H2O/CO2/CH4与煤表面含氧官能团相互作用密度泛函理论研究

doi:10.3969/j.issn.2096-1693.2026.02.015

石油科学通报 ›› 2026, Vol. 11 ›› Issue (2): 605-613. doi: 10.3969/j.issn.2096-1693.2026.02.015

H₂O/CO₂/CH₄与煤表面含氧官能团相互作用密度泛函理论研究

李兵¹^,²(), 郑司建³^,⁴^,^*(), 胡洪清³^,⁴^,⁵, 田钰琛³^,⁴^,⁵, 张贺龙³^,⁴^,⁵, 徐标¹^,², 芮成奇¹^,², 张国鑫³^,⁴^,⁵, 苏升³^,⁴^,⁵, 张越³^,⁴^,⁵, 杨达林³^,⁴^,⁵

¹ 淮南矿业(集团)有限责任公司，淮南 232001
² 安徽省煤矿绿色低碳发展工程研究中心平安煤炭开采工程技术研究院有限责任公司，淮南 232001
³ 江苏省煤基温室气体减排与资源化利用重点实验室，徐州 221008
⁴ 中国矿业大学碳中和研究院，徐州 221008
⁵ 中国矿业大学资源与地球科学学院，徐州 221116

收稿日期:2025-10-22 修回日期:2026-01-12 出版日期:2026-04-15 发布日期:2026-04-30
通讯作者: ^*郑司建(1992年—)，博士，副研究员，硕士生导师，从事煤地质与煤系非常规油气勘探开发、二氧化碳地质封存相关研究工作，sijian.zheng@cumt.edu.cn。
作者简介:李兵(1982年—)，正高级工程师，主要从事煤矿瓦斯治理、深部煤炭安全高效开采等方面的研究，157312030@qq.com。
基金资助:
国家重点研发计划项目(2024YFB4106300);与江苏省自然科学基金资助项目(BK20230184)

Density functional theory study of interaction between H₂O/CO₂/CH₄ and oxygen-containing functional groups on coal surface

LI Bing¹^,²(), ZHENG Sijian³^,⁴^,^*(), HU Hongqing³^,⁴^,⁵, TIAN Yuchen³^,⁴^,⁵, ZHANG Helong³^,⁴^,⁵, XU Biao¹^,², RUI Chengqi¹^,², ZHANG Guoxin³^,⁴^,⁵, SU Sheng³^,⁴^,⁵, ZHANG Yue³^,⁴^,⁵, YANG Dalin³^,⁴^,⁵

¹ Huainan Mining Industry (Group) co., Ltd, Huainan 232001, China
² Ping’an Mining Engineering Technology Research Institute Co., Ltd, Anhui Coal Mine Green and Low Carbon Development Engineering Research Center, Huainan 232001, China
³ Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization, China University of Mining and Technology, Xuzhou 221008, China
⁴ Carbon Neutrality Institute, China University of Mining and Technology, Xuzhou 221008, China
⁵ School of Resources and Geosciences, China University of Mining and Technology, Xuzhou 221116, China

Received:2025-10-22 Revised:2026-01-12 Online:2026-04-15 Published:2026-04-30
Contact: ^*sijian.zheng@cumt.edu.cn

摘要/Abstract

摘要：

运用量子化学密度泛函理论(DFT)模拟方法，从微观角度模拟了煤矿中3种常见分子(H₂O、CO₂、CH₄)在煤表面4种常见含氧官能团上的吸附机理。研究了吸附质分子以及煤中各含氧官能团的静电势，H₂O、CO₂、CH₄与含氧官能团的吸附距离和吸附能以及吸附前后的Mulliken电荷转移量。结果表明：各含氧官能团最大正静电势的大小顺序为-COOH>-OH>-C=O>-OCH₃；最大负静电势的大小顺序为-OH>-OCH₃>-COOH>-C=O。吸附质分子最大正负静电势的大小顺序均为H₂O>CO₂>CH₄。吸附能计算结果表明3种分子的吸附强度存在H₂O>CO₂>CH₄的关系，H₂O在各含氧官能团上的吸附强度顺序为-COOH>-OCH3>-OH>-C=O，CO₂和CH₄吸附强度顺序为-OCH₃>-COOH>-OH>-C=O。Mulliken电荷分析表明，含氧官能团中的氧原子易得电子，吸附质电子转移量越大，吸附越稳定，吸附稳定性顺序为H₂O>CO₂>CH₄。

