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Solid Brønsted acidity boosts adsorption reactivity of nano-adsorbent for water decontamination

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Abstract

Despite the development of various Lewis acidic nano-adsorbents for fluoride removal through inner-sphere coordination, strong competition for hydroxyl ions still hinders efficient water defluoridation. In addition, the critical issue of polysilicate scaling that results from the ubiquitous silicates must be addressed. To tackle these issues, an alternative approach to enhancing adsorption reactivity by modifying nano-adsorbents with dual Lewis and Brønsted acidity is proposed. The feasibility of this approach is demonstrated by growing zirconium phosphate (ZrP) inside a gel-type anion exchanger, N201, to produce nanocomposite ZrP@N201, in which the confined ZrP contained an otherwise metastable amorphous phase with Lewis acidic Zr4+ sites and Brønsted acidic monohydrogen phosphate groups (–O3POH). Compared with the Lewis acidic nano-zirconium oxide analog (HZO@N201), ZrP@N201 exhibited a greatly improved adsorption capacity (117.9 vs. 52.3 mg/g-Zr) and mass transfer rate (3.56 × 10−6vs. 4.55 × 10−7 cm/s), while bulk ZrP produced a thermodynamically stable α-phase with Brønsted acidity that exhibited negligible adsorption capability toward fluoride. The enhanced defluoridation activity of ZrP@N201 is attributed to Brønsted acidity and the increased outer electron density of Zr4+ sites, as corroborated using XPS and solid-state NMR analysis. Moreover, Brønsted acidity strengthens the resistance of ZrP@N201 to silicate, allowing its full regeneration during cyclic defluoridation. Column tests demonstrated 3–10 times the amount of clean water from (waste) for ZrP@N201 as compared to both HZO@N201 and the widely used activated aluminum oxide. This study highlights the potential of developing nano-adsorbents with dual acidities for various environmental remediation applications.

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References

  • Ahmed I, Mondol M M H, Jung M J, Lee G H, Jhung S H (2023). MOFs with bridging or terminal hydroxo ligands: applications in adsorption, catalysis, and functionalization. Coordination Chemistry Reviews, 475: 214912

    Article  CAS  Google Scholar 

  • Alhassan S I, Huang L, He Y, Yan L, Wu B, Wang H (2021). Fluoride removal from water using alumina and aluminum-based composites: a comprehensive review of progress. Critical Reviews in Environmental Science and Technology, 51(18): 2051–2085

    Article  CAS  Google Scholar 

  • Campos-Pereira H, Kleja D B, Sjöstedt C, Ahrens L, Klysubun W, Gustafsson J P (2020). The adsorption of per- and polyfluoroalkyl substances (PFASs) onto ferrihydrite is governed by surface charge. Environmental Science & Technology, 54(24): 15722–15730

    Article  CAS  Google Scholar 

  • Chen J, Yang R, Zhang Z, Wu D (2022). Removal of fluoride from water using aluminum hydroxide-loaded zeolite synthesized from coal fly ash. Journal of Hazardous Materials, 421: 126817

    Article  CAS  Google Scholar 

  • Cheng S, Qian J, Zhang X, Lu Z, Pan B (2023). Commercial gel-type ion exchange resin enables large-scale production of ultrasmall nanoparticles for highly efficient water decontamination. Engineering, 23: 149–156

    Article  CAS  Google Scholar 

  • Cherukumilli K, Delaire C, Amrose S, Gadgil A J (2017). Factors governing the performance of bauxite for fluoride remediation of groundwater. Environmental Science & Technology, 51(4): 2321–2328

    Article  CAS  Google Scholar 

  • Chowdhury S R, Yanful E K, Pratt A R (2012). Chemical states in XPS and Raman analysis during removal of Cr(VI) from contaminated water by mixed maghemite–magnetite nanoparticles. Journal of Hazardous Materials, 235–236: 246–256

    Article  Google Scholar 

  • Du M, Zhang Y, Wang Z, Lv M, Tang A, Yu Y, Qu X, Chen Z, Wen Q, Li A (2022). Insight into the synthesis and adsorption mechanism of adsorbents for efficient phosphate removal: exploration from synthesis to modification. Chemical Engineering Journal, 442: 136147

