the primary decomposition products—CF₄, H₂S, SO₂, and SO₂F₂—were blended with SF₆ with each gas concentration at 10 ppm. Various gas mixtures, including SF₆/CF₄, SF₆/H₂S, SF₆/SO₂, and SF₆/SO₂F₂, were prepared by the dynamic gas mixing system and delivered to the sensor module at a controlled flow rate. The sensing response was quantified by continuously monitoring the resistance change of the coating material on the interdigitated electrodes (IDEs), with data recorded at 1-second intervals.

Figure S2 presents the morphologies and size characteristics of the Zr-MOF-808 nanoparticles. The unmodified particles exhibit a well-defined morphology with distinct edges and an average size of approximately 200 nm. Its intrinsic C, O, and Zr characteristic elements are confirmed by the EDS elemental mapping. After modification with GO, high-resolution TEM is employed to clearly observe the morphologies of the composite material, as illustrated in Fig. 3. As shown in Fig. 3a, when Zr-MOF-808 is composited with GO at a 1:1 mass ratio, the host framework remains intact and exhibits decent transparency. Flocculent material, attributable to GO sheets adhering to the surface, is visible at the particle edges. With the increasing mass ratio of GO, more GO sheets accumulate on the edges and surfaces of the Zr-MOF-808. This leads to a decline in the transparency of the nanoparticles, and more C elements are detected surrounding the framework host in EDS mapping. For the [email protected] composite material, GO sheets almost completely encapsulates the Zr-MOF-808 particles, which is confirmed by the further decrease in light transmittance and the significantly increased C and O elements around.

Figure 4 presents the XRD patterns of various samples. The pristine Zr-MOF-808 exhibits three distinct diffraction peaks near 2θ = 10°, being attributed to the (311), (222), and (400) crystal planes of its intrinsic structure. In terms of the composite materials, a new characteristic peak is formed at 2θ = 11.2°, corresponding to the (001) crystal plane of GO, suggesting the successful incorporation of GO³⁵. Notably, the intensity of this peak increases with the GO ratio, which is attributed to the progressive stacking of GO sheets on the Zr-MOF-808 surface, thereby dominating the diffraction signal. Concurrently, the attenuation of the original diffraction peaks between 20° and 30° further supports this analysis, indicating effective coverage by GO. Figure 5 displays the deconvoluted C 1s XPS spectra of various materials in FTIR spectra. For Zr-MOF-808, three characteristic peaks are observed at 284.8 eV, 286.5 eV, and 288.5 eV, corresponding to C-C, C-O, and O = C-O functional groups, respectively. With the introduction of GO, a continuous increase in the peak intensities of C-O and O = C-O is evident. This can be attributed to the epoxy groups present on the basal planes of GO, as well as the carboxyl groups located at the unsaturated sites along its edges. The enhancement in these oxygen-containing functional groups highlights the effective surface modification and chemical interaction between GO and the metal-organic framework.

Figure 6a compares the Raman spectra of various materials. The graphitic peak (G) and disordered peak (D), located at approximately 1580 cm^− 1 and 1350 cm^− 1 respectively, serve as key indicators for analyzing the structural characteristics in carbon-based materials. These peaks correspond to the in-plane vibration of sp2-hybridized carbon atoms and disorder-induced vibrations arising from structural defects and edges, respectively. The intensity ratio of the D to G (ID/IG) is commonly used to assess the degree of graphitization and structural order within the material: an increase in the ID/IG ratio generally suggests a higher density of defects or enhanced structural disorder, whereas a decrease in this ratio indicates improved graphitization and a more ordered structure. Specifically, the ID/IG ratio of the GO sample is measured at 0.99. In contrast, the composite materials Zr-MOF@GO-1, [email protected], and [email protected] demonstrate ID/IG values of 0.85, 0.79, and 0.97, respectively. The lower ID/IG values observed in all composites compared to pure GO suggest that the introduction of Zr-MOF-808 promotes more ordered stacking and arrangement of the GO sheets. This is primarily attributed to coordination interactions and π-π stacking between GO and Zr-MOF-808, which enhance interlayer adhesion and improve the overall structural regularity. Notably, the ID/IG reaches a minimum value of 0.79 as the mass ratio of Zr-MOF-808 to GO is 1:2 (corresponding to [email protected]), indicating an optimal structural synergy and stacking configuration. After that, as the proportion of GO further increases ([email protected]), the ID/IG value rises to 0.97, implying an excess of GO that could not effectively interact with Zr-MOF-808, leaving some GO domains in a relatively disordered state. This result further confirms that the maximum effective mass ratio for the interaction between Zr-MOF-808 and GO is 1:2.

