Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies

Khan Afsar; Hong Ran; Chen Saisai; Liu Tingting; Kaya Savaş; Chen Weihua; Xu Dayong

doi:null

Your Location：

Home >

Browse articles >

Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies

Updated：2026-05-14

- Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies
- Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies
- 中国化学工程学报（英文） 2026年90卷第2期页码：214-231
- Affiliations：
  
  School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China
  Sivas Cumhuriyet University, Faculty of Science, Department of Chemistry, 58140, Sivas, Turkey
  School of Chemistry and Environmental Science, Shangrao Normal University, Shangrao 334000, China
- Author bio：
  
  Corresponding authors. E-mail addresses: chenweihua419818@sina.com (W. Chen)
  Corresponding authors. E-mail addresses: xdy826@ahpu.edu.cn (D. Xu).
- Funds：
  
  the Major Program of Natural Science Foundation for Higher Education Institutions of Anhui Province(2024AH040021);National College Student Innovation and Entrepreneurship Training Program(202310363071)
- DOI：
  中图分类号：
- 收稿：2025-07-12，
  
  修回：2025-09-16，
  
  录用：2025-09-17，
  
  网络首发：2025-12-03，
  
  纸质出版：2026-02
- Accepted：
Scan QR Code
Khan Afsar, Hong Ran, Chen Saisai, 等. Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies[J]. 中国化学工程学报（英文）, 2026,90(2):214-231.

Khan Afsar, Hong Ran, Chen Saisai, et al. Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 214-231.
Khan Afsar, Hong Ran, Chen Saisai, 等. Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies[J]. 中国化学工程学报（英文）, 2026,90(2):214-231. DOI：

Khan Afsar, Hong Ran, Chen Saisai, et al. Dual-charged, non-swelling amine/carboxyl functionalized Fe—Mn mixed oxide composite for simultaneous removal of anionic and cationic azo dyes: Experimental and DFT studies[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 214-231. DOI：

摘要

Abstract

Iron (Fe) and manganese (Mn) mixed oxide composites are widely recognized for their excellent adsorption performance in wastewater treatment. However

their functionalization for simultaneous removal of both anionic and cationic contaminants remains underexplored. In this study

Fe—Mn mixed oxides were functionalized with poly(acrylic acid) (PAA) and chitosan to introduce carboxylic and amine groups respectively

forming a dual-functionalized composite (PAA—chitosan—FeMn). The material was evaluated for the adsorption of Congo red

reactive blue 19

and methylene blue from aqueous solutions using batch and fixed-bed reactor systems. The composite was characterized before and after adsorption using X-ray photoelectron spectroscope (XPS)

atomic force microscope

scanning electron microscope

high-resolution transmission electron microscope

Fourier transform infrared spectroscope (FTIR)

thermal gravimetric analyzer

and Raman spectroscopy. A marked enhancement in adsorption capacity was observed for all target dyes. Mechanistic investigations using XPS

FTIR

and density functional theory (DFT) indicated that the adsorption process was predominantly governed by electrostatic interactions and hydrogen bonding involving carbon

nitrogen

and oxygen functional groups. XPS analysis further confirmed the active role of Fe and Mn ions in dye binding. Comprehensive studies on adsorption isotherms

kinetics

and thermodynamics were conducted under optimized conditions. The composite exhibited a specific surface area of 27.4 to 68.4 m

·g

-1

before and after dye adsorption and a point of zero charge of 6.5—6.8

facilitating effective adsorption of oppositely charged dyes at nearneutral pH. Batch adsorption experiments demonstrated maximum capacities of 95.0% to 99.7% for both dyes under optimal conditions (pH 8—10

298 K). The PAA—chitosan—FeMn composite demonstrated high adsorption capacity

excellent stability under acidic conditions

and strong selectivity

highlighting its potential for the effective and simultaneous removal of anionic and cationic azo dyes from wastewater.

关键词

Keywords

references

O.z. Edebali, S. Krupčíková, A. Goellner, B. Vrana, M. Muz, L. Melymuk, Tracking aromatic amines from sources to surface waters, Environ. Sci. Technol. Lett. 11 (2024) 397—409.

