Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

Abstract

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized.

• The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K.

• The potential mechanism for Cr(VI) adsorption by NHPC was put forward.

• DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI).

To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).

Graphical abstract

Keywords

Chromium(VI) / Nitrogen-doped porous carbon / Adsorption / Reduction / Loofah sponge

References

[1] Chowdhury S, Mishra R, Saha P, Kushwaha P (2011). Adsorption thermodynamics, kinetics and isosteric heat of adsorption of malachite green onto chemically modified rice husk. Desalination, 265(1–3): 159–168

[2] Du J, Zhang Y, Lv H, Chen A (2021). Silicate-assisted activation of biomass towards N-doped porous carbon sheets for supercapacitors. Journal of Alloys and Compounds, 853: 157091

[3] El Nemr A, Aboughaly R M, El Sikaily A, Ragab S, Masoud M S, Ramadan M S (2021). Utilization of sugarcane bagasse/ZnCl₂ for sustainable production of microporous nano-activated carbons of type I for toxic Cr(VI) removal from aqueous environment. Biomass Conversion and Biorefinery, doi: 10.1007/s13399-021-01445-6

[4] Fazlzadeh M, Khosravi R, Zarei A (2017). Green synthesis of zinc oxide nanoparticles using Peganum harmala seed extract, and loaded on Peganum harmala seed powdered activated carbon as new adsorbent for removal of Cr(VI) from aqueous solution. Ecological Engineering, 103: 180–190

[5] Gao Y, Chen C, Tan X, Xu H, Zhu K (2016). Polyaniline-modified 3D-flower-like molybdenum disulfide composite for efficient adsorption/photocatalytic reduction of Cr(VI). Journal of Colloid and Interface Science, 476: 62–70

[6] Gu H, Lou H, Ling D, Xiang B, Guo Z (2016). Polystyrene controlled growth of zerovalent nanoiron/magnetite on a sponge-like carbon matrix towards effective Cr(VI) removal from polluted water. RSC Advances, 6(111): 110134–110145

[7] Guo C, Ding L, Jin X, Zhang H, Zhang D (2021). Application of response surface methodology to optimize chromium(VI) removal from aqueous solution by cassava sludge-based activated carbon. Journal of Environmental Chemical Engineering, 9(1): 104785

[8] Huang J, Cao Y, Shao Q, Peng X, Guo Z (2017). Magnetic nanocarbon adsorbents with enhanced hexavalent chromium removal: Morphology dependence of fibrillar vs particulate structures. Industrial & Engineering Chemistry Research, 56(38): 10689–10701

[9] Huang Y, Hu H (2020). The interaction of perrhenate and acidic/basic oxygen-containing groups on biochar surface: A DFT study. Chemical Engineering Journal, 381: 122647

[10] Hussain I, Qi J, Sun X, Wang L, Li J (2020). Melamine derived nitrogen-doped carbon sheet for the efficient removal of chromium(VI). Journal of Molecular Liquids, 318: 114052

[11] Inoue T, Okuma O, Masuda K, Yasumuro M, Miura K (2012). Hydrothermal treatment of brown coal to improve the space time yield of a direct liquefaction reactor. Energy & Fuels, 26(4): 2198–2203

[12] Jagiello J, Chojnacka A, Pourhosseini S E M, Wang Z, Beguin F (2021). A dual shape pore model to analyze the gas adsorption data of hierarchical micro-mesoporous carbons. Carbon, 178: 113–124

[13] Ji Q, Hu C, Liu H, Qu J (2018). Development of nitrogen-doped carbon for selective metal ion capture. Chemical Engineering Journal, 350: 608–615

[14] Ji Y, Xu F, Zhang P, Xu Y, Zhang G (2021). Green synthesis of poly(pyrrole methane)-based adsorbent for efficient removal of chromium(VI) from aqueous solution. Journal of Cleaner Production, 293: 126197

[15] Jung C, Heo J, Han J, Her N, Lee S J, Oh J, Ryu J, Yoon Y (2013). Hexavalent chromium removal by various adsorbents: Powdered activated carbon, chitosan, and single/multi-walled carbon nanotubes. Separation and Purification Technology, 106: 63–71

[16] Li H, Li N, Zuo P, Qu S, Shen W (2021). Efficient adsorption-reduction synergistic effects of sulfur, nitrogen and oxygen heteroatom co-doped porous carbon spheres for chromium(VI) removal. Colloids and Surfaces A, Physicochemical and Engineering Aspects, 618: 126502

[17] Li J, He F, Shen X, Hu D, Huang Q (2020a). Pyrolyzed fabrication of N/P co-doped biochars from (NH₄)₃PO₄⁻ pretreated coffee shells and appraisement for remedying aqueous Cr(VI) contaminants. Bioresource Technology, 315: 123840

[18] Li J, Yu H, Zhang X, Zhu R, Yan L (2020b). Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study. Frontiers of Environmental Science & Engineering, 14(3): 52

