接枝内酯基活性炭增强苯乙烯吸附性能研究

doi:10.15541/jim20230473

无机材料学报 ›› 2024, Vol. 39 ›› Issue (4): 390-398.DOI: 10.15541/jim20230473 CSTR: 32189.14.10.15541/jim20230473

所属专题：【材料计算】计算材料(202409)

接枝内酯基活性炭增强苯乙烯吸附性能研究

吴光宇¹^,²(), 舒松¹^,², 张洪伟¹^,², 李建军¹^,³()

1.四川大学建筑与环境学院, 成都 610000
2.国家烟气脱硫工程技术研究中心, 成都 610000
3.四川大学碳中和未来技术学院, 成都 610000

收稿日期:2023-10-13 修回日期:2023-12-04 出版日期:2024-04-20 网络出版日期:2023-12-25
通讯作者: 李建军, 教授. E-mail: jjli@scu.edu.cn
作者简介:吴光宇(1999-), 男, 硕士研究生. E-mail: 1464075183@qq.com
基金资助:
四川省重点研发项目(2023YFS0354)

Enhanced Styrene Adsorption by Grafted Lactone-based Activated Carbon

WU Guangyu¹^,²(), SHU Song¹^,², ZHANG Hongwei¹^,², LI Jianjun¹^,³()

1. College of Architecture and Environment, Sichuan University, Chengdu 610000, China
2. National Engineering Research Center for FGD, Chengdu 610000, China
3. College of Carbon Neutrality Future Technology, Sichuan University, Chengdu 610000, China

Received:2023-10-13 Revised:2023-12-04 Published:2024-04-20 Online:2023-12-25
Contact: LI Jianjun, professor. E-mail: jjli@scu.edu.cn
About author:WU Guangyu (1999-), male, Master candidate. E-mail: 1464075183@qq.com
Supported by:
Key R&D Projects of Sichuan Province(2023YFS0354)

摘要/Abstract

摘要：

活性炭以其丰富的孔道结构和高比表面积而在吸附苯乙烯废气上具有巨大的应用潜力, 然而含氧官能团对弱极性苯乙烯的吸附作用机理尚未明晰。本研究通过酸浸渍法制备改性活性炭AC-S和AC-N, 探究改性活性炭孔径结构、比表面积和含氧官能团的演变规律及其对苯乙烯吸附性能的影响。结果表明, 酸改性可以明显提高活性炭对苯乙烯的吸附量。通过吸附动力学、吸附等温拟合发现, 活性炭改性前后均受物理吸附与化学吸附的复合作用影响, 改性后活性炭更倾向于单层吸附。HNO₃改性活性炭(AC-N)的孔隙结构在苯乙烯有效吸附孔径范围内没有显著改变, 表面含氧官能团含量增加提高了AC-N对苯乙烯的吸附性能。表面含氧官能团分析表明, 内酯基是提高改性活性炭对苯乙烯吸附量的关键因素。密度泛函理论(DFT)计算表明, AC-N上的内酯基官能团与苯乙烯的乙烯基产生强相互作用, 增强了苯乙烯在改性活性炭上的吸附。

关键词: 活性炭, 吸附, 苯乙烯, 含氧官能团, 密度泛函理论(DFT)

Abstract:

Activated carbon's porous nature and high specific surface area make it an effective tool for adsobing waste gas containing styrene. However, the mechanism by which oxygen-containing functional groups adsorb weak-polar styrene remains unclear. This study described the preparation of the modified activated carbon materials AC-S and AC-N using the acid leaching method. The pore structure and specific surface area of modified activated carbon, the evolution of oxygen-containing functional groups, and their impact on the styrene-adsorbing performance were investigated. The results demonstrated that acid modification significantly improved the styrene-adsorbing capacity of activated carbon. Physical and chemical adsorption impacted both modified and unmodified activated carbon materials, as determined by the adsorption kinetics studies and isotherm fitting analyses. Monolayer adsorption was more likely to occur on modified activated carbon. HNO₃-modified activated carbon (AC-N) maintained its effective styrene adsorption pore size range. The increasing number of oxygen-containing functional groups on the surface improved the styrene adsorption performance of AC-N. Study of oxygen-containing functional groups on the surface revealed that lactone group was a key factor in improving the modified activated carbon's ability to adsorb styrene. Density functional theory (DFT) calculations showed that lactone group on AC-N strongly interacted with the vinyl group in styrene, thereby enhancing the styrene adsorption performance of modified activated carbon.

Key words: activated carbon, adsorption, styrene, oxygen-containing functional group, density functional theory (DFT)

中图分类号:

TQ424

吴光宇, 舒松, 张洪伟, 李建军. 接枝内酯基活性炭增强苯乙烯吸附性能研究[J]. 无机材料学报, 2024, 39(4): 390-398.

WU Guangyu, SHU Song, ZHANG Hongwei, LI Jianjun. Enhanced Styrene Adsorption by Grafted Lactone-based Activated Carbon[J]. Journal of Inorganic Materials, 2024, 39(4): 390-398.

