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Catalytically active silver nanoparticles loaded in the lumen of halloysite nanotubes via electrostatic interactions

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Abstract

Halloysites are a kind of aluminosilicate clay with a morphology of a nanotube. The inner wall of halloysite is positively charged, and the external surface is negatively charged. In this work, we propose a simple and facile method to prepare Ag NPs loaded in the lumen of halloysite nanotubes (HNTs). Herein, N-acetyl-l-cysteine modified silver nanoparticles (Ag NPs) with negative charges spontaneously and stably resided in the lumen of HNTs via electrostatic interactions. The images of transmission electron microscopy and scanning transmission electron microscopy showed that Ag NPs with a size of ~2.6 nm were uniformly distributed in the lumen of HNTs. The catalytic activity of the obtained Ag NPs/HNTs composites was evaluated by the reduction reaction of 4-nitrophenol (4-NP) as a model reaction. When the molar ratio of Ag and 4-NP was set at 0.008, the rate constant of the reaction was found to be 0.91 min−1, two times higher than that of Ag NPs adsorbed on the external surface of HNTs. Additionally, no Ag NPs were found in the supernatant after the Ag NPs/HNTs suspension was stirred for 30 min. Such structural stability implies good reusability as a catalyst.

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References

  1. Lvov Y, Wang W, Zhang L, Fakhrullin R (2016) Halloysite clay nanotubes for loading and sustained release of functional compounds. Adv Mater 28:1227–1250

    Article  Google Scholar 

  2. Liu M, Jia Z, Jia D, Zhou C (2014) Recent advance in research on halloysite nanotubes-polymer nanocomposite. Prog Polym Sci 39:1498–1525

    Article  Google Scholar 

  3. Deng S, Zhang J, Ye L (2009) Halloysite–epoxy nanocomposites with improved particle dispersion through ball mill homogenisation and chemical treatments. Compos Sci Technol 69:2497–2505

    Article  Google Scholar 

  4. Liu M, Guo B, Zou Q, Du M, Jia D (2008) Interactions between halloysite nanotubes and 2,5-bis(2-benzoxazolyl) thiophene and their effects on reinforcement of polypropylene/halloysite nanocomposites. Nanotechnology 19:205709

    Article  Google Scholar 

  5. Cong C, Liu J, Wang J et al (2013) Surface modification of halloysite nanotubes with dopamine for enzyme immobilization. ACS Appl Mater Interfaces 5:10559–10564

    Article  Google Scholar 

  6. Zhai R, Zhang B, Liu L, Xie Y, Zhang H, Liu J (2010) Immobilization of enzyme biocatalyst on natural halloysite nanotubes. Catal Commun 12:259–263

    Article  Google Scholar 

  7. Lvov Y, Price R, Gaber B, Ichinose I (2002) Thin film nanofabrication via layer-by-layer adsorption of tubule halloysite, spherical silica, proteins and polycations. Colloid Surf A 198–200:375–382

    Article  Google Scholar 

  8. Das S, Jana S (2015) A facile approach to fabricate halloysite/metal nanocomposites with preformed and in situ synthesized metal nanoparticles: a comparative study of their enhanced catalytic activity. Dalton Trans 44:8906–8916

    Article  Google Scholar 

  9. Liu P, Zhao M (2009) Silver nanoparticle supported on halloysite nanotubes catalyzed reduction of 4-nitrophenol (4-NP). Appl Surf Sci 255:3989–3993

    Article  Google Scholar 

  10. Zou ML, Du ML, Zhu H, Xu CS, Fu YQ (2012) Green synthesis of halloysite nanotubes supported Ag nanoparticles for photocatalytic decomposition of methylene blue. J Phys D Appl Phys 45:325302–325308

    Article  Google Scholar 

  11. Barrientos-Ramírez S, Ramos-Fernández EV, Silvestre-Albero J, Sepúlveda-Escribano A, Pastor-Blas MM, González-Montiel A (2009) Use of nanotubes of natural halloysite as catalyst support in the atom transfer radical polymerization of methyl methacrylate. Microporous Mesoporous Mater 120:132–140

    Article  Google Scholar 

  12. Massaro M, Riela S, Cavallaro G, Colletti CG, Milioto S, Noto R, Parisi F, Lazzara G (2015) Palladium supported on Halloysite-triazolium salts as catalyst for ligand free Suzuki cross-coupling in water under microwave irradiation. J Mol Catal A Chem 408:12–19

