A density functional theory study on the sensing of dissolved gases CO and CO2 in transformer oil using boron-doped nitrogen-based graphene

doi:10.11949/0438-1157.20240693

Abstract

Abstract:

Carbon monoxide (CO) and carbon dioxide (CO₂) are crucial characteristic gases for detecting transformer faults, and their components can effectively reflect the operating status of transformers. To achieve rapid and precise detection of these gases, this paper introduces a novel material, boron (B)-doped nitrogen (N)-based graphene, for detecting dissolved characteristic gases CO and CO₂ in transformer oil. Utilizing density functional theory (DFT), the adsorption and activation behaviors of CO and CO₂ gases on B-doped graphitic-N、pyridinic-N and pyrrolic-N graphene substrates were investigated. Theoretical discussions were conducted on the changes in geometric structure, charge density, electron density of states, and band structure of B-doped nitrogen-based graphene (BN-X/G) following the adsorption of characteristic gases. The results indicated that the adsorption energies of CO and CO₂ on B-doped graphitic-N-based graphene were -0.18 and -0.20 eV, respectively, which have significant performance differences with other doped substrates and show stronger adsorption performance. Electronic localization function (ELF) configurations and Bader charge results revealed that CO and CO₂ transferred charges of 0.013 e and 0.009 e to the BN-G/G substrate, respectively, strengthening the interaction between the characteristic gases and the substrate. Density of states (DOS) outcomes suggested that B doping elevated the p-band center of N-G/G and led to noticeable orbital hybridization between B and graphitic-N atoms, forming covalent bonds that facilitated enhanced adsorption performance. This study provides valuable insights into the adsorption mechanisms of dissolved characteristic gases in transformer oil on heteroatom-doped graphene materials and offers rational guidance for the design of gas sensors.

Key words: transformer oil, graphene, doping, adsorption, CO, CO₂

摘要：

一氧化碳（CO）和二氧化碳（CO₂）是检测变压器故障的重要特征气体，其组分可以有效反映变压器的运行状态。为实现特征气体的快速精准检测，提出了一种利用新型材料硼（B）掺杂氮（N）基石墨烯检测变压器油中溶解特征气体CO和CO₂的方法。结合密度泛函理论（DFT）探究了CO、CO₂气体在B掺杂石墨氮（graphitic-N）、吡啶氮（pyridinic-N）和吡咯氮（pyrrolic-N）石墨烯基底上的吸附和活化行为。从理论上探讨B掺杂氮基石墨烯（BN-X/G）在特征气体吸附后的几何结构、电荷密度、电子态密度以及能带结构的变化。结果显示，CO、CO₂在B掺杂graphitic-N基石墨烯上的吸附能分别为-0.18和-0.20 eV，与其他掺杂基底具有显著的性能差异，表现出更强的吸附性能。电子局域函数（ELF）构型及Bader电荷结果显示，CO和CO₂分别向BN-G/G基底输出0.013 e和0.009 e的电荷转移，加强了特征气体与基底之间的相互作用。态密度（DOS）结果表明，B掺杂提高了N-G/G的p带中心，B与graphitic-N原子之间有明显的轨道杂化现象并形成共价键，促进吸附性能的增强。本研究可为变压器油中溶解性特征气体在杂原子掺杂石墨烯材料的吸附机理及气体传感器的理性设计提供参考。

关键词: 变压器油, 石墨烯, 掺杂, 吸附, CO, CO₂

CLC Number:

TM 855

Tianzi CAI, Haifeng ZHANG, Haidan LIN, Zilong ZHANG, Pengyu ZHOU, Bolin WANG, Xiaonian LI. A density functional theory study on the sensing of dissolved gases CO and CO₂ in transformer oil using boron-doped nitrogen-based graphene[J]. CIESC Journal, 2025, 76(4): 1841-1851.

蔡天姿, 张海丰, 林海丹, 张子龙, 周鹏宇, 王柏林, 李小年. 硼掺杂氮基石墨烯检测变压器油中溶解气体CO和CO₂的密度泛函理论研究[J]. 化工学报, 2025, 76(4): 1841-1851.