S. Zhang, Q. Luo, X. Sun, L. Chi, P. Sun, L. Zhang, Facile synthesis coppermodifi ed titania (Cu/TiO 2 ) nanoparticles for high-efficiency Congo red adsorption, Chin. J. Chem. Eng. 81 (2025) 87—94.

M.S. Shukor, K. Aftab, M. Norazlina, H.M.I. Effendi, A.S.R. Sheikh, S.M. Yunus, Isolation of a novel molybdenum-reducing and azo dye decolorizing enterobacter sp. strain Aft-3 from Pakistan, Chiang Mai Uni. J. Nat. Sci. 15 (2016)95—114.

R. Kumaravel, V.K. Shanmugam, Biomimetic and ecological perspective to-wards decolorization of industrial important Azo Dyes using bacterial cultures—A review, Sustain. Chem. Environ. (2024)100130.

A. Alsbaiee, B.J. Smith, L. Xiao, Y. Ling, D.E. Helbling, W.R. Dichtel, Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer, Nature 529(2016)190—194.

T. Ahmad, Hazardous azo-dyes and aromatic amines from various industrial zones of Punjab province of Pakistan, 19th Global Chemistry, Chromatography & Spectrometry Conference, March 20-21, New York, USA (2019).

H.M. Abd El-Aziz, M.A. Zayed, S.A. Abdel-Gawad, Adsorptive removal of direct red 31 and direct orange 26 azo dyes from aqueous solutions using ficus nano zero valent copper: Linear, non-linear, response surface methodology(RSM), and artificial neural network(ANN)modeling, Adsorpt. Sci. Technol. 42(2024) 02636174241256849.

A. Aslam, F. Batool, S. Noreen, E.A. Abdelrahman, M. Mustaqeem, B.F.A. Al balawi, A. Ditta, Metal oxide-impregnated biochar for Azo dye remediation as revealed through kinetics, thermodynamics, and response surface methodology, ACS Omega 9 (2024) 4300—4316.

L. Abramian, H. El-Rassy, Adsorption kinetics and thermodynamics of azo-dye orange II onto highly porous titania aerogel, Chem. Eng. J. 150(2009)403—410.

A. Khan, A. Naeem, T. Mahmood, B. Ahmad, Z. Ahmad, M. Farooq, T. Saeed, Mechanistic study on methyl orange and congo red adsorption onto polyvinyl pyrrolidone modified magnesium oxide, Int. J. Environ. Sci. Technol. (2022) 1 — 14.

Q. Lu, L. Di, Y. Zhou, Y. Zhou, Efficient removal of bisphenol A from water using a novel organic—inorganic hybrid heterojunction, Sep. Purif. Technol. 353(2025)128099.

H. Yang, H. Zhang, J. Lu, Y. Cui, Y. Wang, X. Wang, J. Xue, H. Cao, Advanced magnetic adsorbents for enhanced phosphorus and fluoride removal from wastewater: mechanistic insights and applications, Sep. Purif. Technol. 353 (2025)128195.

C. Chen, Z. Yan, Z. Ma, D. Ma, S. Xing, W. Li, J. Yang, Q. Han, Magnetic Fe 3 O 4 nanoparticles supported on carbonized corncob as heterogeneous fenton catalyst for efficient degradation of methyl orange, Chin. J. Chem. Eng. 77 (2025)144—155.

Y. Tang, Y. Li, Y. Zhang, C. Mu, J. Zhou, W. Zhang, B. Shi, Nonswelling silica—poly(acrylic acid)composite for efficient and simultaneous removal of cationic dye, heavy metal, and surfactant-stabilized emulsion from wastewater, Ind. Eng. Chem. Res. 59 (2020) 3383—3393.

Q.D. Tsauria, P.L. Gareso, D. Tahir, Systematic review of chitosan-based adsorbents for heavy metal and dye remediation, Integrated Environ. Assess. Manag. 22 (1) (2026) 26—46.

