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Microwave solvothermal decoration of the cellulose surface by nanostructured hybrid Ag/ZnO particles: a joint XPS, XRD and SEM study

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Abstract

The synthesis of hybrid silver/zinc oxide (Ag/ZnO) decoration on the cellulose surface is described. The structures were characterized with X-ray photoelectron spectroscopy (XPS) and corroborated with X-ray diffraction and scanning electron microscopy. Silver nitrate and zinc acetate dihydrate were used as soluble raw materials. Hexamethylenetetraamine was used as the precipitating and reducing agent. The surface of α-cellulose was always treated by hydrogen peroxide before synthesis with a relatively mild effect manifested in water contact angle measurement and XPS high-resolution spectra. The Ag/ZnO decoration system was identified as a true nanodispersed metal/semiconductor hybrid with a unique collective plasmonic structure observed on Ag 3d core lines for the first time. A series of experiments with a single precursor solution contributed to the characterization of the interaction of Ag+ and Zn2+ species with the surface and to the description of the reaction mechanism in the mixed precursor solution. In contrast to previous reports, a specific interaction between the cellulose substrate and Zn2+ was observed. No specific non-thermal effects of microwave heating were observed.

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References

  • Abdul Khalil HPS, Davoudpour Y, Islam MN, Mustapha A, Sudesh K, Dungani R, Jawaid M (2014) Production and modification of nanofibrillated cellulose using various mechanical processes: a review. Carbohyd Polym 99:649–665

    Article  CAS  Google Scholar 

  • Alammar T, Mudring AV (2009) Facile preparation of Ag/ZnO nanoparticles via photoreduction. J Mater Sci 44:3218–3222

    Article  CAS  Google Scholar 

  • Amendola V, Bakr OM, Stellacci F (2010) A study of the surface plasmon resonance of silver nanoparticles by the discrete dipole approximation method: effect of shape. Size, Structure, and Assembly Plasmonics 5:85–97

    Article  CAS  Google Scholar 

  • Ansari SA, Khan MM, Ansari MO, Lee J, Cho MH (2013) Biogenic synthesis, photocatalytic, and photoelectrochemical performance of Ag–ZnO nanocomposite. J Phys Chem C 117:27023–27030

    Article  CAS  Google Scholar 

  • Ashfold MNR, Doherty RP, Ndifor-Angwafor NG, Riley DJ, Sun Y (2007) The kinetics of the hydrothermal growth of ZnO nanostructures. Thin Solid Films 515:8679–8683

    Article  CAS  Google Scholar 

  • Ashraf S, Saifur R, Sher F, Khalid ZM, Mehmood M, Hussain I (2014) Synthesis of cellulose-metal nanoparticle composites: development and comparison of different protocols. Cellulose 21:395–405

    Article  CAS  Google Scholar 

  • Aymonier C, Schlotterbeck U, Antonietti L, Zacharias P, Thomann R, Tiller JC, Mecking S (2002) Hybrids of silver nanoparticles with amphiphilic hyperbranched macromolecules exhibiting antimicrobial properties. Chem Commun 3018–3019

    Article  Google Scholar 

  • Baruah S, Dutta J (2009) Hydrothermal growth of ZnO nanostructures. Sci Technol Adv Mater 10:013001

  • Bazant P, Kuritka I, Hudecek O, Machovsky M, Mrlik M, Sedlacek T (2014a) Microwave-assisted synthesis of Ag/ZnO hybrid filler, preparation, and characterization of antibacterial poly(vinyl chloride) composites made from the same. Polym Composite 35:19–26

    Article  CAS  Google Scholar 

  • Bazant P, Kuritka I, Munster L, Machovsky M, Kozakova Z, Saha P (2014b) Hybrid nanostructured Ag/ZnO decorated powder cellulose fillers for medical plastics with enhanced surface antibacterial activity. J Mater Sci Mater Med 25:2501–2512

    Article  CAS  Google Scholar 

  • Bilecka I, Niederberger M (2010) Microwave chemistry for inorganic nanomaterials synthesis. Nanoscale 2:1358–1374

    Article  CAS  Google Scholar 

  • Biswick T, Jones W, Pacula A, Serwicka E, Podobinski J (2009) Evidence for the formation of anhydrous zinc acetate and acetic anhydride during the thermal degradation of zinc hydroxy acetate, Zn-5(OH)(8)(CH3CO2)(2)center dot 4H(2)O to ZnO. Solid State Sci 11:330–335

