Enhanced Styrene Adsorption by Grafted Lactone-based Activated Carbon

doi:10.15541/jim20230473

Abstract

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)

CLC Number:

TQ424

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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

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

Fig. S1 Schematic illustration of styrene dynamic adsorption device

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

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

Fig. S3 Styrene interacting with graphite layer

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