    Article  Google Scholar 

  13. Massaro M, Riela S, Cavallaro G, Gruttadauria M, Milioto S, Noto R, Lazzara G (2014) Eco-friendly functionalization of natural halloysite clay nanotube with ionic liquids by microwave irradiation for Suzuki coupling reaction. J Organomet Chem 749:410–415

    Article  Google Scholar 

  14. Dzamukova MR, Naumenko EA, Lvov YM, Fakhrullin RF (2014) Enzyme-activated intracellular drug delivery with tubule clay nanoformulation. Sci Rep 5:10560–10570

    Article  Google Scholar 

  15. Lee Y, Jung GE, Cho SJ, Geckeler KE, Fuchs H (2013) Cellular interactions of doxorubicin-loaded DNA-modified halloysite nanotubes. Nanoscale 5:8577–8585

    Article  Google Scholar 

  16. Forsgren J, Jämstorp E, Bredenberg S, Engqvist H, Strømme M (2010) A ceramic drug delivery vehicle for oral administration of highly potent opioids & dagger. J Pharm Sci 99:219–226

    Article  Google Scholar 

  17. Ward CJ, Song S, Davis EW (2010) Controlled release of tetracycline-HCl from halloysite-polymer composite films. J Nanosci Nanotechnol 10:6641–6649

    Article  Google Scholar 

  18. Lvov Y, Aerov A, Fakhrullin R (2014) Clay nanotube encapsulation for functional biocomposites. Adv Colloid Interface Sci 207:189–198

    Article  Google Scholar 

  19. Suh YJ, Kil DS, Chung KS, Abdullayev E, Lvov YM, Mongayt D (2011) Natural nanocontainer for the controlled delivery of glycerol as a moisturizing agent. J Nanosci Nanotechnol 11:661–665

    Article  Google Scholar 

  20. Vergaro V, Lvov YM, Leporatti S (2012) Halloysite clay nanotubes for resveratrol delivery to cancer cells. Macromol Biosci 12:1265–1271

    Article  Google Scholar 

  21. Zhang Y, Liu J, Chen Y, Zhang H, Bing Z (2013) Potent antibacterial activity of a novel silver nanoparticle-halloysite nanotube nanocomposite powder. J Inorg Biochem 118:59–64

    Article  Google Scholar 

  22. Yu L, Zhang Y, Zhang B, Liu J (2014) Enhanced antibacterial activity of silver nanoparticles/halloysite nanotubes/graphene nanocomposites with sandwich-like structure. Sci Rep 4:212–214

    Google Scholar 

  23. Abdullayev E, Sakakibara K, Okamoto K, Wei W, Ariga K, Lvov Y (2011) Natural tubule clay template synthesis of silver nanorods for antibacterial composite coating. ACS Appl Mater Interfaces 3:4040–4046

    Article  Google Scholar 

  24. Wei W, Minullina R, Abdullayev E, Fakhrullin R, Mills D, Lvov Y (2014) Enhanced efficiency of antiseptics with sustained release from clay nanotubes. RSC Adv 4:488–494

    Article  Google Scholar 

  25. Joshi A, Abdullayev E, Vasiliev A, Volkova O, Lvov Y (2012) Interfacial modification of clay nanotubes for the sustained release of corrosion inhibitors. Infect Immun 29:7439–7448

    Google Scholar 

  26. Abdullayev E, Price R, Shchukin D, Lvov Y (2009) Halloysite tubes as nanocontainers for anticorrosion coating with benzotriazole. ACS Appl Mater Interfaces 1:1437–1443

    Article  Google Scholar 

  27. Chi Y, Tu J, Wang M, Li X, Zhao Z (2014) One-pot synthesis of ordered mesoporous silver nanoparticle/carbon composites for catalytic reduction of 4-nitrophenol. J Colloid Interface Sci 423:54–59

    Article  Google Scholar 

  28. Zheng C, Wang H, Liu L, Zhang M, Liang J, Han H (2013) Synthesis and spectroscopic characterization of water-soluble fluorescent ag nanoclusters. Mol Cell Biol 2013:261648

  29. Makwana BA, Vyas DJ, Bhatt KD, Darji S, Jain VK (2015) Novel fluorescent silver nanoparticles: sensitive and selective turn off sensor for cadmium ions. Appl Nanosci 6:1–12

    Google Scholar 

  30. Zhang J, Xu S, Kumacheva E (2005) Photogeneration of fluorescent silver nanoclusters in polymer microgels. Adv Mater 17:2336–2340

