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Evaluation Behavior for the Adsorptive of Ca(II) and Mg(II) Ions (Hardness of Water) from Water by Modified Copper Based on Metal Organic Frameworks and Potentiometric Sensors

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Abstract

This study presents adsorption of Ca(II) and Mg(II) ions from water at different concentration. This causes problems such as corrosion and scaling. MOF–Cu (Cu3(BTC)2) and modified MOF–Cu were study as an adsorbent of Ca2+ and Mg2+ ions from water. The morphology and structure of the MOFs adsorbents were characterized by XRD, FT-IR, nitrogen adsorption/desorption and SEM methods. A batch test with various conditions was studied. The adsorption kinetics and isotherms are described. The experimental data were fitted to second-order-kinetics and Langmuir models. The adsorption capacity of MOF–Cu–GSH (4.6 mg/g (90.2%) and 6.2 mg/g (87.2%)) is higher than Cu3(BTC)2 (9.2 mg/g (81.2%) and 11.3 mg/g (77.4%)) for Ca(II) and Mg(II) ions respectively, through 6 h, 50 ppm, pH 7, 50 mg and 30°C. These potentiometric sensors respond to Mg(II) and Ca(II) ions in the wide linear concentration range of 1.0 × 10–2–1.0 × 10–7 and 1.0 × 10–2–1.3 × 10–7 mol L–1 with Nernstian slopes of 30.04 ± 0.98 and 29.15 ± 0.44 mV decade–1 of Mg(II) and Ca(II) ions and detection limit of 1 × 10–7 and 1.3 × 10–7 mol L–1 for Mg–CPE (electrode IV) and Ca–CPE (electrode X), respectively. The electrodes were pH independent within the range of 2.5–7.5 and 3.0–8.0, with a fast response time of about 7 and 10 s for electrode (IV) and electrode (X), respectively. The results obtained were compared well with those obtained using inductively coupled plasma atomic emission spectrometry (ICP–AES).

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REFERENCES

  1. Zhao, X., Cai, H., Chen, Z., Gong, H., and Feng, Q., Assessing urban lifeline systems immediately after seismic disaster based on emergency resilience, Struct. Infrastruct. Eng., 2016, vol. 12, pp. 1634–1649.

    Article  Google Scholar 

  2. Tegel, M., Schöne, S., Kieback, B., and Röntzsch, L., An efficient hydrolysis of MgH2-based materials, Int. J. Hydrogen Energy, 2017, vol. 42, pp. 2167–2176.

    Article  CAS  Google Scholar 

  3. Sepehr, M.N., Zarrabi, M., Kazemian, H., Amrane, A., Yaghmaian, K., and Ghaffari, H.R., Removal of hardness agents, calcium and magnesium, by natural and alkaline modified pumice stones in single and binary systems, Appl. Surface Sci., 2013, vol. 274, pp. 295–305.

    Article  CAS  Google Scholar 

  4. Sheikholeslami, R., Composite scale formation and assessment by the theoretical Scaling Potential Index (SPI) proposed previously for a single salt, Desalination, 2011, vol. 278, pp. 259–267.

    Article  CAS  Google Scholar 

  5. Fu, L., Wang, J., and Su, Y., Removal of low concentrations of hardness ions from aqueous solutions using electrodeionization process, Sep. Purif. Technol., 2009, vol. 68, pp. 390–406.

    Article  CAS  Google Scholar 

  6. Park, J.-S., Song, J.-H., Yeon, K.-H., and Moon, S.-H., Removal of hardness ions from tap water using electromembrane processes, Desalination, 2007, vol. 202, pp. 1–8.

    Article  CAS  Google Scholar 

  7. Apell, J.N. and Boyer, T.H., Combined ion exchange treatment for removal of dissolved organic matter and hardness, Water Res., 2010, vol. 44, pp. 2419–2430.

    Article  CAS  PubMed  Google Scholar 

  8. Seifi, L., Torabian, A., Kazemian, H., Bidhendi, G.N., Azimi, A.A., Nazmara, S., et al., Adsorption of BTEX on surfactant modified granulated natural zeolite nanoparticles: parameters optimizing by applying taguchi experimental design method, CLEAN–Soil, Air, Water, 2011, vol. 39, pp. 939–948.