    Article  CAS  Google Scholar 

  • Borys NJ, Shafran E, Lupton JM (2013) Surface plasmon delocalization in silver nanoparticle aggregates revealed by subdiffraction supercontinuum hot spots. Sci Rep 3:2090

  • Capilla AV, Aranda RA (1979) Anhydrous zinc (Ii) acetate (CH3–COO)2Zn crystal structure. Communications 8:795–798

    Google Scholar 

  • Chauhan R, Kumar A, Chaudhary RP (2012) Photocatalytic studies of silver doped ZnO nanoparticles synthesized by chemical precipitation method. J Sol–Gel Sci Technol 63:546–553

    Article  CAS  Google Scholar 

  • Cho S, Jung SH, Lee KH (2008) Morphology-controlled growth of ZnO nanostructures using microwave irradiation: from basic to complex structures. J Phys Chem C 112:12769–12776

    Article  CAS  Google Scholar 

  • Compagnini G, Messina GC, D’Urso L, Messina E, Sinatra MG, Puglisi O, Zimbone M (2011) Aggregation phenomena and electromagnetic amplification properties in silver nanoparticles joined through highly conjugated carbon chains. Open Surf Sci J 3

  • De Jong WH, Borm PJA (2008) Drug delivery and nanoparticles: applications and hazards International. J Nanomed 3:133–149

    Article  Google Scholar 

  • Distaso M, Mackovic M, Spiecker E, Peukert W (2012) Early stages of oriented attachment: formation of twin ZnO nanorods under microwave irradiation. Chem-Eur J 18:13265–13268

    Article  CAS  Google Scholar 

  • Dorris GM, Gray DG (1978a) The surface analysis of paper and wood fibres by ESCA (electron spectroscopy for chemical analysis). I. Application to cellulose and lignin. Cellul Chem Technol 12:9–23

    CAS  Google Scholar 

  • Dorris GM, Gray DG (1978b) The surface analysis of paper and wood fibres by ESCA. II. Surface composition of mechanical pulps. Cellul Chem Technol 12:721–734

    CAS  Google Scholar 

  • Dorris GM, Gray DG (1978c) The surface analysis of paper and wood fibres by ESCA. III. Interpretation of carbon (1s) peak shape. Cellul Chem Technol 16:735–743

    Google Scholar 

  • Duan S, Wang R (2013) Bimetallic nanostructures with magnetic and noble metals and their physicochemical applications. Prog Nat Sci Mater Int 23:113–126

    Article  Google Scholar 

  • Fan Z, Lu JG (2005) Zinc oxide nanostructures: synthesis and properties. J Nanosci Nanotechnol 5:1561–1573

    Article  CAS  Google Scholar 

  • Georgekutty R, Seery MK, Pillai SC (2008) A highly efficient Ag–ZnO photocatalyst: synthesis, properties, and mechanism. J Phys Chem C 112:13563–13570

    Article  CAS  Google Scholar 

  • Ghosh S, Goudar VS, Padmalekha KG, Bhat SV, Indi SS, Vasan HN (2012) ZnO/Ag nanohybrid: synthesis, characterization, synergistic antibacterial activity and its mechanism. Rsc Adv 2:930–940

    Article  CAS  Google Scholar 

  • Ghule K, Ghule AV, Chen BJ, Ling YC (2006) Preparation and characterization of ZnO nanoparticles coated paper and its antibacterial activity study. Green Chem 8:1034–1041

    Article  CAS  Google Scholar 

  • Gogoi SK, Gopinath P, Paul A, Ramesh A, Ghosh SS, Chattopadhyay A (2006) Green fluorescent protein-expressing Escherichia coli as a model system for investigating the antimicrobial activities of silver nanoparticles. Langmuir 22:9322–9328

    Article  CAS  Google Scholar 

  • Golic DL et al (2011) Structural characterization of self-assembled ZnO nanoparticles obtained by the sol–gel method from Zn(CH3COO)(2)center dot 2H(2)O. Nanotechnology 22:394603

  • Gu CD, Cheng C, Huang HY, Wong TL, Wang N, Zhang TY (2009) Growth and photocatalytic activity of dendrite-like ZnO@Ag heterostructure nanocrystals. Cryst Growth Des 9:3278–3285

    Article  CAS  Google Scholar 

  • Haskins JF, Hogsed MJ (1950) The alkaline oxidation of cellulose. I. Mechanism of the degradative oxidation of cellulose by hydrogen peroxide in presence of alkali. J Org Chem 15:1264–1274

