极端外电场诱导甲烷对称性破缺促进重整反应活化

王锐; 周玉婷; 王瑜婷; 尹童; 张家敏; 周焮; 谌雪乐; 杨志毫; 税奇军; 魏世勇; 向文军

doi:10.11949/0438-1157.20251447

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极端外电场诱导甲烷对称性破缺促进重整反应活化

能源和环境工程 | 更新时间：2026-09-29

- 极端外电场诱导甲烷对称性破缺促进重整反应活化
- Extreme external electric field induces symmetry breaking of methane and activates its reforming reactions
- 化工学报 2026年77卷第8期页码：4878-4887
- 作者机构：
  
  1.四川文理学院化学化工学院乡村低成本环境治理技术四川省高校重点实验室，四川达州 635000
  2.湖北民族大学化学与环境工程学院，湖北恩施 445000
  3.四川文理学院智能制造学院，四川达州 635000
  4.四川轻化工大学绿色催化四川省高校重点实验室，四川自贡 643000
- 作者简介：
  
  王锐（1992—），男，博士，特聘教授，wangrui@sasu.edu.cn
  向文军（1975—），男，硕士，教授，471236838@qq.com
- 基金信息：
  
  国家自然科学基金项目(22408245;12304276);四川文理学院高层次人才科研启动项目(2022GCC07Z);乡村低成本环境治理技术四川省高校重点实验室开放基金(XCH2024ZB-04);绿色催化四川省高校重点实验室开放基金(LZJ2203)
- DOI：10.11949/0438-1157.20251447
  中图分类号： TQ 019;TQ 511
- 收稿：2025-12-23，
  
  修回：2026-03-04，
  
  纸质出版：2026-08-25
- 稿件说明：
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王锐, 周玉婷, 王瑜婷, 尹童, 张家敏, 周焮, 谌雪乐, 杨志毫, 税奇军, 魏世勇, 向文军. 极端外电场诱导甲烷对称性破缺促进重整反应活化[J]. 化工学报, 2026, 77(8): 4878-4887

WANG Rui, ZHOU Yuting, WANG Yuting, YIN Tong, ZHANG Jiamin, ZHOU Xin, SHEN Xuele, YANG Zhihao, SHUI Qijun, WEI Shiyong, XIANG Wenjun. Extreme external electric field induces symmetry breaking of methane and activates its reforming reactions[J]. CIESC Journal, 2026, 77(8): 4878-4887
王锐, 周玉婷, 王瑜婷, 尹童, 张家敏, 周焮, 谌雪乐, 杨志毫, 税奇军, 魏世勇, 向文军. 极端外电场诱导甲烷对称性破缺促进重整反应活化[J]. 化工学报, 2026, 77(8): 4878-4887 DOI： 10.11949/0438-1157.20251447.

WANG Rui, ZHOU Yuting, WANG Yuting, YIN Tong, ZHANG Jiamin, ZHOU Xin, SHEN Xuele, YANG Zhihao, SHUI Qijun, WEI Shiyong, XIANG Wenjun. Extreme external electric field induces symmetry breaking of methane and activates its reforming reactions[J]. CIESC Journal, 2026, 77(8): 4878-4887 DOI： 10.11949/0438-1157.20251447.

摘要

甲烷（CH

）重整反应制备合成气是天然气转化与高值化利用的基础反应，CH

分子的高对称性是其难以被活化而降低转化效率的关键问题。本研究首先通过密度泛函理论模拟研究CH

及其重整反应所涉及的CO

和H

O等小分子在外电场作用下的电荷布居、电子局域性与偶极矩变化，在此基础上构建甲烷干重整（DRM）和甲烷湿重整反应（SRM）体系并研究外电场作用下DRM和SRM体系的相互作用能、底物分子的电荷及其空间构型。研究显示，极端外电场的存在可促使CH

和CO

等非极性分子的电子再分布，电子密度沿电场反方向增大而发生偏聚，导致CH

分子对称性降低，并且产生诱导偶极矩而被极化；当外电场强度达到1 V/Å（1 Å=0.1 nm）时，CH

的电场诱导偶极矩为0.71 D（1 D≈3.33564×10

-30

C·m），平行于外电场方向的CO

分子两端O原子的Hirshfeld电荷变化量Δ

为0.17，垂直于外电场方向的线性CO

分子发生形态弯曲变化。极性H

O分子在1 V/Å外电场作用下产生的扭矩可导致H

O分子旋转而定向分布。0.1 V/Å外电场作用即可对SRM体系的相互作用能产生明显的增强作用，并且外电场对SRM体系中H

O的调控作用受H

O分子偶极矩以及邻近CH

分子的相互作用共同影响；在1 V/Å外电场作用下，DRM和SRM体系的相互作用能分别增加2.43倍和3.72倍而有助于甲烷重整反应的活化。

Abstract

Methane (CH

) reforming to syngas lays fundamental for transformation and utilization of natural gas

where CH

with high symmetry is hardly to activate

becoming a most challenge. This study first uses density functional theory simulations to investigate the charge population

electronic localization

and dipole moment changes of small molecules such as CO

and H

O invo

lved in the reforming reaction of CH

under an external electric field. Based on this

dry methane reforming (DRM) and wet methane reforming (SRM) systems were constructed

and the interaction energies

substrate molecule charges

and spatial configurations of the DRM and SRM systems under an external electric field were studied. It was found that the strong external electric field could regulate the distribution of electron in molecules

especially for the nonpolar CH

and CO

enhancing the electron density along with the electric field direct

weakening the symmetry of CH

and polarizing it through causing an induced dipole moment. When the intensity of external electric field was 1 V/Å

the induced dipole moment of CH

was 0.71 D

and Hirshfeld charge amount transferring from O_1 to O_2 in CO

was up to 0.17 when CO

was parallel to

while deformation for the vertical CO

. Different with nonpolar CH

and CO

the orientation of H

O would be forced in line with the direct of

driven by a torque due to dipole moment of H

O in an external electric field of 1 V/Å. In SRM system

interaction energy of reactants could be effectively enhanced even at 0.1 V/Å. And the regulation for H

O by

was co-affected by dipole moment of H

O itself and adjacent CH

molecule. At 1 V/Å

the interaction energy of reactants in DRM and SRM systems were improved by 2.43 folds and 3.72 folds

respectively

then being beneficial for activating the CH

reforming reaction.

关键词

Keywords

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