    CAS  Google Scholar 

  9. Furukawa, H., Gándara, F., Zhang, Y.-B., Jiang, J., Queen, W.L., Hudson, M.R., et al., Water adsorption in porous metal–organic frameworks and related materials, J. Am. Chem. Soc., 2014, vol. 136, pp. 4369–4381.

    Article  CAS  PubMed  Google Scholar 

  10. Al-Sabagh, A.M., El-Awamri, A.A., Abdou, M.I., Hussien, H.A., Abd El Fatah, H.M., and Rasmy, W.E., Egyptian diatomite as high fluid loss squeeze slurry in sealing fractures and high permeable formation, Egypt. J. Pet., 2016, vol. 25, pp. 409–421.

    Google Scholar 

  11. Mitri, E., Millucci, L., Merolle, L., Bernardini, G., Vaccari, L., Gianoncelli, A., et al., A new light on Alkaptonuria: a Fourier-transform infrared microscopy (FTIRM) and low energy X-ray fluorescence (LEXRF) microscopy correlative study on a rare disease, Biochim. Biophys. Acta—General Subjects, 2017, vol. 1861, pp. 1000–1008.

    Article  CAS  Google Scholar 

  12. Natasha, N.C. and Lalasari, L.H., Calcium extraction from brine water and seawater using oxalic acid, AIP Conf. Proc., 2017, vol. 1805, no. 1.

  13. Salem, A., Noaman, E., Kandil, E., Badawi, A., and Mostafa, N., Crystal structure and chemotherapeutic efficacy of the novel compound, gallium tetrachloride betaine, against breast cancer using nanotechnology, Tumor Biol., 2016, vol. 37, pp. 11025–11038.

    Article  CAS  Google Scholar 

  14. Asare, G.A., Ngala, R.A., Afriyie, D., Adjei, S., Nyarko, A., Anang-Quartey, Y., et al., Calcium–magnesium imbalance implicated in benign prostatic hyperplasia and restoration by a phytotherapeutic drug—Croton membranaceus Müll.Arg., BMC Complement. Altern. Med., 2017, vol. 17, no. 1, p. 152.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Akl, Z.F. and Ali, T.A., Highly sensitive potentiometric sensors for thorium ions detection using morpholine derivative self-assembled on silver nanoparticles, RSC Adv., 2016, vol. 6, pp. 77854–77862.

    Article  CAS  Google Scholar 

  16. Ali, T.A., Aglan, R.F., Mohamed, G.G., and Mourad, M.A., New chemically modified screen-printed electrode for Co(II) determination in different water samples, Int. J. Electrochem. Sci., 2014, vol. 9, pp. 1812–1826.

    Google Scholar 

  17. Ali, T.A., Azzam, E.M.S., Hegazy, M.A., El-Farargy, A.F.M., and Abd-elaal, A.A., Zinc(II) modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticles for its determination in water samples, J. Industr. Eng. Chem., 2014, vol. 20, pp. 3320–3328.

    Article  CAS  Google Scholar 

  18. Ali, T.A., Eldidamony, A.M., Mohamed, G.G., and Elatfy, D.M., Construction of chemically modified electrode for the selective determination of copper(II) ions in polluted water samples based on new β-cyclodextrine and 1,4-bis(6-bromohexyloxy)benzene ionophores, Int. J. Electrochem. Sci., 2014, vol. 9, pp. 2420–2434.

    Google Scholar 

  19. Ali, T.A., Farag, A.A., and Mohamed, G.G., Potentiometric determination of iron in polluted water samples using new modified Fe(III)-screen printed ion selective electrode, J. Industr. Eng. Chem., 2014, vol. 20, pp. 2394–2400.

    Article  CAS  Google Scholar 

  20. Ali, T.A. and Mohamed, G.G., Modified screen-printed ion selective electrodes for potentiometric determination of sodium dodecylsulfate in different samples, J. AOAC Int., 2015, vol. 98, pp. 116–123.

    Article  CAS  PubMed  Google Scholar 

  21. Ali, T.A., Mohamed, G.G., Al-Sabagh, A.M., and Migahed, M.A., A new screen-printed ion selective electrode for determination of citalopram hydrobromide in pharmaceutical formulation, Fenxi Huaxue/Chinese J. Anal. Chem., 2014, vol. 42, pp. 565–572.