    Article  Google Scholar 

  31. Zhang P, Shao C, Zhang Z et al (2011) In situ assembly of well-dispersed Ag nanoparticles (AgNPs) on electrospun carbon nanofibers (CNFs) for catalytic reduction of 4-nitrophenol. Nanoscale 3:3357–3363

    Article  Google Scholar 

  32. Sarkar K (2015) Synthesis of graphene oxide–silver nanocomposite with photochemically grown silver nanoparticles to use as a channel material in thin film field effect transistors. RSC Adv 5:107811–107821

    Article  Google Scholar 

  33. Rawtani D, Agrawal YK, Prajapati P (2013) Interaction behavior of DNA with Halloysite nanotube-silver nanoparticle-based composite. Bionanoscience 3:73–78

    Article  Google Scholar 

  34. Ouyang J, Guo B, Fu L et al (2016) Radical guided selective loading of silver nanoparticles at interior lumen and out surface of halloysite nanotubes. Mater Des 110:169–178

    Article  Google Scholar 

  35. Sanchez-Ballester NM, Gubbala RV, Tanabe T, Koudelkova E, Liu J, Shrestha LK, Lvov YM, Hill JP, Ariga K, Abe H (2015) Activated interiors of clay nanotubes for agglomeration-tolerant automotive exhaust remediation. J Mater Chem A 3:6614–6619

    Article  Google Scholar 

  36. Wu S, Qiu M, Guo B, Zhang L, Lvov YM (2017) Nanodot-loaded clay nanotubes as green and sustained Radical Scavengers for Elastomer. ACS Sustain Chem Eng 5:1775–1783

    Article  Google Scholar 

  37. VeerabadranNG Price RR, Lvov YM (2007) Clay nanotubes for encapsulation and sustained release of drugs. NANO 02:115–120

    Article  Google Scholar 

  38. Vergaro V, Abdullayev E, Lvov YM, Zeitoun A, Cingolani R, Rinaldi R, Leporatti S (2010) Cytocompatibility and uptake of halloysite clay nanotubes. Biomacromol 11:820–826

    Article  Google Scholar 

  39. Pablo C, Pedro C, Iraida L, Grande HJ, Ibon O (2010) Converting drugs into gelators: supramolecular hydrogels from N-acetyl-l-cysteine and coinage-metal salts. Org Biomol Chem 8:5455–5458

    Article  Google Scholar 

  40. Li W, Zeng X, Wang H, Wang Q, Yang Y (2016) PVA-reinforced glutathione-Ag hydrogels and release of Ag nanoparticles and drugs by UV-triggered controllable disassembly. New J Chem 40:4528–4533

    Article  Google Scholar 

  41. Cavallaro G, Lazzara G, Milioto S (2012) Exploiting the colloidal stability and solubilization ability of clay nanotubes/Ionic surfactant hybrid nanomaterials. J Phys Chem C 116:21932–21938

    Article  Google Scholar 

  42. Wang Q, Liu S, Wang H, Yang Y (2016) In situ pore-forming alginate hydrogel beads loaded with in situ formed nano-silver and their catalytic activity. Phys Chem Chem Phys 18:12610–12615

    Article  Google Scholar 

  43. You J (2014) Fabrication of high-density silver nanoparticles on the surface of alginate microspheres for application in catalytic reaction. J Mater Chem A 2:8491–8499

    Article  Google Scholar 

  44. Shin KS, Choi JY, Chan SP, Jang HJ, Kim K (2009) Facile Synthesis and catalytic application of silver-deposited magnetic nanoparticles. Catal Lett 133:1–7

    Article  Google Scholar 

  45. Liang M, Wang L, Liu X et al (2013) Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts. Nanotechnology 24:385–393

    Google Scholar 

  46. Zhu M, Wang C, Meng D, Diao G (2013) In situ synthesis of silver nanostructures on magnetic Fe3O4@C core–shell nanocomposites and their application in catalytic reduction reactions. J Mater Chem A 1:2118–2125

    Article  Google Scholar 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant 51473057 and 51573064). We are grateful to the Analytical and Testing Center of HUST for TEM measurements.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

    Xiaoping Zeng, Qin Wang, Hong Wang & Yajiang Yang

  2. Key Laboratory for Green Chemical Process of Ministry of Education, School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, 430073, China

    Xiaoping Zeng

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  1. Xiaoping Zeng
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Correspondence to Yajiang Yang.

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Zeng, X., Wang, Q., Wang, H. et al. Catalytically active silver nanoparticles loaded in the lumen of halloysite nanotubes via electrostatic interactions. J Mater Sci 52, 8391–8400 (2017). https://doi.org/10.1007/s10853-017-1073-y

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