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Self-templated microwave-assisted hydrothermal synthesis of two-dimensional holey hydroxyapatite nanosheets for efficient heavy metal removal

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Abstract

Heavy metals have caused serious environmental problems and threat to human health. Ultrathin and holey two-dimensional (2D) nanosheets have recently drawn significant attention as superb adsorbent material to remove heavy metal ions due to their unique physicochemical properties. Herein, we report a self-template-directed ultrafast reaction route to synthesis porous hydroxyapatite (Ca10(PO4)6(OH)2) nanosheets via a microwave-assisted hydrothermal method using poly(allylamine hydrochloride) as an additive. The resulting hydroxyapatite nanosheets showed a high specific surface area (92.9 m2 g−1) and excellent adsorption performance for various heavy metal ions including Pb(II), Cu(II), and Cd(II), with maximum adsorption capacities of 210.5, 31.6, and 24.9 mg g−1, respectively. The adsorption kinetics fitted well with the pseudo-second-order equation and the equilibrium data showed a high correlation coefficient with the Langmuir model. Based on the experimental results and analysis, we can conclude that the sorption of heavy metal ions with the hydroxyapatite nanosheets mainly attributes to surface complexation and cation exchange. The present synthetic strategy allows the fast and massive production of porous hydroxyapatite ultrathin nanosheets and may also potentially be applicable to the fabrication of other metal phosphates with assembled or hierarchical porous structures towards various applications such as water purification.

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References

  • Ahmadifar Z, Dadvand Koohi A (2018) Characterization, preparation, and uses of nanomagnetic Fe3O4 impregnated onto fish scale as more efficient adsorbent for Cu2+ ion adsorption. Environ Sci Pollut Res 25:19687–19700

  • Aklil A, Mouflih M, Sebti S (2004) Removal of heavy metal ions from water by using calcined phosphate as a new adsorbent. J Hazard Mater 112:183–190

  • Andini S, Cioffi R, Montagnaro F, Pisciotta F, Santoro L (2006) Simultaneous adsorption of chlorophenol and heavy metal ions on organophilic bentonite. Appl Clay Sci 31:126–133

  • Caruso F (1998) Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating. Science 282:1111–1114

  • Chen F, Zhu YJ (2016) Large-scale automated production of highly ordered Ultralong hydroxyapatite nanowires and construction of various fire-resistant flexible ordered architectures. ACS Nano 10:11483–11495

  • Chen Y, Tan C, Zhang H, Wang L (2015) Two-dimensional graphene analogues for biomedical applications. Chem Soc Rev 44:2681–2701

  • Chen P, Zhang Z, Duan X, Duan X (2018) Chemical synthesis of two-dimensional atomic crystals, heterostructures and superlattices. Chem Soc Rev 47:3129–3151

  • Coleman JN et al (2011) Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331:568–571

  • Costa DO, Dixon SJ, Rizkalla AS (2012) One- and three-dimensional growth of hydroxyapatite nanowires during sol-gel-hydrothermal synthesis. ACS Appl Mater Interfaces 4:1490–1499

  • Erdem E, Karapinar N, Donat R (2004) The removal of heavy metal cations by natural zeolites. J Colloid Interface Sci 280:309–314

  • Eshraghi F, Nezamzadeh-Ejhieh A (2018) EDTA-functionalized clinoptilolite nanoparticles as an effective adsorbent for Pb(II) removal. Environ Sci Pollut Res 25:14043–14056

  • Fan X, Yu C, Yang J, Ling Z, Hu C, Zhang M, Qiu J (2015) A layered-Nanospace-confinement strategy for the synthesis of two-dimensional porous carbon Nanosheets for high-rate performance supercapacitors. Adv Energy Mater 5:1401761

  • Feng Y, Gong J-L, Zeng G-M, Niu Q-Y, Zhang H-Y, Niu C-G, Deng J-H, Yan M (2010) Adsorption of cd (II) and Zn (II) from aqueous solutions using magnetic hydroxyapatite nanoparticles as adsorbents. Chem Eng J 162:487–494

  • Gan M, Sun S, Zheng Z, Tang H, Sheng J, Zhu J, Liu X (2015) Adsorption of Cr(VI) and cu(II) by AlPO4 modified biosynthetic Schwertmannite. Appl Surf Sci 356:986–997

  • Gong CY, Geng ZG, Dong AL, Ye XX, Wang GZ, Zhang YX (2016) Highly efficient and selective removal of Pb(II) ions by sulfur-containing calcium phosphate nanoparticles. Chin J Chem Phys 29:607–616

  • Gong B, Peng Y, Pan Z, Chen W, Shen Y, Xiao K, Zhang L (2017) Gram-scale synthesis of monodisperse sulfonated polystyrene nanospheres for rapid and efficient sequestration of heavy metal ions. Chem Commun 53:12766–12769