Figures/Tables 11

Fig.1 Schematic representation of the planar geometry and adsorption sites of graphene nanoribbons

Fig.2 Schematic diagram of heteroatom-doped graphene nanoribbon configurations (purple: C; yellow: N; green: B; white: H)

Fig.3 Optimal configuration diagrams and adsorption energies of CO and CO2 gases on various heteroatom-doped graphene nanoribbon systems (purple: C; yellow: N; green: B; red: O; white: H)

Table 1 Bond lengths and distances of CO and CO2 gases adsorbed onto the surface of various heteroatom-doped graphene nanoribbon systems

Structure	Bond length/Å				D/Å
Structure	C—C	B—C	B—N	N—C	CO	CO₂
G	1.421
N-G/G	1.429			1.406	3.229^(O—N)	3.102^(O—N)
BN-G/G	1.428	1.498	1.441	1.410	3.447^(O—B)	3.672^(O—B)
N-P/G	1.445			1.364	3.695^(O—N)	3.621^(O—N)
BN-P/G	1.464	1.538	1.416	1.346	3.767^(O—B)	3.632^(O—B)
N-O/G	1.436			1.398	3.677^(O—N)	3.766^(O—N)
BN-O/G	1.446	1.476	1.357	1.402	3.440^(O—B)	3.475^(O—B)

Fig.4 Differential charge density maps of CO and CO2 adsorption on BN-G/G and BN-O/G

Table 2 Charge transfer quantities for CO and CO2 adsorption on BN-G/G and BN-O/G

Structure	Transfer electron/e
Structure	N	B	C	O1	O2	CO	CO₂
CO/BN-G/G	-1.498	+1.885	+1.059	-1.072		-0.013
CO/BN-O/G	-1.467	+1.913	+1.073	-1.085		-0.012
CO₂/BN-G/G	-1.490	+1.881	+2.076	-1.060	-1.023		-0.009
CO₂/BN-O/G	-1.480	+1.948	+2.087	-1.050	-1.047		-0.008

Fig.5 ELF configuration diagrams for CO and CO2 adsorption on BN-G/G and BN-O/G

Fig.6 Band structures of CO and CO2 adsorption on BN-G/G and BN-O/G

Fig.7 Total and partial density of states for CO and CO2 adsorption on BN-G/G and BN-O/G