[19] Li M, He J, Tang Y, Sun J, Fu H, Wan Y, Qu X, Xu Z, Zheng S (2019). Liquid phase catalytic hydrogenation reduction of Cr(VI) using highly stable and active Pd/CNT catalysts coated by N-doped carbon. Chemosphere, 217: 742–753

[20] Li X, Xing W, Zhuo S, Zhou J, Li F, Qiao S Z, Lu G Q (2011). Preparation of capacitor’s electrode from sunflower seed shell. Bioresource Technology, 102(2): 1118–1123

[21] Li Z, Fan R, Hu Z, Li W, Zhou H, Kang S, Zhang Y, Zhang H, Wang G (2020c). Ethanol introduced synthesis of ultrastable 1T-MoS₂ for removal of Cr(VI). Journal of Hazardous Materials, 394: 122525

[22] Liang X, Fei Y, Xie Q, Liu Y, Lu M, Xia F, Nie Y, Ji J (2019). Sulfuryl fluoride absorption from fumigation exhaust gas by biobased solvents: thermodynamic and quantum chemical analysis. Industrial & Engineering Chemistry Research, 58(12): 5018–5029

[23] Liu B, Zhang Q, Wang Z, Li L, Jin Z, Wang C, Zhang L, Chen L, Su Z (2020a). Nitrogen and sulfur-codoped porous carbon nanospheres with hierarchical micromesoporous structures and an ultralarge pore volume for high-performance supercapacitors. ACS Applied Materials & Interfaces, 12(7): 8225–8232

[24] Liu J, Wang X, Lu Q, Yu R, Chen M, Cai S, Wang X (2016). Synthesis of nitrogen and sulfur co-doped carbon derived from chromium carbide for the high performance supercapacitor. Journal of the Electrochemical Society, 163(14): A2991–A2998

[25] Liu X, Rao L, Yao Y, Chen H (2020b). Phosphorus-doped carbon fibers as an efficient metal-free bifunctional catalyst for removing sulfamethoxazole and chromium(VI). Chemosphere, 246: 125783

[26] Mahmoud M E, Mohamed A K, Salam M A (2021). Self-decoration of N-doped graphene oxide 3-D hydrogel onto magnetic shrimp shell biochar for enhanced removal of hexavalent chromium. Journal of Hazardous Materials, 408: 124951

[27] Marciano J S, Ferreira R R, de Souza A G, Barbosa R F S, de Moura Junior A J, Rosa D S (2021). Biodegradable gelatin composite hydrogels filled with cellulose for chromium(VI) adsorption from contaminated water. International Journal of Biological Macromolecules, 181: 112–124

[28] Mohamed A K, Mahmoud M E (2020). Nanoscale Pisum sativum pods biochar encapsulated starch hydrogel: A novel nanosorbent for efficient chromium(VI) ions and naproxen drug removal. Bioresource Technology, 308: 123263

[29] Nguyen N T, Lee S Y, Chen S S, Nguyen N C, Chang C T, Hsiao S S, Trang L T, Kao C Y, Lin M F, Wang L (2018). Preparation of Zn-doped biochar from sewage sludge for chromium ion removal. Journal of Nanoscience and Nanotechnology, 18(8): 5520–5527

[30] Ramirez A, Ocampo R, Giraldo S, Padilla E, Flórez E, Acelas N (2020). Removal of Cr(VI) from an aqueous solution using an activated carbon obtained from teakwood sawdust: Kinetics, equilibrium, and density functional theory calculations. Journal of Environmental Chemical Engineering, 8(2): 103702

[31] Shang T X, Zhang J, Jin X J, Gao J M (2014). Study of Cr(VI) adsorption onto nitrogen-containing activated carbon preparation from bamboo processing residues. Journal of Wood Science, 60(3): 215–224

[32] Shih Y J, Dong C D, Huang Y H, Huang C P (2020). Loofah-derived activated carbon supported on nickel foam (AC/Ni) electrodes for the electro-sorption of ammonium ion from aqueous solutions. Chemosphere, 242: 125259

[33] Song Y, Wei G, Kopeć M, Rao L, Zhang Z, Gottlieb E, Wang Z, Yuan R, Ye G, Wang J, Kowalewski T, Matyjaszewski K (2018). Copolymer-templated synthesis of nitrogen-doped mesoporous carbons for enhanced adsorption of hexavalent chromium and uranium. ACS Applied Nano Materials, 1(6): 2536–2543

[34] Sun J, Zhang Z, Ji J, Dou M, Wang F (2017). Removal of Cr⁶⁺ from wastewater via adsorption with high-specific-surface-area nitrogen-doped hierarchical porous carbon derived from silkworm cocoon. Applied Surface Science, 405: 372–379

[35] Wan K, Huang L, Yan J, Ma B, Huang X, Luo Z, Zhang H, Xiao T (2021). Removal of fluoride from industrial wastewater by using different adsorbents: A review. Science of the Total Environment, 773: 145535