    Article  CAS  Google Scholar 

  • Du Y, Qiu S, Zhang X, Nie G (2020). Nanoconfined hydrous titanium oxides with excellent acid stability for selective and efficient removal of As(V) from acidic wastewater. Chemical Engineering Journal, 400: 125907

    Article  CAS  Google Scholar 

  • Fan Q, Bao G, Chen X, Meng Y, Zhang S, Ma X (2022). Iron nanoparticles tuned to catalyze CO2 electroreduction in acidic solutions through chemical microenvironment engineering. ACS Catalysis, 12(13): 7517–7523

    Article  CAS  Google Scholar 

  • Fang Z, Deng Z, Liu A, Zhang X, Lv L, Pan B (2021a). Enhanced removal of arsenic from water by using sub-10 nm hydrated zirconium oxides confined inside gel-type anion exchanger. Journal of Hazardous Materials, 414: 125505

    Article  CAS  Google Scholar 

  • Fang Z, Li Z, Zhang X, Pan S, Wu M, Pan B (2021b). Enhanced arsenite removal from silicate-containing water by using redox polymer-based Fe(III) oxides nanocomposite. Water Research, 189: 116673

    Article  CAS  Google Scholar 

  • Gong H, Zhou C, Cui Y, Dai S, Zhao X, Luo R, An P, Li H, Wang H, Hou Z (2020). Direct transformation of glycerol to propanal using zirconium phosphate - supported bimetallic catalysts. ChemSusChem, 13(18): 4954–4966

    Article  CAS  Google Scholar 

  • Gould N S, Li S, Cho H J, Landfield H, Caratzoulas S, Vlachos D, Bai P, Xu B (2020). Understanding solvent effects on adsorption and protonation in porous catalysts. Nature Communications, 11(1): 1060

    Article  CAS  Google Scholar 

  • Han H, Rafiq M K, Zhou T, Xu R, Mašek O, Li X (2019). A critical review of clay-based composites with enhanced adsorption performance for metal and organic pollutants. Journal of Hazardous Materials, 369: 780–796

    Article  CAS  Google Scholar 

  • Indris S, Heitjans P, Roman H E, Bunde A (2000). Nanocrystalline versus microcrystalline Li2O:B2O3 composites: anomalous ionic conductivities and percolation theory. Physical Review Letters, 84(13): 2889–2892

    Article  CAS  Google Scholar 

  • Iriel A, Bruneel S P, Schenone N, Cirelli A F (2018). The removal of fluoride from aqueous solution by a lateritic soil adsorption: kinetic and equilibrium studies. Ecotoxicology and Environmental Safety, 149: 166–172

    Article  CAS  Google Scholar 

  • Kang D, Yu X, Ge M, Lin M, Yang X, Jing Y (2018). Insights into adsorption mechanism for fluoride on cactus-like amorphous alumina oxide microspheres. Chemical Engineering Journal, 345: 252–259

    Article  CAS  Google Scholar 

  • Keyikoglu R, Khataee A, Yoon Y (2022). Layered double hydroxides for removing and recovering phosphate: recent advances and future directions. Advances in Colloid and Interface Science, 300: 102598

    Article  CAS  Google Scholar 

  • Kong L, Tian Y, Pang Z, Huang X, Li M, Yang R, Li N, Zhang J, Zuo W (2019). Synchronous phosphate and fluoride removal from water by 3D rice-like lanthanum-doped La@MgAl nanocomposites. Chemical Engineering Journal, 371: 893–902

    Article  CAS  Google Scholar 

  • Lei X, Lian Q, Zhang X, Karsili T K, Holmes W, Chen Y, Zappi M E, Gang D D (2023). A review of PFAS adsorption from aqueous solutions: current approaches, engineering applications, challenges, and opportunities. Environmental Pollution, 321: 121138

    Article  CAS  Google Scholar 

  • Levenstein R, Hasson D, Semiat R (1996). Utilization of the Donnan effect for improving electrolyte separation with nanofiltration membranes. Journal of Membrane Science, 116(1): 77–92

