Methylene Blue Adsorption Properties of Modified Wolfberry Biochar with EDTA-2Na

doi:10.19894/j.issn.1000-0518.240041

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (7): 1035-1046.DOI: 10.19894/j.issn.1000-0518.240041

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Methylene Blue Adsorption Properties of Modified Wolfberry Biochar with EDTA-2Na

Yan-Jiao REN¹(), Rong-Sheng XU², Ping WANG², Dong SUN², Wan-Dong GENG², Hai-Yong ZHANG³

^1.Xinhua College of Ningxia University，Yinchuan 750021，China
^2.Chemistry and Chemical Engineering College，North Minzu University，Yinchuan 750021，China
^3.Chemistry and Environmental Engineering College，China University of Mining and Technology （Beijing），Beijing 100083，China

Received:2024-02-04 Accepted:2024-05-05 Published:2024-07-01 Online:2024-08-03
Contact: Yan-Jiao REN
About author:ryj844278352@163.com
Supported by:
the Key Research Project of Xinhua College of Ningxia University in 2021(21XHKY02);the Scientific Research Project of Higher Education Institutions of Ningxia Hui Autonomous Region in 2023(NYG2024230);the Research Project of Xinhua College of Ningxia University in 2024(24XHKY13)

Abstract

Abstract:

Biomass activated carbon （CP） was prepared from Ningxia Wolfberry stalk by high temperature carbonization method with H₃PO₄ as activator， and the surface modification was carried out by EDTA-2Na to obtain nitrogen-doped activated carbon （CPE）. X-ray diffraction （XRD）， X-ray photoelectron spectroscopy （XPS）， Fourier transform infrared spectroscopy （FT-IR） and scanning electronic microscopy （SEM） were used to study the surface morphology and chemical structure of EDTA-2Na， to elucidate the modification mechanism of EDTA-2Na and the adsorption mechanism of methylene blue on CPE. The results showed that doping EDTA-2Na can effectively regulate the pore structure and functional groups of biochar， and significantly improve the specific surface area， pore structure and active adsorption site of biochar. The parameters of CPE （specific surface area （816.47 m²/g）， total pore volume （0.4925 cm³/g） and average pore size （2.41 nm） of biochar modified by EDTA-2Na were significantly better than those of CP （241.45 m²/g） and total pore volume （0.1280 cm³/g） and average pore size （2.12 nm）， and stable amino （—NH—， —NH₂—） and pyrrole structure nitrogen were formed on the surface， which constituted the active surface biomass carbon material CPE with good adsorption effect on methylene blue. Under normal temperature and neutral conditions， the maximum adsorption capacity of CPE for MB was 658.8 mg/g， which increased the adsorption rate by 83.92% compared with that of biological carbon CP （adsorption capacity 358.2 mg/g） without N doping. The isothermal adsorption process of CPE for MB was consistent with Langmuir model （R²=0.9896）， and the adsorption kinetics was consistent with quasi-second-order kinetic model （R²=0.99997）. The adsorption process was mainly monolayer chemisorption. It has good recycling performance.

Key words: Wolfberry stalk, H₃PO₄ activation, Ethylenediaminetetraacetic acid disodium salt, Methylene blue adsorption

CLC Number:

O643

Yan-Jiao REN, Rong-Sheng XU, Ping WANG, Dong SUN, Wan-Dong GENG, Hai-Yong ZHANG. Methylene Blue Adsorption Properties of Modified Wolfberry Biochar with EDTA-2Na[J]. Chinese Journal of Applied Chemistry, 2024, 41(7): 1035-1046.

Figures/Tables 15

Fig.1 Isothermal absorption and desorption curves （A） and aperture distribution curves （B）

Table 1 Specific surface area and pore structure parameters of activated carbon

Sample	V_mic/（cm³·g^-1）	V_mes/（cm³·g^-1）	V_tot/（cm³·g^-1）	S_BET/（cm²·g^-1）	D_p/nm
CP	0.096 3	0.031 8	0.128 0	241.45	2.12
CPE	0.380 0	0.112 6	0.492 5	816.47	2.41

Fig.2 SEM images of CP （A） and CPE （B）

Fig.3 FT-IR spectra of CP and CPE

Fig.4 XRD pattern of CP and CPE

Fig.5 XPS full spectra of CPE and CP （A）， N1s spectra （B）， P2p spectra （C）， C1s spectra （D） and O1s spectra （E） of CPE and CP