[36] Wang J, Zhao W, Li Z, Ding K, Jin Z (2019). Investigation on into the adsorption of Cu(II), Pb(II) and Cr(VI) on hollow mesoporous silica using microcalorimetry. Journal of Thermal Analysis and Calorimetry, 137(4): 1443–1450

[37] Wei J, Cai W (2020). One-step hydrothermal preparation of N-doped carbon spheres from peanut hull for efficient removal of Cr(VI). Journal of Environmental Chemical Engineering, 8(6): 104449

[38] Wu Y, Zhang J, Jin X J, Gao J M, Zhao Q (2014). Study of Cr(VI) adsorption onto nitrogen-enriched activated carbon from waste medium density fiberboard. Wood Science and Technology, 48(4): 713–725

[39] Xiao F, Cheng J, Cao W, Yang C, Chen J, Luo Z (2019). Removal of heavy metals from aqueous solution using chitosan-combined magnetic biochars. Journal of Colloid and Interface Science, 540: 579–584

[40] Yang J, Li C, Yang B, Kang S, Zhang Z (2018). Study on adsorption of chromium (VI) by activated carbon from cassava sludge. IOP Conference Series: Earth and Environmental Science, 128: 012017

[41] Yang K, Fox J (2018). DPF soot as an adsorbent for Cu(II), Cd(II), and Cr(VI) compared with commercial activated carbon. Environmental Science and Pollution Research International, 25(9): 8620–8635

[42] Yang K, Gao Q, Tan Y, Tian W, Qian W, Zhu L, Yang C (2016). Biomass-derived porous carbon with micropores and small mesopores for high-performance lithium-sulfur batteries. Chemistry–A European Journal, 22(10): 3239–3244

[43] Yang P, Guo D, Chen Z, Cui B, Xiao B, Liu S, Hu M (2017). Removal of Cr (VI) from aqueous solution using magnetic biochar synthesized by a single step method. Journal of Dispersion Science and Technology, 38(11): 1665–1674

[44] Yao Y, Mi N, He C, Zhang Y, Yin L, Li J, Wang W, Yang S, He H, Li S, Ni L (2020). A novel colloid composited with polyacrylate and nano ferrous sulfide and its efficiency and mechanism of removal of Cr(VI) from Water. Journal of Hazardous Materials, 399: 123082

[45] Yu F, Wang M, Huang B, Peng Q, Huang Y (2017). Acid-treatment effect on the N-doped porous carbon obtained from fish scales for Cr(VI) removal. Chemical Papers, 71(11): 2261–2269

[46] Yuan X, An N, Zhu Z, Sun H, Zheng J, Jia M, Lu C, Zhang W, Liu N (2018). Hierarchically porous nitrogen-doped carbon materials as efficient adsorbents for removal of heavy metal ions. Process Safety and Environmental Protection, 119: 320–329

[47] Zhang R, Li D, Sun J, Cui Y, Sun Y (2020a). In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution. Frontiers of Environmental Science & Engineering, 14(4): 68

[48] Zhang T, Wei S, Waterhouse G I N, Fu L, Liu L, Shi W, Sun J, Ai S (2020b). Chromium (VI) adsorption and reduction by humic acid coated nitrogen-doped magnetic porous carbon. Powder Technology, 360: 55–64

[49] Zhang Y, Wang Y, Zhang H, Li Y, Zhang Z, Zhang W (2020c). Recycling spent lithium-ion battery as adsorbents to remove aqueous heavy metals: Adsorption kinetics, isotherms, and regeneration assessment. Resources, Conservation and Recycling, 156: 104688

[50] Zhao N, Zhao C, Lv Y, Zhang W, Du Y, Hao Z, Zhang J (2017). Adsorption and coadsorption mechanisms of Cr(VI) and organic contaminants on H₃PO₄ treated biochar. Chemosphere, 186: 422–429

[51] Zhou S, Zhang B, Liao Z, Zhou L, Yuan Y (2020). Autochthonous N-doped carbon nanotube/activated carbon composites derived from industrial paper sludge for chromate (VI) reduction in microbial fuel cells. Science of the Total Environment, 712: 136513

[52] Zhou X, Chen F, Bai T, Long B, Liao Q, Ren Y, Yang J (2016). Interconnected highly graphitic carbon nanosheets derived from wheat stalk as high performance anode materials for lithium ion batteries. Green Chemistry, 18(7): 2078–2088

[53] Zhu S, Wang S, Yang X, Tufail S, Chen C, Wang X, Shang J (2020). Green sustainable and highly efficient hematite nanoparticles modified biochar-clay granular composite for Cr(VI) removal and related mechanism. Journal of Cleaner Production, 276: 123009

[54] Zuo K, Huang X, Liu X, Gil Garcia E M, Kim J, Jain A, Chen L, Liang P, Zepeda A, Verduzco R, Lou J, Li Q (2020). A hybrid metal-organic framework-reduced graphene oxide nanomaterial for selective removal of chromate from water in an electrochemical process. Environmental Science & Technology, 54(20): 13322–13332

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