    Article  CAS  Google Scholar 

  • Li Q, Chen Z, Wang H, Yang H, Wen T, Wang S, Hu B, Wang X (2021). Removal of organic compounds by nanoscale zero-valent iron and its composites. Science of the Total Environment, 792: 148546

    Article  CAS  Google Scholar 

  • Lin J Y, Chen Y L, Hong X Y, Huang C, Huang C P (2020). The role of fluoroaluminate complexes on the adsorption of fluoride onto hydrous alumina in aqueous solutions. Journal of Colloid and Interface Science, 561: 275–286

    Article  CAS  Google Scholar 

  • Liufu S C, Xiao H N, Li Y P (2005). Adsorption of polyelectrolyte on the surface of ZnO nanoparticles and the stability of colloidal dispersions. Chinese Science Bulletin, 50(15): 1570–1575

    Article  CAS  Google Scholar 

  • Luo J, Luo X, Crittenden J, Qu J, Bai Y, Peng Y, Li J (2015). Removal of antimonite (Sb(III)) and antimonate (Sb(V)) from aqueous solution using carbon nanofibers that are decorated with zirconium oxide (ZrO2). Environmental Science & Technology, 49(18): 11115–11124

    Article  CAS  Google Scholar 

  • Meenakshi, Maheshwari R C (2006). Fluoride in drinking water and its removal. Journal of Hazardous Materials, 137(1): 456–463

    Article  CAS  Google Scholar 

  • Mohapatra M, Anand S, Mishra B K, Giles D E, Singh P (2009). Review of fluoride removal from drinking water. Journal of Environmental Management, 91(1): 67–77

    Article  CAS  Google Scholar 

  • Pan B, Xu J, Wu B, Li Z, Liu X (2013). Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles. Environmental Science & Technology, 47(16): 9347–9354

    Article  CAS  Google Scholar 

  • Pan Y, Liu C J, Ge Q (2008). Adsorption and protonation of CO2 on partially hydroxylated γ-Al2O3 surfaces: a density functional theory study. Langmuir, 24(21): 12410–12419

    Article  CAS  Google Scholar 

  • Pica M, Donnadio A, Casciola M (2018). From microcrystalline to nanosized α-zirconium phosphate: synthetic approaches and applications of an old material with a bright future. Coordination Chemistry Reviews, 374: 218–235

    Article  CAS  Google Scholar 

  • Pillai P, Dharaskar S, Sinha M K, Sillanpää M, Khalid M (2020). Iron oxide nanoparticles modified with ionic liquid as an efficient adsorbent for fluoride removal from groundwater. Environmental Technology & Innovation, 19: 100842

    Article  Google Scholar 

  • Podgorski J, Berg M (2022). Global analysis and prediction of fluoride in groundwater. Nature Communications, 13(1): 4232

    Article  CAS  Google Scholar 

  • Qiu H, Ye M, Zhang M D, Zhang X, Zhao Y, Yu J (2021). Nano-hydroxyapatite encapsulated inside an anion exchanger for efficient defluoridation of neutral and weakly alkaline water. ACS ES&T Engineering, 1(1): 46–54

    Article  CAS  Google Scholar 

  • Qu X, Zhai P, Shi L, Qu X, Bilal A, Han J, Yu X (2023). Distribution, enrichment mechanism and risk assessment for fluoride in groundwater: a case study of Mihe-Weihe River Basin, China. Frontiers of Environmental Science & Engineering, 17(6): 70

    Article  CAS  Google Scholar 

  • Ravi M, Sushkevich V L, Van Bokhoven J A (2020). Towards a better understanding of Lewis acidic aluminium in zeolites. Nature Materials, 19(10): 1047–1056

    Article  CAS  Google Scholar 

  • Rengarajan G T, Enke D, Steinhart M, Beiner M (2008). Stabilization of the amorphous state of pharmaceuticals in nanopores. Journal of Materials Chemistry, 18(22): 2537–2539

    Article  CAS  Google Scholar 

  • Shen D, Song Y, Chen X, Zhou Y, Li H, Pan J (2022). Fabricating ultrafine zirconium oxide based composite sorbents in “soft confined space” for efficiently removing fluoride from environmental water. Chemical Engineering Journal, 444: 136199