Fig.8 Potential energy diagrams for CO and CO2 adsorption on BN-G/G

Fig.9 Changes in the adsorption content of dissolved gases in oil

References 43

1	Ni J M, Yang B Q, Jia F F, et al. Theoretical investigation of the sensing mechanism of the pure graphene and Al,B,N,P doped mono-vacancy graphene-based methane[J]. Chemical Physics Letters, 2018, 710: 221-225.
2	Skorupska M, Ilnicka A, Lukaszewicz J P. Modified graphene foam as a high-performance catalyst for oxygen reduction reaction[J]. RSC Advances, 2023, 13(36): 25437-25442.
3	Gui Y G, Xu L N, Ding Z Y, et al. Co, Rh decorated GaNNTs for online monitoring of characteristic decomposition products in oil-immersed transformer[J]. Applied Surface Science, 2021, 561: 150072.
4	Zhang J, Wang Y Q, Wei Z, et al. Ni-decorated ZnO monolayer for sensing CO and HCHO in dry-type transformers: a first-principles theory[J]. Chemosensors, 2022, 10(8): 307.
5	Yuan T, Fu C, Gong Y J, et al. First-principles insights into Cu-decorated GaN monolayers for sensing CO and HCHO in dry-type transformers[J].ACS Omega, 2021, 6(29): 19127-19133.
6	Simões A N, Lustosa G M M M, de Souza Morita E, et al. Room-temperature SnO₂-based sensor with Pd-nanoparticles for real-time detection of CO dissolved gas in transformer oil[J]. Materials Chemistry and Physics, 2024, 311: 128576.
7	Li Z, Zhang Q R, Wang Z T, et al. A highly sensitive low-pressure TDLAS sensor for detecting dissolved CO and CO₂ in transformer insulating oil[J]. Optics & Laser Technology, 2024, 174: 110622.
8	Zeng Q L, Wang L H, Zhu H, et al. Estimating daily concentrations of near-surface CO, NO₂, and O₃ simultaneously over China based on spatiotemporal multi-task transformer model[J]. Atmospheric Environment, 2024, 316: 120193.
9	Gui Y G, Liu Z C, Ji C, et al. Adsorption behavior of metal oxides (CuO, NiO, Ag₂O) modified GeSe monolayer towards dissolved gases (CO, CH₄, C₂H₂, C₂H₄) in transformer oil[J]. Journal of Industrial and Engineering Chemistry, 2022, 112: 134-145.
10	Wang H M, Wu H L, Cui H. First-principles screening in Cu-embedded PtSe₂ monolayer as a potential gas sensor upon CO and HCHO in dry-type transformers[J]. Computational and Theoretical Chemistry, 2022, 1209: 113586.
11	Cui H, Jia P F, Peng X Y, et al. Adsorption and sensing of CO and C₂H₂ by S-defected SnS₂ monolayer for DGA in transformer oil: a DFT study[J]. Materials Chemistry and Physics, 2020, 249: 123006.
12	Xie R J, Lu J B, Wang J. High performance room temperature CO gas sensor based on CuO/ TiO₂/N-MWCNTs ternary nanocomposites[J]. Journal of Industrial and Engineering Chemistry, 2024, 131: 248-256.
13	Wu H, Fang J, Yuan S, et al. Exploration on the application of copper oxide particles doped janus ZrSSe in detecting dissolved gases in oil-immersed transformers: a DFT study[J]. Materials Today Chemistry, 2024, 38: 102038.
14	He T, Liu H C, Zhang J, et al. DFT study on the adsorption and sensing properties of dissolved gases (H₂, CO and CH₄) in transformer oil on PdO-doped In₂O₃ (110) surfaces[J]. Chemical Physics Letters, 2023, 832: 140865.
15	Zhao P P, Tang M C, Zhang D Z. Adsorption of dissolved gas molecules in the transformer oil on metal (Ag, Rh, Sb)-doped PdSe₂ momlayer: a first-principles study[J]. Applied Surface Science, 2022, 600: 154054.
16	Chen Z W, Zhang X X, Xiong H, et al. Dissolved gas analysis in transformer oil using Pt-doped WSe₂ monolayer based on first principles method[J]. IEEE Access, 2019, 7: 72012-72019.
17	Zhang Y S, Yan S C, Zhu Y W. Gas-sensing properties of Ti, Zr, V, and Nb-modified Ti₃C₂O₂ for decomposed gases in locomotive electric transformers: a DFT study[J]. Dalton Transactions, 2024, 53(8): 3548-3558.
18	Zhang B S, Zhang J Q, Huang Y, et al. Burning process and fire characteristics of transformer oil[J]. Journal of Thermal Analysis and Calorimetry, 2020, 139(3): 1839-1848.
19	Saeid M, Zeinoddini-Meymand H, Kamel S, et al. Interaction of transformer oil parameters on each other and on transformer health index using curve estimation regression method[J]. International Transactions on Electrical Energy Systems, 2022, 2022: 7548533.
20	Prasojo R A, Diwyacitta K, Suwarno, et al. Transformer paper expected life estimation using ANFIS based on oil characteristics and dissolved gases (case study: Indonesian transformers)[J]. Energies, 2017, 10(8): 1135.
21	Jia L F, Chen J X, Cui X S, et al. Gas sensing mechanism and adsorption properties of C₂H₄ and CO molecules on the Ag₃-HfSe₂ monolayer: a first-principle study[J]. Frontiers in Chemistry, 2022, 10: 911170.