    Article  CAS  Google Scholar 

  • Huang CJ, Li CH, Wang HL, Lin TN (2010) Effects of formic acid on the chemical state and morphology of as-synthesized and annealed ZnO films. World Academy of Science Engineering and Technology 65:266–270

    Google Scholar 

  • Jiang F (2013) Ligand controlled growth of aqueous II–VI semiconductor nanoparticles and their self-assembly. Doctoral thesis, The University of Arizona

  • Johansson LS, Campbell JM (2004) Reproducible XPS on biopolymers: cellulose studies. Surf Interface Anal 36:1018–1022

    Article  CAS  Google Scholar 

  • John A, Ko HU, Kim DG, Kim J (2011) Preparation of cellulose-ZnO hybrid films by a wet chemical method and their characterization. Cellulose 18:675–680

    Article  CAS  Google Scholar 

  • Jud C, Clift MJD, Petri-Fink A, Rothen-Rutishauser B (2013) Nanomaterials and the human lung: What is known and what must be deciphered to realise their potential advantages? Swiss Med Wkly 143:w13758

  • Khlebtsov BN, Khanadeyev VA, Khlebtsov NG (2008) Collective plasmon resonances in monolayers of metal nanoparticles and nanoshells. Opt Spectrosc 104:282–294

    Article  CAS  Google Scholar 

  • Kim IS, Jeong EK, Kim DY, Kumar M, Choi SY (2009) Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation. Appl Surf Sci 255:4011–4014

    Article  CAS  Google Scholar 

  • Kongdee A, Bechtold T (2009) Influence of ligand type and solution pH on heavy metal ion complexation in cellulosic fibre: model calculations and experimental results. Cellulose 16:53–63

    Article  CAS  Google Scholar 

  • Lee HY, Wu BK, Chern MY (2007) Study on the formation of zinc peroxide on zinc oxide with hydrogen peroxide treatment using X-ray photoelectron spectroscopy (XPS). Electron Mater Lett 10:51–55

    Article  Google Scholar 

  • Leiro J, Minni E, Suoninen E (1983) Study of plasmon structure in XPS spectra of silver and gold. J Phys F: Met Phys 13:215–221

    Article  CAS  Google Scholar 

  • Lewin M, Ettinger A (1969) Oxidation of cellulose by hydrogen peroxide. Cellulose Chem Technol 3:9–20

    CAS  Google Scholar 

  • Li YL, Zhao XA, Fan WL (2011) Structural, electronic, and optical properties of Ag-doped ZnO nanowires: first principles study. J Phys Chem C 115:3552–3557

    Article  CAS  Google Scholar 

  • Lidstrom P, Tierney J, Wathey B, Westman J (2001) Microwave assisted organic synthesis—a review. Tetrahedron 57:9225–9283

    Article  CAS  Google Scholar 

  • Lu WW, Liu GS, Gao SY, Xing ST, Wang JJ (2008) Tyrosine-assisted preparation of Ag/ZnO nanocomposites with enhanced photocatalytic performance and synergistic antibacterial activities. Nanotechnology 19:445711

  • Mar LG, Timbrell PY, Lamb RN (1993) An XPS study of zinc-oxide thin-film growth on copper using zinc acetate as a precursor. Thin Solid Films 223:341–347

    Article  CAS  Google Scholar 

  • Marambio-Jones C, Hoek EMV (2010) A review of the antibacterial effects of silver nanomaterials and potential implications for human health and the environment. J Nanopart Res 12:1531–1551

    Article  CAS  Google Scholar 

  • Maria LCS, Santos ALC, Oliveira PC, Valle ASS, Barud HS, Messaddeq Y, Ribeiro SJL (2010) Preparation and antibacterial activity of silver nanoparticles impregnated in bacterial cellulose. Polimeros 20:72–77

    CAS  Google Scholar 

  • Miller DJ, Biesinger MC, McIntyre NS (2002) Interactions of CO2 and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination? Surf Interface Anal 33:299–305

    Article  CAS  Google Scholar 

  • Mitchell R, Carr CM, Parfitt M, Vickerman JC, Jones C (2005) Surface chemical analysis of raw cotton fibres and associated materials. Cellulose 12:629–639