H. Xia, H. Wang, Y. Zhang, Fabrication and application of magnetic MgFe 2 O 4 -OH@ biochar composites decorated with β-ketoenamine for Pb(II)and Cd(II) adsorption and immobilization from aqueous solution, Sep. Purif. Technol. 354(2025)129320.

J. Qi, G. Zhang, H. Li, Efficient removal of arsenic from water using a granular adsorbent: Fe—Mn binary oxide impregnated chitosan bead, Bioresour. Technol. 193(2015)243—249.

C. Lee, W. Yang, R.G. Parr, Development of the Colle-Salvetti correlationenergy formula into a functional of the electron density, Phys. Rev. B 37 (1988) 785.

A.D. Becke, Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98 (1993) 5648—5652.

P.J. Hay, W.R. Wadt, Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg, J. Chem. Phys. 82 (1985) 270—283.

I.S. Ufimtsev, T.J. Martinez, Quantum chemistry on graphical processing units. 3. Analytical energy gradients, geometry optimization, and first principles molecular dynamics, J. Chem. Theor. Comput. 5 (2009) 2619—2628.

A.V. Titov, I.S. Ufimtsev, N. Luehr, T.J. Martinez, Generating efficient quantum chemistry codes for novel architectures, J. Chem. Theor. Comput. 9 (2013) 213—221.

J. Kästner, J.M. Carr, T.W. Keal, W. Thiel, A. Wander, P. Sherwood, DL-FIND: an open-source geometry optimizer for atomistic simulations, J. Phys. Chem. 113 (2009)11856—11865.

T. Goumans, C.R.A. Catlow, W.A. Brown, J. Kästner, P. Sherwood, An embedded cluster study of the formation of water on interstellar dust grains, Phys. Chem. Chem. Phys. 11 (2009)5431—5436.

L.-P. Wang, C. Song, Geometry optimization made simple with translation and rotation coordinates, J. Chem. Phys. 144(2016)214108.

S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J. Chem. Phys. 132(2010)154104.

N. Islam, S. Kaya, Conceptual Density Functional Theory and Its Application in the Chemical Domain, CRC press, (2018).

S. Kaya, C. Kaya, N. Islam, Maximum hardness and minimum polarizability principles through lattice energies of ionic compounds, Phys. B Condens. Matter 485(2016)60—66.

T. Koopmans, Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms, Physica 1(1934)104—113.

A. Wang, B. Li, Y. Wang, X. Sun, Z. Huang, S. Bian, K. Fan, H. Shang, Adsorption behavior of Congo red on a carbon material based on humic acid, New J. Chem. 46(2022)498—510.

R.-L. Tseng, S.-K. Tseng, F.-C. Wu, Preparation of high surface area carbons from corncob with KOH etching plus CO 2 gasification for the adsorption of dyes and phenols from water, Colloids Surf. A Physicochem. Eng. Asp. 279 (2006) 69—78.

L. Chen, D. Zhao, S. Chen, X. Wang, C. Chen, One-step fabrication of amino functionalized magnetic graphene oxide composite for uranium (VI) removal, J. Colloid Interface Sci. 472(2016)99—107.

J.M. Rosenholm, R.M. Korpi, E. Lammentausta, S. Lehtonen, P. Lehenkari, R. Niemi, W. Xiao, J. Zhang, D. Lindberg, H. Gu, Novel, fast-processed crystalline and amorphous manganese oxide nanoparticles for stem cell labeling, Inorg. Chem. Front. 2(2015)640—648.

A. Khan, S. Xiao, Y. Xie, S. Kaya, S. Zareen, N. Muhammad, K. Parveen, D. Xu, Rbpromoted Fe/CeO 2 nanocatalyst for aniline conversion into az oxybenzene, DFT calculations and mechanism, New J. Chem. 49 (2025) 921—934.

Y. Wang, L. He, G. Dang, H. Li, X. Li, Polypyrrole-functionalized magnetic Bi 2 MoO 6 nanocomposites as a fast, efficient and reusable adsorbent for removal of ketoprofen and indomethacin from aqueous solution, J. Colloid Interface Sci. 592 (2021) 51—65.