图/表 16

图1 AC、AC-S和AC-N的(a)XRD谱图, (b)Raman谱图, (c)N2吸脱附等温线和(d)孔径分布图

Fig. 1 (a) XRD patterns, (b) Raman spectra, (c) N2 adsorption-desorption isotherms, and (d) pore size distributions of AC, AC-S, and AC-N Colorful figures are available on website

表1 AC、AC-S和AC-N的孔径结构特征

Table 1 Textural characteristics of AC, AC-S, and AC-N

Sample	S_BET/ (m²•g^-1)	V_micro/ (cm³•g^-1)	V_meso/ (cm³•g^-1)	V_total/ (cm³•g^-1)
AC	485.51	0.12	0.21	0.33
AC-S	558.10	0.14	0.24	0.38
AC-N	348.88	0.06	0.21	0.27

图2 AC、AC-S和AC-N的(a)表面官能团含量和(b)FT-IR谱图

Fig. 2 (a) Amounts of surface functional groups and (b) FT-IR spectra of AC, AC-S, and AC-N

图3 AC、AC-S和AC-N对苯乙烯的(a)穿透曲线和(b)饱和吸附量

Fig. 3 (a) Breakthrough curves and (b) saturation adsorption capacity for the adsorption of styrene by AC, AC-S, and AC-N Colorful figures are available on website

图4 (a)AC, (b)AC-S和(c)AC-N的吸附动力学及其(d)吸附等温线拟合

Fig. 4 Adsorption kinetics of (a) AC, (b) AC-S and (c) AC-N, and (d) correspoding adsorption isotherm fitting Colorful figures are available on website

图5 苯乙烯(a~d)与羟基作用, (e~h)与内酯基作用以及(j~m)与羧基作用的构型

Fig. 5 Configurations of (a-d) styrene interacting with hydroxyl group, (e-h) styrene interacting with lactone group, and (j-m) styrene interacting with the carboxyl group

图6 苯乙烯在内酯基上最佳吸附构型的(a)切面图和(b)ELF

Fig. 6 (a) Section view and (b) ELF of optimal adsorption configuration of styrene on the lactone group

图7 活性炭上内酯基与苯乙烯相互作用的吸附机理

Fig. 7 Adsorption mechanism of interaction between styrene and lactone group on activated carbon

表S1 AC、AC-S、AC-N吸附苯乙烯的动力学参数

Table S1 Kinetic parameters of styrene adsorption by AC, AC-S, and AC-N

Sample	PFO			PSO
Sample	q_e/(mg•g^-1)	k₁/min^-1	R²	q_e/(mg•g^-1)	k₂/(g•mg^-1•min^-1)	R²
AC	123	0.0041	0.99	184	1.59×10^-5	0.99
AC-S	319	0.0015	0.99	548	1.59×10^-6	0.99
AC-N	338	0.0014	0.99	595	1.29×10^-6	0.99

表S2 苯乙烯吸附的Langmuir和Freundlich模型拟合参数

Table S2 Fitting parameters of the Langmuir and Freundlich models for styrene adsorption

Isotherm model	Parameter	AC	AC-S	AC-N
Langmuir	q_e/(mg•g^-1)	239	317	281
	K_L/(m³•mg^-1)	0.25	0.40	0.42
	R²	0.98	0.99	0.97
	RMSE	3.53	3.86	5.39
Freundlich	K_F/((mg•g^-1)·(m³•mg^-1)^1/ⁿ)	59.82	122.75	102.76
	n	2.06	2.63	2.69
	R²	0.99	0.95	0.93
	RMSE	2.73	7.74	8.52

表S3 AC、AC-S和AC-N的表面官能团含量

Table S3 Amounts of surface functional groups of AC, AC-S, and AC-N

Sample	Hydroxyl group/(mmol•g^-1)	Lactone group/(mmol•g^-1)	Carboxyl group/(mmol•g^-1)	Total/(mmol•g^-1)
AC	0.10	0.01	0.02	0.13
AC-S	0.21	0.82	0.15	1.18
AC-N	0.14	0.63	0.37	1.14

表S4 AC、AC-S、AC-N表面C1s的XPS分析结果

Table S4 XPS results of C1s on the surface of AC, AC-S, and AC-N

Sample	Relative content/%
Sample	C-C	C-O	C=O/COOH	O-C=O
AC	70.67	20.99	2.91	5.43
AC-S	65.14	16.56	4.99	13.32
AC-N	72.94	6.70	14.57	5.79

图S1 苯乙烯动态吸附装置示意图

Fig. S1 Schematic illustration of styrene dynamic adsorption device

图S2 活性炭的SEM形貌

Fig. S2 SEM morphologies of activated carbon (a) AC; (b) AC-S; (c) AC-N

图S3 AC、AC-S和AC-N的(a)C1s XPS谱图和(b)含氧官能团的相对含量

Fig. S3 (a) C1s XPS spectra and (b) relative contents of oxygen-containing functional groups for AC, AC-S and AC-N

图S4 苯乙烯与石墨层作用

Fig. S3 Styrene interacting with graphite layer

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接枝内酯基活性炭增强苯乙烯吸附性能研究

Enhanced Styrene Adsorption by Grafted Lactone-based Activated Carbon

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