Table 2 Results of XPS analysis of surface elements of two activated carbons

Sample		C/%	N/%	O/%	P/%
CP	Total percentage/%	58.76	3.14	31.14	6.96
CPE	Total percentage/%	83.71	4.59	10.61	1.09

Fig.6 Effect of adsorption time （A） and pH （B） on MB adsorption

Fig.7 Quasi-first-order kinetic model， quasi-second-order kinetic model and in-particle diffusion model of CP （A， C， E） and CPE （B， D， F） for MB

Table 3 Main parameters of the three dynamic models

Sample	Pseudo-first order model			Pseudo-second order model
Sample	q_e/（mg·g^-１）	K₁/min^-1	R²	q_e/（mg·g^-1）	K₂/min^-1	R²
CP	39.3	0.006 1	0.921 06	370.4	0.000 611	0.999 9
CPE	112.3	0.008 1	0.976 5	662.3	0.000 213	0.999 97
Sample	Intraparticle diffusion model
Sample	K_id1/（mg·g^-1·min^-1/2）	C₁	$R 12$	K_id2/（mg·g^-1·min^-1/2）	C₂	$R 22$
CP	25.501 8	151.417 3	0.838 9	0.045 57	367.703 0	0.932 8
CPE	58.012 6	137.331 9	0.955 1	0.402 3	642.076 9	0.601 9

Table 3 Main parameters of the three dynamic models

Sample	Pseudo-first order model			Pseudo-second order model
Sample	q_e/（mg·g^-１）	K₁/min^-1	R²	q_e/（mg·g^-1）	K₂/min^-1	R²
CP	39.3	0.006 1	0.921 06	370.4	0.000 611	0.999 9
CPE	112.3	0.008 1	0.976 5	662.3	0.000 213	0.999 97
Sample	Intraparticle diffusion model
Sample	K_id1/（mg·g^-1·min^-1/2）	C₁	$R 12$	K_id2/（mg·g^-1·min^-1/2）	C₂	$R 22$
CP	25.501 8	151.417 3	0.838 9	0.045 57	367.703 0	0.932 8
CPE	58.012 6	137.331 9	0.955 1	0.402 3	642.076 9	0.601 9

Fig.8 Isothermal adsorption model of CP （A， C） and CPE （D， E） for MB

Table 4 Parameters of Langmuir and Freundlich isothermal adsorption models

Sample	Langmuir			Freundlich
Sample	q_e/（mg·g^－1）	K_L/min^－1	R²	K_F（ $m g 1 + 1 n$ ·g^-1· $L - 1 n$ ）	1/n	R²
CP	349.7	0.098 42	0.986 0	31.850 8	0.516 2	0.931 8
CPE	657.9	0.043 48	0.989 6	14.375 1	0.350 3	0.496 2

Table 4 Parameters of Langmuir and Freundlich isothermal adsorption models

Sample	Langmuir			Freundlich
Sample	q_e/（mg·g^－1）	K_L/min^－1	R²	K_F（ $m g 1 + 1 n$ ·g^-1· $L - 1 n$ ）	1/n	R²
CP	349.7	0.098 42	0.986 0	31.850 8	0.516 2	0.931 8
CPE	657.9	0.043 48	0.989 6	14.375 1	0.350 3	0.496 2

Fig.9 Recycles of activated carbon in degradation of MB

Fig.10 Possible adsorption mechanism of N structure of CPE

Table 5 Comparison of nitrogen doping modification methods and MB adsorption effects of common biomass activated carbon

Biomass	Adsorption	Specific surface area/（m²·g^-1）	Pass	Nitrogenous species	MB adsorption capacity/（mg·g^-1）	Ref.
Peanut shell	K₂CO₃+Melamine	1 922.27	Micropore and mesopore	Quaternary nitrogen， pyridinium oxide nitrogen	480.5	［31］
Corn stalk	KHCO₃+Urea	1 871	Mesopore	Pyrrole N and pyridine N	491	［32］
Sichuan pepper seed	H₃PO₄	740	Micropore and mesopore	-	495	［33］
Bamboo	Urea+KHCO₃	1 693	Mesopore	Pyridine nitrogen， pyrrole nitrogen and amino nitrogen	499.3	［34］
Wolfberry stalk	H₃PO₄+EDTA-2Na	816.47	Micropore and mesopore	Amido（—NH—， —NH₂—） and pyrrole nitrogen	658.8	This work

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Methylene Blue Adsorption Properties of Modified Wolfberry Biochar with EDTA-2Na

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