  • Guo H-P, Ruan B-Y, Luo W-B, Deng J, Wang J-Z, Liu H-K, Dou S-X (2018) Ultrathin and edge-enriched holey nitride Nanosheets as bifunctional Electrocatalysts for the oxygen and hydrogen evolution reactions. ACS Catal 8:9686–9696

  • Hao Q, Song Y, Mo Z, Mishra S, Pang J, Liu Y, Lian J, Wu J, Yuan S, Xu H, Li H (2019) Highly efficient adsorption of oils and pollutants by porous ultrathin oxygen-modified BCN Nanosheets. ACS Sustain Chem Eng 7:3234–3242

  • Jang SH, Jeong YG, Min BG, Lyoo WS, Lee SC (2008) Preparation and lead ion removal property of hydroxyapatite/polyacrylamide composite hydrogels. J Hazard Mater 159:294–299

    Article  CAS  Google Scholar 

  • Janica I, Del Buffa S, Mikolajczak A, Eredia M, Pakulski D, Ciesielski A, Samori P (2018) Thermal insulation with 2D materials: liquid phase exfoliated vermiculite functional nanosheets. Nanoscale 10:23182–23190

    Article  CAS  Google Scholar 

  • Jevtić M, Mitrić M, Škapin S, Jančar B, Ignjatović N, Uskoković D (2008) Crystal structure of hydroxyapatite nanorods synthesized by sonochemical homogeneous precipitation. Cryst Growth Des 8:2217–2222

    Article  CAS  Google Scholar 

  • Jiang S-D, Yao Q-Z, Zhou G-T, Fu S-Q (2012) Fabrication of hydroxyapatite hierarchical hollow microspheres and potential application in water treatment. J Phys Chem C 116:4484–4492

    Article  CAS  Google Scholar 

  • Johnsson MS-A, Nancollas GH (1992) The role of brushite and octacalcium phosphate in apatite formation. Crit Rev Oral Biol Med 3:61–82

    Article  CAS  Google Scholar 

  • Kalavathy MH, Karthikeyan T, Rajgopal S, Miranda LR (2005) Kinetic and isotherm studies of Cu(II) adsorption onto H3PO4-activated rubber wood sawdust. J Colloid Interface Sci 292:354–362

    Article  CAS  Google Scholar 

  • Koutsopoulos S (2002) Synthesis and characterization of hydroxyapatite crystals: a review study on the analytical methods. J Biomed Mater Res 62:600–612

    Article  CAS  Google Scholar 

  • Lee J, Ham S, Choi D, Jang DJ (2018) Facile fabrication of porous ZnS nanostructures with a controlled amount of S vacancies for enhanced photocatalytic performances. Nanoscale 10:14254–14263

    Article  CAS  Google Scholar 

  • Lei W, Portehault D, Liu D, Qin S, Chen Y (2013) Porous boron nitride nanosheets for effective water cleaning. Nat Commun 4:1777

    Article  CAS  Google Scholar 

  • Leofanti G, Padovan M, Tozzola G, Venturelli B (1998) Surface area and pore texture of catalysts. Catal Today 41:207–219

    Article  CAS  Google Scholar 

  • Li Z, Pan Z, Wang Y (2019) Enhanced adsorption of cationic Pb(II) and anionic Cr(VI) ions in aqueous solution by amino-modified nano-sized illite-smectite clay. Environ Sci Pollut Res 26:11126–11139

    Article  CAS  Google Scholar 

  • Liu J, Yang J, Yang Q, Wang G, Li Y (2005) Hydrothermally stable thioether-bridged mesoporous materials with void defects in the pore walls. Adv Funct Mater 15:1297–1302

    Article  CAS  Google Scholar 

  • Mortazavian S, An H, Chun D, Moon J (2018) Activated carbon impregnated by zero-valent iron nanoparticles (AC/nZVI) optimized for simultaneous adsorption and reduction of aqueous hexavalent chromium: material characterizations and kinetic studies. Chem Eng J 353:781–795

    Article  CAS  Google Scholar 

  • Mouflih M, Aklil A, Sebti S (2005) Removal of lead from aqueous solutions by activated phosphate. J Hazard Mater 119:183–188

    Article  CAS  Google Scholar 

  • Mouslmani M, Rosenholm JM, Prabhakar N, Peurla M, Baydoun E, Patra D (2015) Curcumin associated poly(allylamine hydrochloride)-phosphate self-assembled hierarchically ordered nanocapsules: size dependent investigation on release and DPPH scavenging activity of curcumin. RSC Adv 5:18740–18750

