Adsorption mechanism of methyl orange by using the magnetic biochar -Based on density functional theory and batch adsorption experiment study
WANG Shi-sheng1,2, ZHANG Meng-meng1, SHENG Guang-hong1,2, TIAN Yong-pan3, LIU Yi-yun1,2, ZHANG Hui-juan1,2, LIU Yong-xin1
1. School of Energy and Environment, Anhui University of Technology, Ma'anshan 243002, China; 2. Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education, Anhui University of Technology, Ma'anshan 243032, China; 3. School of Metallurgical Engineering, Anhui University of Technology, Ma'anshan 243032, China
Abstract：Magnetic biochar (Fe3O4@C-NH2) was used as the adsorbent for removal of Methyl Orange (MO) in this study. The effects of concentration, temperature and pH on the adsorption performance were investigated, and then the Spectroscopic analysis and density functional theory were used to reveal the adsorption mechanism. The results demonstrated that the adsorption kinetics followed the pseudo-second-order model and the Freundlich model, and the process owned the characteristics of spontaneity, endothermic and entropy increasing. The equilibrium adsorption capacity decreased with the increment of pH (3~10). Spectroscopic analysis showed that the adsorption forces contain the hydrogen bonding, π-π bond accumulation, π-π electron donor-acceptor (EDA) and electrostatic interaction. According to the analysis of electrostatic potential and frontier orbit, the binding energy and energy gap of carboxyl group wereEads= -139.08kJ/mol, Egap= 3.07eV respectively, which were higher than those of hydroxyl group (Eads = -94.47kJ/mol, Egap = 3.16eV), amino group (Eads = -76.10kJ/mol, Egap = 3.17eV) and aromatic ring (Eads= -41.99kJ/mol, Egap = 3.18eV). It was found that the hydrophobic action existed in the adsorption process; besides, the hydrogen bond and π-π EDA were the main forces in the process based on the results integrating the independent gradient model and Hirshfeld partition and Atoms in molecules (IGMH-AIM).
王诗生, 张梦梦, 盛广宏, 田勇攀, 刘轶鋆, 章慧娟, 刘永兴. 磁性生物炭吸附水中甲基橙的作用机制——基于密度泛函理论与实验研究[J]. 中国环境科学, 2023, 43(9): 4596-4605.
WANG Shi-sheng, ZHANG Meng-meng, SHENG Guang-hong, TIAN Yong-pan, LIU Yi-yun, ZHANG Hui-juan, LIU Yong-xin. Adsorption mechanism of methyl orange by using the magnetic biochar -Based on density functional theory and batch adsorption experiment study. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(9): 4596-4605.
苏龙,张海波,程红艳,等.木耳菌糠生物炭对阳离子染料的吸附性能研究[J]. 中国环境科学, 2021,41(2):693-703. Su L, Zhang H B, Cheng H Y, et al. Study on adsorption properties of biochar derived from spent Auricularia auricula substrate for cationic dyes[J]. China Environmental Science, 2021,41(2):693-703.
[2]
Zhou Y B, Lu J, Zhou Y, et al. Recent advances for dyes removal using novel adsorbents:A review[J]. Environmental Pollution, 2019,252:352-365.
[3]
Zhao Y J, Zhu L, Li W H, et al. Insights into enhanced adsorptive removal of Rhodamine B by different chemically modified garlic peels:Comparison, kinetics, isotherms, thermodynamics and mechanism[J]. Journal of Molecular Liquids, 2019,293:111516.
[4]
Chen B, Long F X, Chen S J, et al. Magnetic chitosan biopolymer as a versatile adsorbent for simultaneous and synergistic removal of different sorts of dyestuffs from simulated wastewater[J]. Chemical Engineering Journal, 2020,385:123926.
[5]
Zhang H, Li R H, Zhang Z Q. A versatile EDTA and chitosan bi-functionalized magnetic bamboo biochar for simultaneous removal of methyl orange and heavy metals from complex wastewater[J]. Environmental Pollution, 2022,293:118517.