Figure 7 compares the adsorption performance of three composite materials on four SF₆ mixtures containing 10 ppm SO₂ or H₂S or SO₂F₂ or CF₄, where the variation of electrical resistivity (R/R0) serves as the measurement indicator²⁷. The introduction of GO enhances the electrical conductivity of the composite material, hence reducing the sensitive response to variations in ΔR values. In Zr-MOF@GO-1, The ΔR changes caused by different gases have been reduced to the observable range, but the response rates are still relatively close, making it difficult to effectively distinguish. Notably, a higher GO content ([email protected]) further reduces the response rate but, crucially, enables clear discrimination between gases at 60 seconds. The R/R0 values follow the order: SO₂/SF₆ < H₂S/SF₆ < SO₂F₂/SF₆ < CF₄/SF₆, providing a valuable criterion for classifying discharge types. Nevertheless, an excessive amount of GO ([email protected]) renders the composite overly conductive, resulting in a loss of gas discrimination capability.

To further elucidate the underlying mechanism of the differences in resistivity variations after Zr-MOF@GO adsorbs different gases, the adsorption characteristics and charge transfer processes of various composite materials are systematically explored using DFT analyses. The corresponding composite molecular models of Zr-MOF@GO with CF₄, SF₆, H₂S, SO₂, and SO₂F₂ are constructed, and the calculated results are demonstrated in Figure S3.

Figure 8a displays the differential charge density of these gas adsorption models, where yellow and blue regions represent the tendency of electron loss and gain, respectively. During gas adsorption, Zr atoms tend to lose electrons. Notably, the SO₂ and SO₂F₂ models exhibit significantly larger blue regions, indicating their stronger electron-accepting ability. Based on molecular orbital theory, we further analyzed the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), as shown in Fig. 8b. The LUMO and HOMO energy levels of the pristine Zr-MOF@GO are − 3.95 eV and − 5.43 eV, respectively, with a band gap of 1.48 eV. After gas adsorption, the band gap of the composite material decreases, facilitating electron transition from HOMO to LUMO and thereby enhancing electrical conductivity. In particular, the band gap of the SO₂-adsorbed composite decreases significantly to 1.09 eV, indicating a notable improvement in conductivity. To investigate the mechanism behind the band gap reduction in the Zr-MOF@GO/SO₂ system, we further analyzed the density of states (DOS), as shown in Figure S4. The results reveal that the introduction of SO₂ leads to the emergence of new orbital occupations near − 4.27 eV after adsorption, while no significant changes are observed at other energy positions. By comparing with the total orbital occupations, the changes near − 4.29 eV, 0.86 eV, and 1.24 eV in the system are attributed to the contribution of SO₂ after adsorption. Further analysis of the occupations of the Zr 4d and 5s orbitals in the adsorption substrate and the O 2s and 2p orbitals in the SO₂ molecule clearly shows an overlap between the O 2p and Zr 4d orbitals near − 4.29 eV and − 5.57 eV (Figure S4). This overlap suggests the presence of bonded adsorption between Zr-MOF@GO and SO₂ gas molecules. Similarly, as shown in Figures S5–S8, bonded adsorption also occurs between Zr-MOF@GO and SF₆, H₂S, and SO₂F₂, but no such effect is observed for CF₄. In addition, Fig. 8c compares the adsorption energies between Zr-MOF@GO and various gases. The results indicate higher adsorption energies for H₂S, SO₂, and SO₂F₂, which may be attributed to their stronger molecular polarity compared to SF₆ and CF₄, thereby enhancing intermolecular interactions with Zr-MOF@GO. In summary, the Zr-MOF@GO composite exhibits strong bonded adsorption with H₂S, SO₂F₂ and SO₂, weak interaction with SF₆, and primarily van der Waals adsorption with CF₄.

By comparing Fig. 7 and Figure S1, it is observed that the introduction of GO effectively slows down the gas adsorption rate of MOFs. In the MOFs@GO system, distinct resistance variation trends can be clearly observed upon exposure to different gas components. Moreover, as the GO content increases, this attenuation effect becomes more pronounced. Combined with XRD, TEM, Raman, XPS and SEM (Figure S2), it is confirmed that the reduction in adsorption effectiveness results from the wrapping of MOFs by GO, which inhibits MOFs adsorption efficiency. This finding overcomes the limitations of intrinsic MOFs materials in discriminative gas detection and demonstrates the effectiveness of the composite modification of Zr-MOF-808 with GO for the selective detection of SF₆ decomposition products.