    Article  CAS  Google Scholar 

  • Smith R C, Li J Z, Padungthon S, Sengupta A K (2015). Nexus between polymer support and metal oxide nanoparticles in hybrid nanosorbent materials (HNMs) for sorption/desorption of target ligands. Frontiers of Environmental Science & Engineering, 9(5): 929–938

    Article  CAS  Google Scholar 

  • Tangjitjaroenkit S, Pranudta A, Chanlek N, Nguyen T T, Kuster A T, Kuster A C, El-Moselhy M M, Padungthon S (2021). Fluoride removal by hybrid cation exchanger impregnated with hydrated Al(III) oxide nanoparticles (HCIX-Al) with novel closed-loop recyclable regeneration system. Reactive & Functional Polymers, 169: 105067

    Article  CAS  Google Scholar 

  • Tao W, Zhong H, Pan X, Wang P, Wang H, Huang L (2020). Removal of fluoride from wastewater solution using Ce-AlOOH with oxalic acid as modification. Journal of Hazardous Materials, 384: 121373

    Article  CAS  Google Scholar 

  • ten Elshof J E, Yuan H, Gonzalez Rodriguez P (2016). Two-dimensional metal oxide and metal hydroxide nanosheets: synthesis, controlled assembly and applications in energy conversion and storage. Advanced Energy Materials, 6(23): 1600355

    Article  Google Scholar 

  • Theiss F L, Couperthwaite S J, Ayoko G A, Frost R L (2014). A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides. Journal of Colloid and Interface Science, 417: 356–368

    Article  CAS  Google Scholar 

  • Wang G, Yan T, Shen J, Zhang J, Zhang D (2021). Capacitive removal of fluoride ions via creating multiple capture sites in a modulatory heterostructure. Environmental Science & Technology, 55(17): 11979–11986

    Article  CAS  Google Scholar 

  • Wang X M, Li N, Li J Y, Feng J J, Ma Z, Xu Y T, Sun Y C, Xu D M, Wang J, Gao X L, et al. (2019a). Fluoride removal from secondary effluent of the graphite industry using electrodialysis: optimization with response surface methodology. Frontiers of Environmental Science & Engineering, 13(4): 51

    Article  Google Scholar 

  • Wang Z, Chen Y, Wang L, Zheng J, Fan Y, Zhang S (2023). Rapid and efficient removal of toxic ions from water using Zr-based MOFs@PIM hierarchical porous nanofibre membranes. Chemical Engineering Journal, 452: 139198

    Article  CAS  Google Scholar 

  • Wang Z, Jiang Y, Yi X, Zhou C, Rawal A, Hook J, Liu Z, Deng F, Zheng A, Hunger M, et al. (2019b). High population and dispersion of pentacoordinated AlV species on the surface of flame-made amorphous silica-alumina. Science Bulletin, 64(8): 516–523

    Article  CAS  Google Scholar 

  • Xia G, Li L, Guo Z, Gu Q, Guo Y, Yu X, Liu H, Liu Z (2013). Stabilization of NaZn(BH4)3via nanoconfinement in SBA-15 towards enhanced hydrogen release. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 1(2): 250–257

    CAS  Google Scholar 

  • Yan Q, Lian C, Huang K, Liang L, Yu H, Yin P, Zhang J, Xing M (2021). Constructing an acidic microenvironment by MoS2 in heterogeneous Fenton reaction for pollutant control. Angewandte Chemie International Edition, 60(31): 17155–17163

    Article  CAS  Google Scholar 

  • Zhang J, Tian C, Xu Y, Chen J, Xiao L, Wu G, Jin F (2023a). Effective removal of fluorine ions in phosphoric acid by silicate molecular sieve synthesized by hexafluorosilicic acid. Separation and Purification Technology, 305: 122395

    Article  CAS  Google Scholar 

  • Zhang P, Li Y, Zhang Y, Hou R, Zhang X, Xue C, Wang S, Zhu B, Li N, Shao G (2020a). Photogenerated electron transfer process in heterojunctions: in situ irradiation XPS. Small Methods, 4(9): 2000214