Z. Lan, Y. Lin, C. Yang, Lanthanum-iron incorporated chitosan beads for adsorption of phosphate and cadmium from aqueous solutions, Chem. Eng. J. 448(2022)137519.

A. Gupta, V.S. Chauhan, N. Sankararamakrishnan, Preparation and evaluation of iron—chitosan composites for removal of As (III) and As (V) from arsenic contaminated real life groundwater, Water Res. 43(2009)3862—3870.

Y. Haldorai, J.-J. Shim, Multifunctional chitosan-copper oxide hybrid material: photocatalytic and antibacterial activities, Int. J. Photoenergy 2013 (2013) 245646.

V. Selen, Ö. Güler, Modeling of Congo red adsorption onto multi-walled carbon nanotubes using response surface methodology: kinetic, isotherm and thermodynamic studies, Arabian J. Sci. Eng. 46 (2021) 6579—6592.

N.B. Milosavljević, M.Ð. Ristić, A.A. Perić-Grujić, J.M. Filipović, S.B. Štrbac, Z.L. Rakočević, M.T.K. Krušić, Removal of Cu 2+ ions using hydrogels of chitosan, itaconic and methacrylic acid: FTIR, SEM/EDX, AFM, kinetic and equilibrium study, Colloids Surf. A Physicochem. Eng. Asp. 388 (2011) 59—69.

S. Kaya, C. Kaya, A new equation for calculation of chemical hardness of groups and molecules, Mol. Phys. 113 (2015)1311—1319.

S. Kaya, A. Robles-Navarro, E. Mejía, T. Gómez, C. Cardenas, On the prediction of lattice energy with the fukui potential: some supports on hardness maximization in inorganic solids, J. Phys. Chem. 126(2022)4507—4516.

M.H. Al-Omari, A. Abu-Rayyan, A.H. Ragab, M.A. Taher, E.-S.M. El-Sayed, A. Elfiky, A. Taha, M.F. Mubarak, Optimized Congo red dye adsorption using ZnCuCr-Based MOF for sustainable wastewater treatment, Langmuir 41 (2025)5947—5961.

M. Özacar, https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=108582986&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=108582986&type=small https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=108582986&type=middle .A. Şengil, A kinetic study of metal complex dye sorption onto pine sawdust, Process Biochem. 40 (2005) 565—572.

T. Venkatesha, R. Viswanatha, Y.A. Nayaka, B. Chethana, Kinetics and thermodynamics of reactive and vat dyes adsorption on MgO nanoparticles, Chem. Eng. J. 198 (2012) 1—10.

T. Mahmood, A. Khan, A. Naeem, M. Hamayun, M. Muska, M. Farooq, F. Hussain, Adsorption of Ni (II) ions from aqueous solution onto a fungus Pleurotus ostreatus, Desalination Water Treat. 57 (2016)7209—7218.

F. Hassan, Y. Shao, B. Mu, Y. Yang, Sorption behavior of artificial keratin fibers from feathers with anionically charged azo and anthraquinone dyes for potential industrial applications, Int. J. Biol. Macromol. 284 (2025) 137923.

A. Bukhari, I. Ijaz, H. Zain, E. Gilani, A. Nazir, A. Bukhari, S. Raza, S. Hussain, S. S. Alarfaji, Y. Naseer, Removal of eosin dye from simulated media onto lemon peel-based low cost biosorbent, Arab. J. Chem. 15 (2022)103873.

X.N. Xu, Y.L. Wen, Y.X. Zhao, B. Wang, M.H. Fan, Z.J. Chen, S.Y. Guo, W. Huang, High-efficient removal of dye across a wide pH range over alkali lignin-based adsorbent: batch experiments and DFT mechanistic analysis, Sep. Purif. Technol.363(2025) 132322.

H. Gao, J. Jiang, Y. Huang, H. Wang, J. Sun, Z. Jin, J. Wang, J. Zhang, Synthesis of hydrogels for adsorption of anionic and cationic dyes in water: ionic liquid as a crosslinking agent, SN Appl. Sci. 4(2022)118.