After gas introduction, the resistance of the MOFs@GO system increases. Using the response curve of MOFs@GO to pure SF₆ gas as a control, the change in material resistance is significantly smaller when the gas mixture contains SO₂, H₂S, or SO₂F₂ than that of the pure SF₆ and CF₄-containing systems. Combined with simulation results, it is evident that gas adsorption in MOFs@GO involves both van der Waals interactions and chemical adsorption, with van der Waals forces playing the dominant role. The overall resistivity shows an increasing trend; however, chemical adsorption causes a delay in the resistance rise. Due to the lowest adsorption energy of MOFs@GO for CF₄, van der Waals adsorption predominates entirely, which instead enhances the resistance increase after adsorption. In the case of SO₂F₂, chemical adsorption promotes the charge transfer process, leading to the emergence of a resistivity hysteresis effect. Notably, after SO₂ adsorption on Zr-MOF-808, new energy states form near the LUMO level of the composite system, accompanied by molecular orbital overlap, which reduces the bandgap to a minimum of 0.86 eV (Figure S4). This facilitates electron excitation and transfer, resulting in the most pronounced hysteresis effect.

Based on the differences in the hysteresis effect of the increase in resistance of MOFS@GO caused by the adsorption of different gases, it can be effectively used to identify various components of SF₆ decomposition products after internal discharge in GIS equipment at room temperature, with a detection accuracy of up to 10 ppm. This makes Zr-MOF-808@GO a potential application in sensing and detection in this field.

In summary, this study successfully developed a Zr-MOF@GO composite via a distributed vacuum impregnation method, achieving uniform coating of GO on the surface of Zr-MOF-808. The coating effectiveness at different mass ratios was systematically characterized using TEM, SEM, XRD, and XPS. The results indicate that a mass ratio of 1:2 between Zr-MOF-808 and GO enables homogeneous coverage of GO over Zr-MOF-808. The minimal ID/IG ratio observed in the Raman spectrum further confirms the optimal interfacial interaction between GO and Zr-MOF-808 at this ratio. This finding overcomes the limitations of intrinsic Zr-MOF-808 in gas sensing applications and extends its functional scope.

Gas sensing tests revealed that, compared to pristine Zr-MOF-808, the Zr-MOF@GO composite significantly suppresses abrupt resistance changes induced by gas adsorption, thereby facilitating more observable sensing outcomes. At the optimal 1:2 ratio, the composite exhibited the highest discrimination capability among different decomposition products, with the following order of responsiveness: CF₄ < SO₂F₂ < H₂S < SO₂. Furthermore, through DFT calculations and frontier molecular orbital simulations, the mechanism underlying the differential resistance response was elucidated. The composite material enables discriminative detection of SF₆ decomposition gases at room temperature, with a detection limit reaching the 10 ppm level.

This work provides an effective modification strategy to enhance the gas sensing performance of Zr-MOF-808, offers both theoretical and experimental support for the identification of SF₆ decomposition gases at room temperature, and establishes a theoretical foundation for the design of high-performance gas sensor materials.

Primary Data

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Conflict of Interest

The authors declare no conflict of interest.

Funding Information

This research was funded by by the State Grid Economic And Technological Research Institute Co,.LTD innovation project ZZKJ-2024-39.

Author Contribution

T.L. wrote the main manuscript text, and mainly focus on methodology, visualization, formal analysis. Y.X. focus on supervision. Z.H, T.Z and Y.Z focus on validation and investigation. T.L., Z.G and L.W contribute in conceptualization and supervision. Y.Z.,L.W and Y.X contribute in visualization and supervision. T.L., Z.H and Y.Z also contribute in software and validation. T.Z., Y.Z, Z.G and L.W also contribute in supervision writing-review and editing . All authors reviewed the manuscript.

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Study on Adsorption Characteristics and Sensing Performance of Zr-MOF-808@GO for SF6 Discharge Decomposition Gas

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1. Introduction

2. Materials and Methods

2.1. Materials

2.2. Experimental method

2.3. Calculation method

2.4. Characterizations

3. Results and Discussions

4. Conclusions

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Primary Data

Conflict of Interest

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