氮掺杂浓度对石墨烯基氨气传感器性能的影响机理

doi:10.19595/j.cnki.1000-6753.tces.242396

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摘要 “双碳”目标下氢能储运是构建清洁低碳能源体系的重要手段,氨是富氢载体和良好的储氢介质,是大规模、长距离储运氢的有效方式。然而,氨气具有一定的毒性和易燃易爆特性,因此开发高性能氨气传感技术具有重要意义。该文制备了不同掺杂浓度的氮掺杂石墨烯基氨气传感器,并进行了表征与气敏测试,基于第一性原理计算了氮掺杂石墨烯-氨气吸附体系的能量与结构参数,探讨了氮掺杂浓度对传感器性能的影响机理。结果表明：当石墨烯中氮的原子含量百分比小于1.44%时,吡啶氮所占比例较高,其对氨气的吸附能为-0.26 eV,吸附距离为2.637 Å（1 Å=1× 10^-10 m）,转移电荷量为0.04 e（1 e=1.602×10^-19 C）,吸附性能优于本征石墨烯,可提升传感器性能;超过1.44%时,吡咯氮含量较高,其对氨气的吸附能为-0.08 eV,吸附距离为3.005 Å,转移电荷量为0.02 e,吸附性能比本征石墨烯差,使传感器性能下降。因此,掺杂氮原子含量百分比在1.4%左右时,石墨烯中吡啶氮占主导地位,传感器性能最优。该文可为掺杂浓度对氮掺杂石墨烯基氨气传感器性能的调控提供相应的理论基础。

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	王建宇
	郑钦仁
	折俊艺
	沈祉衡
	夏凌寒
	张欣
	陈玉
	成永红
	孟国栋

关键词 ：石墨烯, 氮掺杂, 掺杂浓度, 第一性原理, 氨气传感器

Abstract：Ammonia (NH₃), with a hydrogen storage capacity of 17.7%, is considered a promising hydrogen energy carrier under the goal of dual-carbon(carbon neutrality and carbon peaking). However, due to its high volatility and toxicity, the online detection of NH₃ is essential for safe ammonia-hydrogen storage and transport. Gas sensors based on gas-sensitive materials are widely used for NH₃ detection, but intrinsic graphene exhibits weak physical adsorption to most gases, limiting its sensing performance. Doping, functionalization, and compositing are effective strategies for improving graphene-based gas sensors. However, the effect of different nitrogen doping concentrations on NH₃ sensing performance remains underexplored.
Firstly, graphene sensors with different nitrogen doping (NG) concentrations were prepared, and their morphology, structure and chemical composition were systematically characterized. The influence of nitrogen doping concentration on the structural properties of graphene was analyzed. Secondly, the gas sensing response of sensors with different doping concentrations was tested, and the influence of doping concentration on sensor performance was analyzed. Finally, the energy and structural parameters of the nitrogen-doped graphene-NH3 adsorption system were calculated based on the first-principles, and the influence mechanism of doping concentration on gas sensing performance was discussed.
The gas sensitivity tests show that the NG30 sensor exhibits optimal performance, with an 11.7% response, a maximum selectivity coefficient of 80, a sensitivity of 0.11%/10^-6, a minimum detection limit of 71×10^-9, and response/recovery times of 373/568 s. Long-term exposure tests showed that NG sensors maintained over 90% of their initial response even after multiple NH₃ exposure cycles, demonstrating excellent stability and repeatability. Computational simulations indicate that when the nitrogen content in graphene is below 1.44%, pyridine nitrogen dominates, resulting in stronger NH₃ adsorption with an adsorption energy of -0.26 eV, an adsorption distance of 2.637 Å (1 Å=1×10^-10 m), and a charge transfer of 0.04 e (1 e=1.602×10^-19 C). This enhanced adsorption improves sensor performance. In contrast, when the nitrogen content exceeds 1.44%, pyrrole nitrogen becomes dominant, leading to weaker adsorption with an adsorption energy of -0.08 eV, an adsorption distance of 3.005 Å, and a charge transfer of 0.02 e, thereby deteriorating sensor performance. Further analysis reveals that nitrogen doping influences graphene's electronic structure, altering its conductivity and adsorption characteristics. Density functional theory (DFT) calculations indicate that pyridine nitrogen contributes to a higher density of states near the Fermi level, facilitating charge transfer during NH₃ adsorption. In contrast, pyrrole nitrogen introduces localized states that weaken adsorption interactions. The experimental findings align with theoretical predictions, confirming that optimal NH₃ sensing performance is achieved at a nitrogen doping concentration of 1.44%.
The following conclusions can be drawn from the analysis: (1) When the doping concentration is low, the doped nitrogen atoms in graphene are mainly pyridine nitrogen. When the doping concentration increases, the relative content of pyrrole nitrogen increases. (2) If the nitrogen doping concentration is too high, the performance of the sensor will deteriorate. (3) Pyridine nitrogen can enhance the adsorption of graphene to NH₃, while pyrrole nitrogen will weaken the adsorption. The performance of nitrogen-doped graphene-based NH₃ sensor increases with the increase of pyridine nitrogen content, and deteriorates with the increase of pyrrole nitrogen content.

Key words： Graphene nitrogen doping doping concentration first principles ammonia sensor

收稿日期: 2024-12-31

PACS:	TM23
	TP212

基金资助:中央高校基本科研业务费（xzy012023152, xtr062023001, xtr052025002）和陕西省创新能力支撑计划资金（2024RS-CXTD-22）资助项目

通讯作者: 孟国栋男,1985年生,博士,教授,博士生导师,研究方向为二维材料与器件应用、微纳尺度绝缘与放电等离子体、电力设备绝缘状态评估及检测诊断技术等。E-mail: gdmengxjtu@xjtu.edu.cn

作者简介: 王建宇男,2003年生,博士研究生,研究方向为二维材料与器件应用、微纳尺度绝缘与放电等离子体。E-mail: 2203712763@stu.xjtu.edu.cn

引用本文:

王建宇, 郑钦仁, 折俊艺, 沈祉衡, 夏凌寒, 张欣, 陈玉, 成永红, 孟国栋. 氮掺杂浓度对石墨烯基氨气传感器性能的影响机理[J]. 电工技术学报, 2026, 41(1): 289-301. Wang Jianyu, Zheng Qinren, She Junyi, Shen Zhiheng, Xia Linghan, Zhang Xin, Chen Yu, Cheng Yonghong, Meng Guodong. Influence Mechanism of Nitrogen Doping Concentration on the Performance of Ammonia Sensor Based on Graphene. Transactions of China Electrotechnical Society, 2026, 41(1): 289-301.

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https://dgjsxb.ces-transaction.com/CN/10.19595/j.cnki.1000-6753.tces.242396 https://dgjsxb.ces-transaction.com/CN/Y2026/V41/I1/289

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