Y.S. Reddy, T.J. Jose, B. Dinesh, R.N. Kumar, P.S. Kumar, K. Kaviyarasu, Equilibrium, kinetic, and thermodynamic study of direct yellow 12 dye adsorption by biomass-derived porous graphitic activated carbon, Biomass Convers. Biorefinery 15 (2025) 6817—6833.

A. Khan, M. Arif, Z. Han, Y. Xie, C. Ni, Mechanism and performances of methyl orange and Congo red adsorption by MnO 2 —PVP composite, Water Pract. Technol. 19 (2024) 1047—1060.

Z. Liu, B. Gao, H. Han, Y. Li, H. Fu, D. Wei, A green cross-linking method for the preparation of renewable three-dimensional graphene sponges for efficient adsorption of Congo red dye, Chin. J. Chem. Eng. 66 (2024) 84—93.

W. Xiang, X. Zhang, R. Xiao, Y. Zhang, Three-dimensional porous bimetallic metal—organic framework/gelatin aerogels: a readily recyclable peroxymonosulfate activator for efficient and continuous organic dye removal, Chin. J. Chem. Eng. 71 (2024) 193—202.

A.M. Aljeboree, F.H. Abdulrazzak, Z.M. Saleh, H.A. Abbas, A.F. Alkaim, Eco-friendly adsorption of cationic (methylene blue) and anionic (Congo red) dyes from aqueous solutions using sawdust, Eng. Proc. 59 (2024) 213.

A. Labena, A.E. Abdelhamid, A.S. Amin, S. Husien, L. Hamid, G. Safwat, A. Diab, A.A. Gobouri, E. Azab, Removal of methylene blue and Congo red using adsorptive membrane impregnated with dried Ulva fasciata and Sargassum dentifolium, Plants 10(2021)384.

H.C. Firmino, E.P. Nascimento, K.C. Costa, L.C. Arzuza, R.N. Araujo, B.V. Sousa, G.A. Neves, M.A. Morales, R.R. Menezes, High-efficiency adsorption removal of Congo red dye from water using magnetic NiFe 2 O 4 nanofibers: an efficient adsorbent, Materials 18 (2025) 754.

M. Harja, G. Buema, D. Bucur, Recent advances in removal of Congo red dye by adsorption using an industrial waste, Sci. Rep. 12(2022) 6087.

H.N. Hamad, S. Idrus, Recent developments in the application of bio-wastederived adsorbents for the removal of methylene blue from wastewater: a review, Polymers 14 (2022) 783.

R.A. Hakro, M. Mehdi, R.F. Qureshi, R.B. Mahar, M. Khatri, F. Ahmed, Z. Khatri, I.S. Kim, Efficient removal of reactive blue-19 dye by co-electrospun nanofibers, Mater. Res. Express 8 (2021) 055502.

C. Liang, Q. Shi, J. Feng, J. Yao, H. Huang, X. Xie, Adsorption behaviors of cationic methylene blue and anionic reactive blue 19 dyes onto nanocarbon adsorbent carbonized from small precursors, Nanomaterials 12 (2022) 1814.

A. Khan, A. Naeem, T. Mahmood, N. Muhammad, S. Hussain, Fixed-bed column adsorption of methyl orange by poly (vinyl pyrrolidone)-functionalized manganese oxide, J. Chem. Technol. Biotechnol. 97 (2022) 2898—2903.

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Efficiency and sustainability for removing organic pollutants in aqueous solution: An innovative composite material

Kinetics of hydrogen sulfide removal from coke oven gas over faujasite zeolite: Experimental and modeling studies

Adsorption of ciprofloxacin on (Zn-Al) LDHs modified 3D reduced graphene oxide: Response surface methodology, adsorption equilibrium, kinetic and thermodynamic studies

Magnetic polyacrylonitrile/ZIF-8/Fe3O4 nanocomposite bead as an efficient iodine adsorbent and antibacterial agent

Preparation of waterborne polyurethane/β-cyclodextrin composite nanosponge by ion condensation method and its application in removing of dyes from wastewater