Porous BN for selective adsorption of sulfur-containing compounds from fuel oil: DFT study

Qiaoling LI; Xiaoyu WU; Xuewei WANG; Zhi XIE; Xiaofei YU; Xiaojing YANG; Yang HUANG; Lanlan LI

doi:10.11949/0438-1157.20200359

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Porous BN for selective adsorption of sulfur-containing compounds from fuel oil: DFT study

Thermodynamics | 更新时间：2025-11-25

- Porous BN for selective adsorption of sulfur-containing compounds from fuel oil: DFT study
- CIESC Journal Vol. 71, Issue 10, Pages: 4601-4610(2020)
- 作者机构：
  
  河北工业大学材料科学与工程学院，天津 300130
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200359
  CLC： O 641
- Received：07 April 2020，
  
  Revised：2020-05-16，
  
  Published：05 October 2020
- 稿件说明：
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李巧灵, 吴晓宇, 王学伟, 谢智, 于晓飞, 杨晓婧, 黄阳, 李兰兰. 多孔BN选择性去除燃油中硫化合物的密度泛函理论研究[J]. 化工学报, 2020, 71(10): 4601-4610

LI Qiaoling, WU Xiaoyu, WANG Xuewei, XIE Zhi, YU Xiaofei, YANG Xiaojing, HUANG Yang, LI Lanlan. Porous BN for selective adsorption of sulfur-containing compounds from fuel oil: DFT study[J]. CIESC Journal, 2020, 71(10): 4601-4610
李巧灵, 吴晓宇, 王学伟, 谢智, 于晓飞, 杨晓婧, 黄阳, 李兰兰. 多孔BN选择性去除燃油中硫化合物的密度泛函理论研究[J]. 化工学报, 2020, 71(10): 4601-4610 DOI： 10.11949/0438-1157.20200359.

LI Qiaoling, WU Xiaoyu, WANG Xuewei, XIE Zhi, YU Xiaofei, YANG Xiaojing, HUANG Yang, LI Lanlan. Porous BN for selective adsorption of sulfur-containing compounds from fuel oil: DFT study[J]. CIESC Journal, 2020, 71(10): 4601-4610 DOI： 10.11949/0438-1157.20200359.

摘要

选择性去除燃油中的硫化物对环境和人类健康具有重要意义。采用基于密度泛函理论（DFT）和含色散矫正的密度泛函理论（D-DFT）的方法，研究了多孔氮化硼（p-BN）及其空位缺陷对燃油中噻吩类硫化物及非硫化物的吸附行为及吸附选择性。结果表明：B—N极性键与硫化物极性分子之间的分子间力使p-BN能选择性去除燃油中的二苯并噻吩（DBT）；引入N、B空位缺陷后，缺陷能级与S原子形成化学相互作用并伴随电荷转移，进一步增强了p-BN对硫化物的吸附。通过对N、B空位缺陷形成能的计算，预测了合成含V

、V

的p-BN所需的化学条件：在富硼条件下，采用B

作为B源比采用B、α-B

和BH

等更有利于V

的形成；而在富氮环境下采用N

作为N源比采用N

、NH

等更有利于V

形成。为实验上有目的地合成高效吸附脱硫材料提供理论依据。

Abstract

Selective removal of sulfides in fuel oil is of great significance to the environment and human health. In this work

using density functional theory (DFT) with and without long-range dispersion correction

via

Grimme􀆳

s scheme (D-DFT)

the adsorption behavior and adsorption selectivity of dibenzothiophene (DBT)

-hexadecane

and

-octane and toluene on the porous boron nitrides (p-BN) with/without vacancy defect have been studied. On perfect p-BN

the adsorption energy (

ads

) was calculated to be 1.395

0.600 and 0.457 eV (PBE+D) for single DBT

-hexadecane and

-octane molecules respectively

indicating that the adsorption of DBT on p-BN is highly preferred over

-hexadecane. The strong adsorption of DBT on p-BN was attributed to the intermolecular force that derived from the interaction between the B—N polar bond and the permanent dipole of DBT molecule. With the introduction of nitrogen (V

) and boron (V

) vacancy defects

the

ads

of DBT increased to 1.650 and 1.875 eV (PBE+D) and the

ads

of the

-hexadecane is only 0.400 and 0.600 eV (PBE+D)

respectively. The electronic structure [calculations density of states (DOS)

the highest occupied molecular orbital (HOMO)

total charge density together with charge density difference

and Hirshfeld charges]

reveal that the chemical interactions between the defect level and S atom in sulfide enhanced the adsorption of DBT molecule on p-BN. For practical application

other sulfur-containing organic compounds including 4

6-dimethyldibenzothiophene (4

6-DMDBT)

thiophene (T)

benzothiophene (BT) and carbide toluene in fuel oil are also considered and p-BN still tends to selectively adsorb sulfides from carbides preferentially

suggesting that p-BN with/without vacancy defect is promising for the removal of sulfur-containing organic compounds from fuel oil. Finally

the defect formation energies were estimated to evaluate the energetic stability of defective p-BN. The growth of V

or V

strongly depends on the chemical environment. Under boron-rich conditions

the use of B

as the B source is more conducive to the formation of V

than the use of B

α-B

and BH

etc

. Contrastingly

the use of N

as the N source in the nitrogen-rich environment is more beneficial to the formation of V

than the use of N

. Our results provide a useful guidance for the design and fabrication of porous BN sorbent for sulfur-containing organic matter removing from fuel oil.

关键词

Keywords

references

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