22	Cui H, Chen D C, Zhang Y, et al. Dissolved gas analysis in transformer oil using Pd catalyst decorated MoSe₂ monolayer: a first-principles theory[J]. Sustainable Materials and Technologies, 2019, 20: e0094.
23	Qiao H, Zhang X B, Wang P, et al. Metal oxide decorated GeTe monolayer as promising materials for dissolved gases in transformer oil[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2024, 31(2): 904-911.
24	Zeng T T, Ma D L, Gui Y G. Gas-sensitive performance study of metal (Au, Pd, Pt)/ZnO heterojunction gas sensors for dissolved gases in transformer oil[J]. Langmuir, 2024, 40(18): 9819-9830.
25	Xu Z L. Ni-decorated PtS₂ monolayer as a strain-modulated and outstanding sensor upon dissolved gases in transformer oil: a first-principles study[J]. ACS Omega, 2023, 8(6): 6090-6098.
26	Zheng H B, Yang E C, Wu S Y, et al. Investigation on formation mechanisms of carbon oxides during thermal aging of cellulosic insulating paper[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2022, 29(4): 1226-1233.
27	Zhao P P, Li T T, Zhang D Z. Adsorption of dissolved gas molecules in the transformer oil on silver-modified (002) planes of molybdenum diselenide monolayer: a DFT study[J]. Journal of Physics: Condensed Matter, 2021, 33(48): 485201.
28	Wang X R, Gui Y G, Ding Z Y, et al. Density functional theory study of Pd, Pt, and Au modified GeSe for adsorption and sensing of dissolved gases in transformer oil[J]. Surfaces and Interfaces, 2022, 31: 101994.
29	Qian G C, Hu J, Wang S, et al. Adsorption and sensing properties of dissolved gas in oil on Cr-doped InN monolayer: a density functional theory study[J]. Chemosensors, 2022, 10(1): 30.
30	Mu L, Chen D C, Cui H. Single Pd atom embedded Janus HfSeTe as promising sensor for dissolved gas detection in transformer oil: a density functional theory study[J]. Surfaces and Interfaces, 2022, 35: 102398.
31	Jung Mi H, Kwak M, Ahn J, et al. Highly sensitive and selective acetylene CuO/ZnO heterostructure sensors through electrospinning at lean O₂ concentration for transformer diagnosis[J]. ACS Sensors, 2024, 9(1): 217-227.
32	Mann S, Mudahar I, Sharma H, et al. Lattice thermal conductivity of pure and doped (B, N) graphene[J]. Materials Research Express, 2020, 7(9): 095003.
33	Siburian R, Sebayang K, Supeno M, et al. Effect of N-doped graphene for properties of Pt/N-doped graphene catalyst[J]. ChemistrySelect, 2017, 2(3): 1188-1195.
34	张芳芳, 韩敏, 赵娟, 等. 单空缺石墨烯负载的Pd单原子催化剂上NO还原的密度泛函理论研究[J]. 化工学报, 2021, 72(3): 1382-1391.
	Zhang F F, Han M, Zhao J, et al. DFT study on reduction of NO over Pd atom anchored on single-vacancy graphene[J]. CIESC Journal, 2021, 72(3): 1382-1391.
35	Gao Q Q. A DFT study of the ORR on M-N₃ (M = Mn, Fe, Co, Ni, or Cu) co-doped graphene with moiety-patched defects[J]. Ionics, 2020, 26(5): 2453-2465.
36	Jo W K, Jin Y J. 2D graphene-assisted low-cost metal (Ag, Cu, Fe, or Ni)-doped TiO₂ nanowire architectures for enhanced hydrogen generation[J]. Journal of Alloys and Compounds, 2018, 765: 106-112.
37	Singla M, Sharma D, Jaggi N. Effect of transition metal (Cu and Pt) doping/co-doping on hydrogen gas sensing capability of graphene: a DFT study[J]. International Journal of Hydrogen Energy, 2021, 46(29): 16188-16201.
38	马生贵, 田博文, 周雨薇, 等. 氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究[J]. 化工学报, 2021, 72(9): 4496-4503.
	Ma S G, Tian B W, Zhou Y W, et al. DFT study of adsorption of H₂S on N-doped Stone-Wales defected graphene[J]. CIESC Journal, 2021, 72(9): 4496-4503.
39	Gui Y G, Peng X, Liu K, et al. Adsorption of C₂H₂, CH₄ and CO on Mn-doped graphene: atomic, electronic, and gas-sensing properties[J]. Physica E: Low-Dimensional Systems and Nanostructures, 2020, 119: 113959.
40	Zhao C J, Wu H R. A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: a DFT study[J]. Applied Surface Science, 2018, 435: 1199-1212.
41	Zheng Z Q, Wang H L. Different elements doped graphene sensor for CO₂ greenhouse gases detection: the DFT study[J]. Chemical Physics Letters, 2019, 721: 33-37.
42	Avramov P V, Kudin K N, Scuseria G E. Single wall carbon nanotubes density of states: comparison of experiment and theory[J]. Chemical Physics Letters, 2003, 370(5/6): 597-601.
43	Yue Y X, Zuo F M, Wang B L, et al. Highly efficient catalyst for 1,1,2-trichloroethane dehydrochlorination via BN₃ frustrated Lewis acid-base pairs[J]. Nano Research, 2024, 17(6): 4773-4781.

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A density functional theory study on the sensing of dissolved gases CO and CO₂ in transformer oil using boron-doped nitrogen-based graphene

硼掺杂氮基石墨烯检测变压器油中溶解气体CO和CO₂的密度泛函理论研究

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