[6]
Gurav R, Bhatia S K, Choi T R, et al. Adsorptive removal of synthetic plastic components bisphenol-A and solvent black-3dye from single and binary solutions using pristine pinecone biochar[J]. Chemosphere, 2022,296:134034.
[7]
Chen X Y, Li H P, Liu W Y, et al. Effective removal of methyl orange and rhodamine B from aqueous solution using furfural industrial processing waste:furfural residue as an eco-friendly biosorbent[J]. Colloids and Surfaces A,2019,583:123976.
[8]
Saini K, Sahoo A, Biswas B, et al. Preparation and characterization of lignin-derived hard templated carbon(s):Statistical optimization and methyl orange adsorption isotherm studies[J]. Bioresource Technology, 2021,342:125924.
[9]
Zhao H X, Yang Y, Shu X, et al. Adsorption of organic molecules on mineral surfaces studied by first-principle calculations:A review[J]. Advances in Colloid and Interface Science, 2018,256:230-241.
[10]
Yin Q Q, Si L H, Wang R K, et al. DFT study on the effect of functional groups of carbonaceous surface on ammonium adsorption from water[J]. Chemosphere, 2022,287:132294.
[11]
Achour Y, Bahsis L, Ablouh E-H, et al. Insight into adsorption mechanism of Congo red dye onto Bombax Buonopozense bark Activated-carbon using Central composite design and DFT studies[J]. Surfaces and Interfaces, 2021,23:100977.
[12]
Li Y, Shi M X, Xia M Z, et al. The enhanced adsorption of Ampicillin and Amoxicillin on modified montmorillonite with dodecyl dimethyl benzyl ammonium chloride:Experimental study and density functional theory calculation[J]. Advanced Powder Technology, 2021,32:3465-3475.
[13]
Zhang H L, Zhao F, Xia M Z, et al. Microscopic adsorption mechanism of montmorillonite for common ciprofloxacin emerging contaminant:Molecular dynamics simulation and Multiwfn wave function analysis[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2021,614:126186.
[14]
王诗生,赵大唯,章慧娟,等.磁性氮掺杂碳材料活化过硫酸盐降解酸性橙7[J]. 环境科学学报, 2022,42(4):1-10. Wang S S, Zhao D W, Zhang H J, et al. Magnetic N-doped carbonaceous materials activated persulfate for degradation of Acid Orange 7[J]. Acta Scientiae Circumstantiae, 2022,42(4):1-10.
[15]
王诗生,刘玉虎,盛广宏,等.磁性氨基功能化生物炭对水中Cr(Ⅵ)的吸附去除特性及机制[J]. 环境科学学报, 2023,43(4):289-297. Wang S S, Liu Y H, Sheng G H, et al.Adsorption performance and mechanism of Cr(Ⅵ) from aqueous solution by magnetic amino-functionalized biochar[J]. Acta Scientiae Circumstantiae, 2023, 43(3):289-297.
[16]
Lu T, Chen F. Multiwfn:a multifunctional wavefunction analyzer[J]. Computational Chemistry, 2012,33(5):580-92.
[17]
Lu T, Chen Q X. Independent gradient model based on Hirshfeld partition:A new method for visual study of interactions in chemical systems[J]. Computational Chemistry, 2022,43:539-555.
[18]
余剑,丁恒,张智霖,等.改性菱角壳生物炭吸附水中土霉素性能与机理[J]. 中国环境科学, 2021,41(12):5688-5700. Yu J, Ding H, Zhang Z L, et al. Sorption characteristics and mechanism of oxytetracycline in water by modified biochar derived from chestnut shell[J]. China Environmental Science, 2021,41(12):5688-5700.
[19]
Subbaiah M V, Kim D S. Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder:Kinetics, isotherms, and thermodynamic studies[J]. Ecotoxicology and Environmental Safety, 2016,128:109-117.