关键词: 含氧官能团, 密度泛函理论, 吸附能, 静电势, 吸附质

Abstract:

Using quantum chemical Density Functional Theory (DFT) simulations, the adsorption mechanisms of three common molecular species in coal mines (H₂O, CO₂, and CH₄) onto four prevalent oxygen-containing functional groups on coal surfaces were investigated from a microscopic perspective. The electrostatic potentials of the adsorbate molecules and the functional groups were evaluated, along with the adsorption distances, adsorption energies, and Mulliken charge transfer before and after adsorption. The results indicate that the order of maximum positive electrostatic potential for the functional groups is:-COOH>-OH>-C=O>-OCH₃. The order of maximum negative electrostatic potential is:-OH>-OCH₃>-COOH>-C=O. For the adsorbate molecules, the order of both maximum positive and negative electrostatic potentials is H₂O>CO₂>CH₄. Adsorption energy calculations reveal that the adsorption strength of the three molecules follows the trend H₂O>CO₂>CH₄. Specifically, the adsorption strength of H₂O on the various functional groups follows the order -COOH>-OCH₃> -OH>-C=O, whereas the adsorption strengths of CO₂ and CH₄ follow the order -OCH₃>-COOH>-OH>-C=O. Mulliken charge analysis demonstrates that oxygen atoms in the functional groups readily accept electrons. A greater amount of electron transfer from the adsorbate correlates with a more stable adsorption configuration. The stability order of adsorption is confirmed as H₂O>CO₂>CH₄.

Key words: oxygen-containing functional groups, density functional theory, adsorption energy, electrostatic potential, adsorbates

中图分类号:

李兵, 郑司建, 胡洪清, 田钰琛, 张贺龙, 徐标, 芮成奇, 张国鑫, 苏升, 张越, 杨达林. H₂O/CO₂/CH₄与煤表面含氧官能团相互作用密度泛函理论研究[J]. 石油科学通报, 2026, 11(2): 605-613.

LI Bing, ZHENG Sijian, HU Hongqing, TIAN Yuchen, ZHANG Helong, XU Biao, RUI Chengqi, ZHANG Guoxin, SU Sheng, ZHANG Yue, YANG Dalin. Density functional theory study of interaction between H₂O/CO₂/CH₄ and oxygen-containing functional groups on coal surface[J]. Petroleum Science Bulletin, 2026, 11(2): 605-613.

https://sykxtb.cup.edu.cn/CN/Y2026/V11/I2/605

图/表 14

图1 含氧官能团片段结构模型

Fig. 1 Oxygen-containing functional group model

图2 吸附质分子模型

Fig. 2 Molecular modelling of adsorbates

图3 吸附质分子初始吸附构型

Fig. 3 Initial adsorption configuration of adsorbate molecules

图4 含氧官能团静电势能投影

Fig. 4 Electrostatic potential energy projection of oxygen-containing functional groups

图5 吸附质分子静电势能分布投影

Fig. 5 Projection of electrostatic potential energy distribution of adsorbent molecules

图6 H₂O在不同吸附构型下吸附距离

Fig. 6 H₂O adsorption distances in different adsorption con-figurations

图7 CO₂在不同吸附构型下吸附距离

Fig. 7 CO₂ adsorption distances in different adsorption con-figurations

图8 CH₄在不同吸附构型下吸附距离

Fig. 8 CH₄ adsorption distances in different adsorption con-figurations

图9 吸附质分子最优吸附构型下吸附距离与吸附能

Fig. 9 Adsorption distance and energy of adsorbate molecule under optimal adsorption configuration

图10 H₂O吸附后各原子电荷改变量

Fig. 10 Change in charge of each atom after adsorption of H₂O molecule

图11 CO₂吸附后各原子电荷改变量

Fig. 11 Change in charge of each atom after adsorption of CO₂ molecule

图12 CH₄吸附后各原子电荷改变量

Fig. 12 Change in charge of each atom after adsorption of CH₄ molecule

图13 吸附后H₂O分子键长及H-O-H键角改变量

Fig. 13 The change of H₂O molecular bond length and H-O-H bond Angle after adsorption

图14 吸附后含氧官能团氧原子电荷改变量

Fig. 14 The amount of oxygen atom charge change after adsorption of oxygen-containing functional groups

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H₂O/CO₂/CH₄与煤表面含氧官能团相互作用密度泛函理论研究

Density functional theory study of interaction between H₂O/CO₂/CH₄ and oxygen-containing functional groups on coal surface

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