    Article  CAS  Google Scholar 

  • Oyanedel-Craver VA, Smith JA (2006) Effect of quaternary ammonium cation loading and pH on heavy metal sorption to Ca bentonite and two organobentonites. J Hazard Mater 137:1102–1114

    Article  CAS  Google Scholar 

  • Peng L, Xiong P, Ma L, Yuan Y, Zhu Y, Chen D, Luo X, Lu J, Amine K, Yu G (2017) Holey two-dimensional transition metal oxide nanosheets for efficient energy storage. Nat Commun 8:15139

    Article  Google Scholar 

  • Puziy AM, Poddubnaya OI, Socha RP, Gurgul J, Wisniewski M (2008) XPS and NMR studies of phosphoric acid activated carbons. Carbon 46:2113–2123

    Article  CAS  Google Scholar 

  • Shahzad A, Rasool K, Miran W, Nawaz M, Jang J, Mahmoud KA, Lee DS (2017) Two-dimensional Ti3C2Tx MXene nanosheets for efficient copper removal from water. ACS Sustain Chem Eng 5:11481–11488

    Article  CAS  Google Scholar 

  • Shawabkeh R, Al-Harahsheh A, Hami M, Khlaifat A (2004) Conversion of oil shale ash into zeolite for cadmium and lead removal from wastewater. Fuel 83:981–985

    Article  CAS  Google Scholar 

  • Shu C, Yanwei W, Hong L, Zhengzheng P, Kangde Y (2005) Synthesis of carbonated hydroxyapatite nanofibers by mechanochemical methods. Ceram Int 31:135–138

    Article  CAS  Google Scholar 

  • Sitko R, Turek E, Zawisza B, Malicka E, Talik E, Heimann J, Gagor A, Feist B, Wrzalik R (2013) Adsorption of divalent metal ions from aqueous solutions using graphene oxide. Dalton Trans 42:5682–5689

    Article  CAS  Google Scholar 

  • Stojanovic ZS, Ignjatovic N, Wu V, Zunic V, Veselinovic L, Skapin S, Miljkovic M, Uskokovic V, Uskokovic D (2016) Hydrothermally processed 1D hydroxyapatite: mechanism of formation and biocompatibility studies. Mat Sci Eng C-Mater 68:746–757

    Article  CAS  Google Scholar 

  • Su Y, Cui M, Zhu J, Wu Y, Wei Y, Bian S (2017) A facile synthesis of nanosheet-structured barium carbonate spheres with a superior adsorption capacity for Cr(VI) removal. J Mater Sci 53:4078–4088

    Article  CAS  Google Scholar 

  • Sun Q, Lou J-T, Kang F, Chen J-F, Wang J-X (2014) Facile preparation of hydroxyapatite nanotubes assisted by needle-like calcium carbonate. Powder Technol 261:49–54

    Article  CAS  Google Scholar 

  • Tian P, Han XY, Ning GL, Fang HX, Ye JW, Gong WT, Lin Y (2013) Synthesis of porous hierarchical MgO and its superb adsorption properties. ACS Appl Mater Interfaces 5:12411–12418

    Article  CAS  Google Scholar 

  • Timchenko PE, Timchenko EV, Pisareva EV, Vlasov MY, Red’kin NA, Frolov OO (2017) Spectral analysis of allogeneic hydroxyapatite powders. J Phys Conf Ser 784:012060

    Article  CAS  Google Scholar 

  • Wang K, Wei M, Morris MA, Zhou H, Holmes JD (2007) Mesoporous titania nanotubes: their preparation and application as electrode materials for rechargeable lithium batteries. Adv Mater 19:3016–3020

    Article  CAS  Google Scholar 

  • Wang SJ, Ge X, Xue JY, Fan HM, Mu LJ, Li YP, Xu H, Lu JR (2011) Mechanistic processes underlying biomimetic synthesis of silica nanotubes from self-assembled ultrashort peptide templates. Chem Mater 23:2466–2474

    Article  CAS  Google Scholar 

  • Wang X, Feng H, Wu Y, Jiao L (2013) Controlled synthesis of highly crystalline MoS2 flakes by chemical vapor deposition. J Am Chem Soc 135:5304–5307

    Article  CAS  Google Scholar 

  • Wei Z, Xing R, Zhang X, Liu S, Yu H, Li P (2013) Facile template-free fabrication of hollow nestlike α-Fe2O3 nanostructures for water treatment. ACS Appl Mater Interfaces 5:598–604

    Article  CAS  Google Scholar 

  • Xia X, Wang Y, Ruditskiy A, Xia Y (2013) 25th anniversary article: galvanic replacement: a simple and versatile route to hollow nanostructures with tunable and well-controlled properties. Adv Mater 25:6313–6333

