改性石墨烯基传感器对SF<sub>6</sub>分解组分H<sub>2</sub>S的吸附机理及检测特性研究

doi:10.19595/j.cnki.1000-6753.tces.220842

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Abstract

H₂S is one of the important decomposition products of SF₆. It is the characteristic component in the event of high energy partial discharge or strong overheating fault, and can reflect the severity of the fault.The gas sensor method is a method using gas sensitive materials to detect the gas composition and concentration, and is often used to detect SF₆ decomposed components.The gas sensing materials based on intrinsic graphene only show weak physical adsorption for most gases. Therefore, the sensing performance of graphene gas sensing materials and graphene gas sensors can be improved through various optimization methods such as doping, functionalization of functional groups, and composite.However, there are few studies on the properties of metal and functional group functionalized co-modified graphene in gas sensing detection at present.Based on this, three different modification methods including metal doping, functional group functionalization, doping and functional group functionalization co-modification were selected to improve the gas sensitivity of intrinsic graphene to H₂S.
Firstly, the modification models of epoxy graphene (G-O), palladium doped graphene (Pd-G) and epoxy and palladium Co-doped graphene (Pd-G-O) are established, and the modification mechanism is analyzed. Secondly, the adsorption models of modified graphene for H₂S are built, and the adsorption effect of H₂S is analyzed from adsorption energy, density of state, orbitand desorption time.Thirdly, G-O, Pd-G and Pd-G-O sensing materials and planar gas sensors are prepared based on the oxidation-reduction method and drop coating method. The gas sensing performance for H₂S are tested based on the micro gas sensing test platform.Finally, the response ability of the modified graphene sensors to H₂S is evaluated from temperature characteristics, concentration characteristics, response-recovery characteristics and stability.
The simulation results of the modified models show that, the epoxy group effectively increases the energy gap of intrinsic graphene, from 0.049 eV to 0.218 eV. The doping of Pd introduces a new impurity level at the Fermi level, which effectively improves the charge transfer of intrinsic graphene. Through the co-doping of epoxy group and Pd, the energy gap reaches 0.214 eV, and the graphene system is more stable and the charge transfer ability is enhanced. In G-O adsorbing H₂S system, the adsorption energy and charge transfer are -1.326 eV and 0.003 e, respectively. The adsorption energy is the largest, but the charge transfer capacity is extremely weak.In the system of H₂S adsorbed on Pd-G, the charge transfer is 0.254 e, and the minimum adsorption energy is -0.897 eV. In Pd-G-O adsorbing H₂S system, the co-modified graphene system shows the best adsorption performance, with the adsorption energy of -1.015 eV, which corresponds to a strong charge transfer value of 0.281 e. The results of gas sensitivity test show that, the optimum working temperature of G-O, Pd-G and Pd-G-O sensors is 225, 175 and 175 ℃ respectively. The lower detection limits for H₂S are 6.9, 2.3, 0.5 μL/L. The response recovery time of Pd-G-O to 50 μL/L of H₂S is 23/18 s. The response value is 10.02, which is the 1.818 and 1.538 times of that of G-O and Pd-G.
The following conclusions can be drawn from the analysis: (1) The stability and charge transfer ability of Pd-G-O system have been improved. The energy gap of intrinsic graphene is increased and metal energy level appears at Fermi energy level through the co-doping of epoxy group and Pd. (2) G-O, Pd-G, Pd-G-O improved the adsorption performance of intrinsic graphene for H₂S. The Absolute value of adsorption energy is G-O>Pd-G-O>Pd-G; The charge transfer value is Pd-G-O>Pd-G>G-O. Among them, Pd-G-O shows great adsorption effect and charge transfer ability, attributing to the strong hybridization between the S 3p orbital and the Pd 4d orbital. (3) Pd-G-O sensor shows excellent gas sensing performance, and can be used as a promising gas sensor material for detecting H₂S. Pd-G-O gas sensor shows the advantages of low operating temperature, low detection limit and high response value, suitable for the detection of trace H₂S.

Key words： Modified graphene SF₆ decomposed component H₂S detection adsorption mechanism detection characteristics

Received: 17 May 2022

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TM855

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	Gao Xin
	Li Zhihui
	Liu Yupeng
	Chen Weigen
	Zhou Qu

Cite this article:

Gao Xin,Li Zhihui,Liu Yupeng等. Study on Adsorption Mechanism and Detection Characteristics of Modified Graphene Sensors for SF₆ Decomposed Component H₂S[J]. Transactions of China Electrotechnical Society, 2023, 38(13): 3606-3618.

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https://dgjsxb.ces-transaction.com/EN/10.19595/j.cnki.1000-6753.tces.220842 OR https://dgjsxb.ces-transaction.com/EN/Y2023/V38/I13/3606

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