[20]
Jiang T, Liang Y D, He Y J, et al. Activated carbon NiFe2O4 magnetic composite a magnetic adsorbent for the adsorptionof methyl orange[J]. Journal of Environmental Chemical Engineering, 2015,3:1740-1751.
[21]
Bhowmik K L, Debnath A, Nath R K, et al. Synthesis and characterization of mixed phase manganese ferrite and hausmannite magnetic nanoparticle as potential adsorbent for methyl orange from aqueous media:Artificial neural network modeling[J]. Journal of Molecular Liquids, 2016,219:1010-1022.
[22]
Shi Y W, Song G B, Li A Q, et al. Graphene oxide-chitosan composite aerogel for adsorption of methyl orange and methylene blue:Effect of pH in single and binary systems[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2022,641:129595.
[23]
Morais da Silva P M, Camparotto N G, Figueiredo Neves T D, et al. Effective removal of basic dye onto sustainable chitosan beads Batch and fixed-bed column adsorption, beads stability and mechanism[J]. Sustainable Chemistry and Pharmacy, 2020,18:100348.
[24]
Pan X M, Zhang M M, Liu H L, et al. Adsorption behavior and mechanism of acid orange 7and methylene blue on self-assembled three-dimensional MgAl layered double hydroxide:Experimental and DFT investigation[J]. Applied Surface Science, 2020,522:146370.
[25]
Tang J Y, Ma Y F, Cui S, et al. Insights on ball milling enhanced iron magnesium layered double oxides bagasse biochar composite for ciprofloxacin adsorptive removal from water[J]. Bioresource Technology, 2022,359:127468.
[26]
Wang Z R, Jang H M. Comparative study on characteristics and mechanism of levofloxacin adsorption on swine manure biochar[J]. Bioresource Technology, 2022,351:127025.
[27]
Cheng L, Jia Y H, Liu X M, et al. Insights into interfacial interaction mechanism of dyes sorption on a novel hydrochar:Experimental and DFT study[J]. Chemical Engineering Science, 2021,233:116432.
[28]
Feng Z Y, Chen N, Liu T, et al. KHCO3 activated biochar supporting MgO for Pb (II) and Cd (II) adsorption from water:Experimental study and DFT calculation analysis[J]. Journal of Hazardous Materials, 2022,426:128059.
[29]
Huang J, Cao S R, Liu Z H, et al. High-efficiency removal of methcathinone from water using a novel DES modified magnetic biochar nanocomposite[J]. Journal of Environmental Chemical Engineering, 2022,10(5):108456.
[30]
Peng X, Chen L, Liu S J, et al. Insights into the interfacial interaction mechanisms of p-arsanilic acid adsorption on ionic liquid modified porous cellulose[J]. Journal of Environmental Chemical Engineering, 2021,9:105225.
[31]
Sun Y, Gu Y P, Zhang H R, et al. Adsorption properties of macroporous exchangers functionalized with various weak-base groups for aromatic acids:Coupling DFT simulation with batch experiments[J]. Journal of Environmental Chemical Engineering, 2021,9:106026.
[32]
Cheng Y Z, Wang B Y, Shen J M, et al. The enhanced adsorption of Ampicillin and Amoxicillin on modified montmorillonite with dodecyl dimethyl benzyl ammonium chloride:Experimental study and density functional theory calculation[J]. Advanced Powder Technology, 2022,432:128757.
[33]
Abo El Naga A O, Shaban S A, El Kady F Y A. Metal organic framework-derived nitrogen-doped nanoporous carbon as an efficient adsorbent for methyl orange removal from aqueous solution[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018,93:363-373.
[34]
Hu Z T, Ding Y, Shao Y C, et al. Banana peel biochar with nanoflake-assembled structure for cross contamination treatment in water:Interaction behaviors between lead and tetracycline[J]. Chemical Engineering Journal, 2021,420:129807.