    Article  CAS  Google Scholar 

  22. Ali, T.A., Mohamed, G.G., Omar, M.M., and Abdrabou, V.N., Improved determination of mebeverine hydrochloride in urine, serum and pharmaceutical preparations utilizing a modified carbon paste electrode, Int. J. Electrochem. Sci., 2015, vol. 10, pp. 2439–2454.

    CAS  Google Scholar 

  23. Ali, T.A., Soliman, M.H., Mohamed, G.G., Farag, A.B., and Samah, M.K., Development of a new modified screen-printed and carbon paste electrodes for selective determination of cetyltrimethylammonium bromide in different water samples, Int. J. Electrochem. Sci., 2015, vol. 10, pp. 3192–3206.

    CAS  Google Scholar 

  24. Frag, E.Y.Z., Ali, T.A., Mohamed, G.G., and Awad, Y.H.H., Construction of different types of ion-selective electrodes. characteristic performances and validation for direct potentiometric determination of orphenadrine citrate, Int. J. Electrochem. Sci., 2012, vol. 7, pp. 4443–4464.

    CAS  Google Scholar 

  25. Abudu, N., Miller, J.J., and Elin, R.J., The effect of thiocyanate on the nova ion-selective electrode for magnesium, J. Clin. Ligand Assay, 2007, vol. 29, pp. 182–184.

    Google Scholar 

  26. Gasser, S., Scherr, E., and Gasser, R., An ion-selective microelectrode study on the effect of acidification on free intracellular magnesium cardiac guinea pig papillary muscle, Trace Elements Electrolytes, 2008, vol. 25, pp. 14–20.

    Article  CAS  Google Scholar 

  27. Mosayebzadeh, Z., Ansari, R., and Arvand, M., Preparation of a solid-state ion-selective electrode based on polypyrrole conducting polymer for magnesium ion, J. Iranian Chem. Soc., 2014, vol. 11, pp. 447–456.

    Article  CAS  Google Scholar 

  28. Ali, T.A. and Mohamed, G.G., Determination of Mn(II) ion by a modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) in different water samples, Sens. Actuat. B: Chem., 2014, vol. 202, pp. 699–707.

    Article  CAS  Google Scholar 

  29. Ali, T.A., Mohamed, G.G., Azzam, E.M.S., and Abd-Elaal, A.A., Thiol surfactant assembled on gold nanoparticles ion exchanger for screen-printed electrode fabrication. Potentiometric determination of Ce(III) in environmental polluted samples, Sens. Actuat. B: Chem., 2014, vol. 191, pp. 192–203.

    Article  CAS  Google Scholar 

  30. Qu, J., Wu, L., Liu, H., Li, J., Lv, H., Fu, X., et al., A novel electrochemical biosensor based on DNA for rapid and selective detection of cadmium, Int. J. Electrochem. Sci., 2014, vol. 10, pp. 4020–4028.

    Google Scholar 

  31. Zamani, H.A., Nezhadali, A., and Saghravanian, M., Magnesium-PVC membrane sensor based on 4,5-Bis(benzoylthio)-1,3-dithiole-2-thione, Anal. Lett., 2008, vol. 41, pp. 2727–2742.

    Article  CAS  Google Scholar 

  32. Abiman, P., Wildgoose, G.G., Crossley, A., and Compton, R.G., Quantitative studies of metal ion adsorption on a chemically modified carbon surface: adsorption of Cd (II) and Hg (II) on glutathione modified carbon, Electroanalysis, 2009, vol. 21, pp. 897–903.

    Article  CAS  Google Scholar 

  33. Li, H., Cui, Z., and Han, C., Glutathione-stabilized silver nanoparticles as colorimetric sensor for Ni2+ ion, Sens. Actuat. B: Chem., 2009, vol. 143, pp. 87–92.

    Article  CAS  Google Scholar 

  34. Yan, M., Wang, D., Ni, J., Qu, J., Yan, Y., and Chow, C.W., Effect of polyaluminum chloride on enhanced softening for the typical organic-polluted high hardness North-China surface waters, Separat. Pur. Technol., 2008, vol. 62, pp. 401–406.

    Article  CAS  Google Scholar 

  35. Ke, F., Qiu, L.-G., Yuan, Y.-P., Peng, F.-M., Jiang, X., Xie, A.-J., et al., Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water, J. Hazard. Mater., 2011, vol. 196, pp. 36–43.