    Article  CAS  Google Scholar 

  • Zhang Q, Du X, Ma X, Hao X, Guan G, Wang Z, Xue C, Zhang Z, Zuo Z (2015). Facile preparation of electroactive amorphous α-ZrP/PANI hybrid film for potential-triggered adsorption of Pb2+ ions. Journal of Hazardous Materials, 289: 91–100

    Article  CAS  Google Scholar 

  • Zhang X, Shen J, Pan S, Qian J, Pan B (2020b). Metastable zirconium phosphate under nanoconfinement with superior adsorption capability for water treatment. Advanced Functional Materials, 30(12): 1909014

    Article  CAS  Google Scholar 

  • Zhang X, Zhang L, Li Z, Jiang Z, Zheng Q, Lin B, Pan B (2017). Rational design of antifouling polymeric nanocomposite for sustainable fluoride removal from NOM-Rich water. Environmental Science & Technology, 51(22): 13363–13371

    Article  CAS  Google Scholar 

  • Zhang X Q, Trinh T T, van Santen R A, Jansen A P (2011). Mechanism of the initial stage of silicate oligomerization. Journal of the American Chemical Society, 133(17): 6613–6625

    Article  CAS  Google Scholar 

  • Zhang Y, De Azambuja F, Parac-Vogt T N (2021). The forgotten chemistry of group(IV) metals: a survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters. Coordination Chemistry Reviews, 438: 213886

    Article  CAS  Google Scholar 

  • Zhang Y, Wang L, Zhang R, He C, Jia L, Wang X, Feng X, Jiang T, Xie B, Ma X, et al. (2023b). Steering electron density of Zr sites using ligand effect in Bio-beads for efficient defluoridation. Advanced Functional Materials, 33(20): 2213999

    Article  CAS  Google Scholar 

  • Zhao X, Zhang Y, Pan S, Zhang X, Zhang W, Pan B (2021). Utilization of gel-type polystyrene host for immobilization of nano-sized hydrated zirconium oxides: a new strategy for enhanced phosphate removal. Chemosphere, 263: 127938

    Article  CAS  Google Scholar 

  • Zhou G, Yang L, Luo C, Liu H, Li P, Cui Y, Liu L, Yu X, Zeng Q, Chen J, et al. (2019). Low-to-moderate fluoride exposure, relative mitochondrial DNA levels, and dental fluorosis in Chinese children. Environment International, 127: 70–77

    Article  CAS  Google Scholar 

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Acknowledgements

We greatly appreciate the financial support from the National Key Research and Development Program of China (No. 2022YFC3205300) and the National Natural Science Foundation of China (No. 22122604).

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Authors and Affiliations

  1. State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, 210023, China

    Sikai Cheng, Zhixian Li, Xiaolin Zhang & Bingcai Pan

  2. Environmental Materials and Pollution Control Laboratory, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, 230031, China

    Kaisheng Zhang

  3. State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, China

    Qingrui Zhang

  4. Hebei Key Laboratory of Heavy Metal Deep-remediation in Water and Resource Reused, Qinhuangdao, 066004, China

    Qingrui Zhang

  5. Research Center for Environmental Nanotechnology (ReCENT), Nanjing University, Nanjing, 210023, China

    Xiaolin Zhang & Bingcai Pan

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  1. Sikai Cheng
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  2. Zhixian Li
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  3. Kaisheng Zhang
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  4. Qingrui Zhang
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Correspondence to Xiaolin Zhang.

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Conflict of Interest The author Bingcai Pan is an Editorial Board Member of Frontiers of Environmental Science & Engineering. The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Highlights

• Nanoconfinement growth produces metastable ZrP with dual Lewis and Brønsted acidity.

• Lewis acid sites’ adsorption affinity rises with reduced outer electron density.

• Brønsted acidity suppresses competitive OH− adsorption onto Lewis acidic sites.

• Brønsted acidity enhances silicate resistance, enabling refreshment of the used ZrP.

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Cheng, S., Li, Z., Zhang, K. et al. Solid Brønsted acidity boosts adsorption reactivity of nano-adsorbent for water decontamination. Front. Environ. Sci. Eng. 18, 81 (2024). https://doi.org/10.1007/s11783-024-1841-2

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  • DOI: https://doi.org/10.1007/s11783-024-1841-2

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