N2在页岩干酪根上的吸附特征

doi:10.19596/j.cnki.1001-246x.8333

摘要/Abstract

摘要：

采用密度泛函理论的wB97XD方法、RDG函数方法和counterpoise correction理论，研究氮气在干酪根C₂₈H₁₄O和氮掺杂干酪根C₂₇H₁₄ON上的吸附特征。结果表明：N₂在干酪根上的活性吸附位点为苯环上方中心位置，吸附能在8~10 kJ·mol^-1之间，N₂和干酪根之间的相互作用主要是范德华相互作用和空间排斥作用。氮掺杂改变了干酪根的构型和电子云分布，导致含氮杂环不再是稳定的活性吸附位点，增强了排斥作用，使吸附能略有减小。研究结果对理解干酪根吸附小分子的特征有重要意义，能够为页岩气的开采提供理论支持。

关键词: 页岩气, 干酪根, 吸附, wB97XD, RDG函数

Abstract:

Density functional theory wB97XD method, RDG function method and counterpoise correction theory were used to study adsorption characteristics of N₂ on shale kerogen C₂₈H₁₄O and nitrogen-doped shale kerogen C₂₇H₁₄ON. It shows that the active adsorption site is located on the central position above the benzene ring for N₂ adsorbed on both kerogen C₂₈H₁₄O and nitrogen-doped kerogen C₂₇H₁₄ON. The adsorption energy is in the range of 8~10 kJ·mol^-1, which shows that the main interaction between nitrogen molecule and kerogens is van der Waals interaction and steric repulsion. Nitrogen doping changes the geometric configuration and electron cloud distribution of kerogen. As a result, the nitrogen-containing heterocycle is no longer a stable active site. The adsorption energy is a little lower than that of N₂ adsorbed on C₂₈H₁₄O, but it is still in the range of 8~10 kJ·mol^-1. The main interaction force between N₂ and C₂₇H₁₄ON is still van der Waals interaction and steric repulsion. This work is significant for understanding adsorption characteristics of small molecules on kerogens. It provides theoretical support for the exploring of shale gas.

Key words: shale gas, kerogen, adsorption, wB97XD, RDG function

中图分类号:

TG147

朱元强, 靳赛赛, 孙青青. N₂在页岩干酪根上的吸附特征[J]. 计算物理, 2021, 38(6): 707-712.

Yuanqiang ZHU, Saisai JIN, Qingqing SUN. Adsorption Characteristics of N₂ on Shale Kerogen[J]. Chinese Journal of Computational Physics, 2021, 38(6): 707-712.

图/表 5

图1 N2在干酪根C28H14O和氮掺杂干酪根C27H14ON上的吸附构型(键长单位: nm)

Fig.1 Configurations of N2 adsorbed on kerogen C28H14O and N-doped kerogen C27H14ON (unit of bond length : nm)

表1 N2在干酪根C28H14O和氮掺杂干酪根C27H14ON上的吸附能

Table 1 Adsorption energy of N2 on kerogen C28H14O and N-doped kerogen C27H14ON

构型	吸附能E/(kJ·mol^-1)	构型	吸附能E/(kJ·mol^-1)
C_A	9.857	C_B	9.831
C_C	9.630	C_D	8.134
C_E	9.177
N-C_A	9.146	N-C_B	9.524
N-C_C	9.685	N-C_D	8.907

表2 N2与干酪根C28H14O和氮掺杂干酪根C27H14ON之间的CHelpG电荷转移与MK电荷转移

Table 2 CHelpG and MK charge transfer between N2 and kerogen C28H14O and N-doped kerogen C27H14ON

构型	CHelpG(Δq)	MK(Δq)	构型	CHelpG(Δq)	MK(Δq)
C_A	-0.032 092	-0.008 584	C_B	-0.032 886	-0.008 587
C_C	-0.033 062	-0.010 621	C_D	-0.031 442	-0.013 607
C_E	-0.029 809	-0.008 745
N-C_A	-0.031 154	-0.006 188	N-C_B	-0.032 631	-0.009 709
N-C_C	-0.031 080	-0.006 393	N-C_D	-0.024 852	-0.005 012

图2 N2在干酪根C28H14O和氮掺杂干酪根C27H14ON界面吸附的散点图

Fig.2 Scatter diagrams of N2 adsorbed on kerogen C28H14O and N-doped kerogen C27H14ON interface

图3 N2在干酪根C28H13O和氮掺杂C27H13ON界面吸附的RDG等值面填色图

Fig.3 RDG isosurfaces of N2 adsorbed on kerogen C28H14O and N-doped kerogen C27H14ON interface

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N₂在页岩干酪根上的吸附特征

Adsorption Characteristics of N₂ on Shale Kerogen

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