    Article  CAS  PubMed  Google Scholar 

  36. Holland, P.L., Cramer, C.J., Wilkinson, E.C., Mahapatra, S., Rodgers, K.R., Itoh, S., et al., Resonance Raman spectroscopy as a probe of the Bis (μ-oxo) dicopper core, J. Am. Chem. Soc., 2000, vol. 122, pp. 792–802.

    Article  CAS  Google Scholar 

  37. Jun, W., Wei-Ping, W., Lu, L., and Bin, X., Self-assembly of water cluster in Cu (II) complexes and magnetic property, J. Molec. Struct., 2013, vol. 1036, pp. 174–179.

    Article  CAS  Google Scholar 

  38. Shindo, H. and Brown, T.L., Infrared spectra of complexes of L-cysteine and related compounds with zinc(II), cadmium(II), mercury(II), and lead(II) 1, J. Am. Chem. Soc., 1965, vol. 87, pp. 1904–1909.

    Article  CAS  PubMed  Google Scholar 

  39. Silver, J., Hamed, M.Y., and Morrison, I.E., Studies of the reactions of ferric iron with glutathione and some related thiols. Part V. Solid complexes containing FeII and glutathione or FeIII with oxidized glutathione, Inorg. Chim. Acta, 1985, vol. 107, pp. 169–178.

    Article  CAS  Google Scholar 

  40. Mahmoud Fathy, T., Abdou, M., El-Bellihi, A.-H.A., and Awadallah, A.E., Study the adsorption of Ca(II) and Mg(II) on high cross-linked polystyrene divinyl benzene resin, Int. J. Modern Chem., 2015, vol. 7, pp. 36–44.

    Google Scholar 

  41. Onundi, Y.B., Mamun, A., Al Khatib, M., and Ahmed, Y.M., Adsorption of copper, nickel and lead ions from synthetic semiconductor industrial wastewater by palm shell activated carbon, Int. J. Environ. Sci. Technol., 2010, vol. 7, pp. 751–758.

    Article  CAS  Google Scholar 

  42. Hartono, T., Wang, S., Ma, Q., and Zhu, Z., Layer structured graphite oxide as a novel adsorbent for humic acid removal from aqueous solution, J. Colloid Interface Sci., 2009, vol. 333, pp. 114–119.

    Article  CAS  PubMed  Google Scholar 

  43. Bhatnagar, A. and Jain, A., A comparative adsorption study with different industrial wastes as adsorbents for the removal of cationic dyes from water, J. Colloid Interface Sci., 2005, vol. 281, pp. 49–55.

    Article  CAS  PubMed  Google Scholar 

  44. Al-Asheh, S. and Duvnjak, Z., Sorption of heavy metals by canola meal, Water, Air, Soil Pollut., 1999, vol. 114, pp. 251–276.

    Article  CAS  Google Scholar 

  45. Mahatmanti, F.W., Nuryono, N., and Narsito, N., Adsorption of Ca (II), Mg (II), Zn (II), and Cd (II) on chitosan membrane blended with rice hull ash silica and polyethylene glycol, Indonesian J. Chem., 2016, vol. 16, pp. 45–52.

    Article  CAS  Google Scholar 

  46. Fosso-Kankeu, E., Waanders, F., Maloy, E., and Steyn, B., Reduction of salinity and hardness of water using copolymerized biopolymers, Proc. Int. Mine Water Association Conf., Leipzig, Dec. 2016, vol. 1.

  47. Horsfall, M., Jr. and Spiff, A.I., Effects of temperature on the sorption of Pb2+ and Cd2+ from aqueous solution by Caladium bicolor (Wild Cocoyam) biomass, Electron. J. Biotechnol., 2005, vol. 8, pp. 43–50.

    Google Scholar 

  48. Antropov, L.I., Theoretical Electrochemistry, Moscow: Mir Publ., 1977.

    Google Scholar 

  49. Ali, T.A., Mohamed, G.G., and Farag, A.H., Electroanalytical studies on Fe(III) ion-selective sensors based on 2-methyl-6-(4-methylenecyclohex-2-en-1-yl)hept-2-en-4-one ionophore, Int. J. Electrochem. Sci., 2015, vol. 10, pp. 564–578.