    Article  CAS  Google Scholar 

  • Xia X, Shen J, Cao F, Wang C, Tang M, Zhang Q, Wei S (2019) A facile synthesis of hydroxyapatite for effective removal strontium ion. J Hazard Mater 368:326–335

    Article  CAS  Google Scholar 

  • Xingfu Z, Zhaolin H, Yiqun F, Su C, Weiping D, Nanping X (2008) Microspheric organization of multilayered ZnO nanosheets with hierarchically porous structures. J Phys Chem C 112:11722–11728

    Article  CAS  Google Scholar 

  • Yan Z, Fu L, Yang H, Ouyang J (2018) Amino-functionalized hierarchical porous SiO2-AlOOH composite nanosheets with enhanced adsorption performance. J Hazard Mater 344:1090–1100

    Article  CAS  Google Scholar 

  • Yavuz Ö, Altunkaynak Y, Güzel F (2003) Removal of copper, nickel, cobalt and manganese from aqueous solution by kaolinite. Water Res 37:948–952

    Article  CAS  Google Scholar 

  • Ying Y, Liu Y, Wang X, Mao Y, Cao W, Hu P, Peng X (2015) Two-dimensional titanium carbide for efficiently reductive removal of highly toxic chromium(VI) from water. ACS Appl Mater Interfaces 7:1795–1803

    Article  CAS  Google Scholar 

  • Zhang Q, Wang W, Goebl J, Yin Y (2009) Self-templated synthesis of hollow nanostructures. Nano Today 4:494–507

    Article  CAS  Google Scholar 

  • Zhang Z, Li M, Chen W, Zhu S, Liu N, Zhu L (2010) Immobilization of lead and cadmium from aqueous solution and contaminated sediment using nano-hydroxyapatite. Environ Pollut 158:514–519

    Article  CAS  Google Scholar 

  • Zhang X-J, Lin D-Y, Yan X-H, Wang X-X (2011) Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution. J Cryst Growth 336:60–66

    Article  CAS  Google Scholar 

  • Zhang S, Gao H, Li J, Huang Y, Alsaedi A, Hayat T, Xu X, Wang X (2017) Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis. J Hazard Mater 321:92–102

    Article  CAS  Google Scholar 

  • Zhao Y, Li F, Zhang R, Evans DG, Duan X (2002) Preparation of layered double-hydroxide nanomaterials with a uniform crystallite size using a new method involving separate nucleation and aging steps. Chem Mater 14:4286–4291

    Article  CAS  Google Scholar 

  • Zhao G, Li J, Ren X, Chen C, Wang X (2011) Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management. Environ Sci Technol 45:10454–10462

    Article  CAS  Google Scholar 

  • Zhou J, Cheng Y, Yu J, Liu G (2011) Hierarchically porous calcined lithium/aluminum layered double hydroxides: facile synthesis and enhanced adsorption towards fluoride in water. J Mater Chem 21:19353

    Article  CAS  Google Scholar 

  • Zhu JH, Yu SH, Xu AW, Cölfen H (2009) The biomimetic mineralization of double-stranded and cylindrical helical BaCO3 nanofibres. Chem Commun 9:1106–1108

    Article  CAS  Google Scholar 

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Funding

This work was supported by the Shenzhen Science and Technology Innovation Committee (Grant No. JCYJ20170817111443306, JCYJ20170412154335393, and KQTD2016022619584022). Additional supports were provided by the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme 2018, Guangdong Provincial Key Laboratory of Soil and Groundwater Pollution Control (Grant No. 2017B030301012), and the National Natural Science Foundation of China (Grant No. 21571004).

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Authors and Affiliations

  1. School of Environmental Science and Engineering, Guangdong Provincial Key Laboratory of Soil and Groundwater Pollution Control, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, China

    Yiping Su, Jing Wang, Shun Li & Zuotai Zhang

  2. Beijing Key Lab of New Energy Materials and Technology, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, China

    Yiping Su

  3. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, China

    Shun Li

  4. Anhui Province Key Laboratory of Metallurgical Emission Reduction and Resources, Metallurgical Reduction and Comprehensive Utilization of Resources of Key Laboratory of Ministry of Education, Anhui University of Technology, Maanshan, 243002, Anhui, China

    Jianhua Zhu

  5. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China

    Weishu Liu

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  1. Yiping Su
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Correspondence to Shun Li, Weishu Liu or Zuotai Zhang.

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Su, Y., Wang, J., Li, S. et al. Self-templated microwave-assisted hydrothermal synthesis of two-dimensional holey hydroxyapatite nanosheets for efficient heavy metal removal. Environ Sci Pollut Res 26, 30076–30086 (2019). https://doi.org/10.1007/s11356-019-06160-4

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