    CAS  Google Scholar 

  50. Ali, T.A., Mohamed, G.G., Omar, M.M., and Hanafy, N.M., Construction and performance characteristics of chemically modified carbon paste electrodes for the selective determination of Co(II) ions in water samples, J. Industr. Eng. Chem., 2017, vol. 47, pp. 102–111.

    Article  CAS  Google Scholar 

  51. Ali, T.A., Mohamed, G.G., and Othman, A.R., Design and construction of new potentiometric sensors for determination of copper(II) ion based on copper oxide nanoparticles, Int. J. Electrochem. Sci., 2015, vol. 10, pp. 8041–8057.

    CAS  Google Scholar 

  52. Ali, T.A., Mohamed, G.G., El-Dessouky, M.M.I., Abou El Ella, S.M., and Mohamed, R.T.F., Modified carbon paste ion selective electrodes for the determination of iron (III) in water, soil and fish tissue samples, Int. J. Electrochem. Sci., 2013, vol. 8, pp. 1469–1486.

    Google Scholar 

  53. Ali, T.A., Mohamed, G.G., El-Dessouky, M.M.I., Abou El-Ella, S.M., and Mohamed, R.T.F., Modified screen-printed electrode for potentiometric determination of copper(II) in water samples, J. Solution Chem., 2013, vol. 42, pp. 1336–1354.

    Article  CAS  Google Scholar 

  54. Mohamed, G.G., Ali, T.A., El-Shahat, M.F., Al-Sabagh, A.M., and Migahed, M.A., New screen-printed ion-selective electrodes for potentiometric titration of cetyltrimethylammonium bromide in different civilic media, Electroanalysis, 2010, vol. 22, pp. 2587–2599.

    Article  CAS  Google Scholar 

  55. Mohamed, G.G., Ali, T.A., El-Shahat, M.F., Migahed, M.A., and Al-Sabagh, A.M., Novel screen-printed electrode for the determination of dodecyltrimethylammonium bromide in water samples, Drug Test. Anal., 2012, vol. 4, pp. 1009–1013.

    Article  CAS  PubMed  Google Scholar 

  56. Mohamed, G.G., El-Shahat, M.F., Al-Sabagh, A.M., Migahed, M.A., and Ali, T.A., Septonex-tetraphenylborate screen-printed ion selective electrode for the potentiometric determination of Septonex in pharmaceutical preparations, Analyst, 2011, vol. 136, pp. 1488–1495.

    Article  CAS  PubMed  Google Scholar 

  57. Ali, T.A., Aglan, R.F., Mohamed, G.G., and Mourad, M.A., New chemically modified screen-printed electrode for Co (II) determination in different water samples, Int. J. Electrochem. Sci., 2014, vol. 9, pp. 1812–1826.

    Google Scholar 

  58. Ali, T.A. and Mohamed, G.G., Potentiometric determination of La(III) in polluted water samples using modified screen-printed electrode by self-assembled mercapto compound on silver nanoparticles, Sens. Actuators, B: Chem., 2015, vol. 216, pp. 542–550.

    Article  CAS  Google Scholar 

  59. Ali, T.A. and Mohamed, G.G., Multi-walled carbon nanotube and nanosilica chemically modified carbon paste electrodes for the determination of mercury(II) in polluted water samples, Anal. Methods, 2015, vol. 7, pp. 6280–6289.

    Article  CAS  Google Scholar 

  60. Ali, T.A., Mohamed, G.G., El-Dessouky, M.M., and Ragheb, R.M., Highly selective potentiometric determination of 1-dodecyl-5-methyl-1H-benzo[d][1,2,3]triazol-1-ium bromide surfactant in polluted water samples using 1,4-bis-(8-Mercaptooctyloxy)-benzene ionophore, Int. J. Electrochem. Sci., 2015, vol. 10, pp. 4820–4831.

    CAS  Google Scholar 

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Tamer Awad Ali, El Salam, H.M., Ali, H.R. et al. Evaluation Behavior for the Adsorptive of Ca(II) and Mg(II) Ions (Hardness of Water) from Water by Modified Copper Based on Metal Organic Frameworks and Potentiometric Sensors. Russ J Electrochem 55, 621–636 (2019). https://doi.org/10.1134/S1023193519070024

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