    Article  CAS  Google Scholar 

  • Moezzi A, McDonagh A, Dowd A, Cortie M (2013) Zinc hydroxyacetate and its transformation to nanocrystalline zinc oxide. Inorg Chem 52:95–102

    Article  CAS  Google Scholar 

  • Mohapatra S (2014) Tunable surface plasmon resonance of silver nanoclusters in ion exchanged soda lime glass. J Alloy Compd 598:11–15

    Article  CAS  Google Scholar 

  • Morones JR, Elechiguerra JL, Camacho A, Holt K, Kouri JB, Ramirez JT, Yacaman MJ (2005) The bactericidal effect of silver nanoparticles. Nanotechnology 16:2346–2353

    Article  CAS  Google Scholar 

  • Motshekga SC, Ray SS, Onyango MS, Momba MNB (2013) Microwave-assisted synthesis, characterization and antibacterial activity of Ag/ZnO nanoparticles supported bentonite clay. J Hazard Mater 262:439–446

    Article  CAS  Google Scholar 

  • Moulder JF, Stickle WF, Sobol PE, Bomben KD, Chastain J, King RCJr (1995) Handbook of X-ray photoelectron spectroscopy: a reference book of standard spectra for identification and interpretation of XPS data. Physical Electronics Inc., Eden Prairie

  • Nam S, Condon BD (2014) Internally dispersed synthesis of uniform silver nanoparticles via in situ reduction of [Ag(NH3)2]+ along natural microfibrillar substructures of cotton fiber. Cellulose 21:2963–2972

  • Naumkin AV, Kraut-Vass A, Gaarenstroom SW, Powell CJ (2012) NIST standard reference database 20, version 4.1

  • Pal S, Tak YK, Song JM (2007) Does the antibacterial activity of silver nanoparticles depend on the shape of the nanoparticle? A study of the gram-negative bacterium Escherichia coli. Appl Environ Microbiol 73:1712–1720

    Article  CAS  Google Scholar 

  • Panacek A et al (2006) Silver colloid nanoparticles: synthesis, characterization, and their antibacterial activity. J Phys Chem B 110:16248–16253

    Article  CAS  Google Scholar 

  • Powell CJ (1991) Formal databases for surface-analysis—the current situation and future-trends. Surf Interface Anal 17:308–314

    Article  CAS  Google Scholar 

  • Pradhan D, Leung KT (2008) Controlled growth of two-dimensional and one-dimensional ZnO nanostructures on indium tin oxide coated glass by direct electrodeposition. Langmuir 24:9707–9716

    Article  CAS  Google Scholar 

  • Sahu RK, Ganguly K, Mishra T, Mishra M, Ningthoujam RS, Roy SK, Pathak LC (2012) Stabilization of intrinsic defects at high temperatures in ZnO nanoparticles by Ag modification. J Colloid Interface Sci 366:8–15

    Article  CAS  Google Scholar 

  • Sannino A, Demitri C, Madaghiele M (2009) Biodegradable cellulose-based hydrogels: design and applications. Materials 2:353–373

    Article  CAS  Google Scholar 

  • Schon G (1973) Esca studies of Ag, Ag2O and AgO. Acta Chem Scand 27:2623–2633

    Article  CAS  Google Scholar 

  • Silva AR, Unali G (2011) Controlled silver delivery by silver-cellulose nanocomposites prepared by a one-pot green synthesis assisted by microwaves. Nanotechnology 22:315605

  • Siqueira G, Bras J, Dufresne A (2010) Cellulosic bionanocomposites: a review of preparation, properties and applications. Polymers 2:728–765

    Article  CAS  Google Scholar 

  • Sirolli V, Di Stante S, Stuard S, Di Liberato L, Amoroso L, Cappelli P, Bonomini M (2000) Biocompatibility and functional performance of a polyethylene glycol acid-grafted cellulosic membrane for hemodialysis. Int J Artif Organs 23:356–364

    CAS  Google Scholar 

  • Smetana AB, Klabunde KJ, Marchin GR, Sorensen CM (2008) Biocidal activity of nanocrystalline silver powders and particles. Langmuir 24:7457–7464

    Article  CAS  Google Scholar 

  • Song J, Rojas OJ (2013) Approaching super-hydrophobicity from cellulosic materials: a review. Nord Pulp Pap Res J 28:216–238

    Article  CAS  Google Scholar 

  • Vanniekerk JN, Schoening FRL, Talbot JH (1953) The crystal structure of zinc acetate dihydrate, Zn(CH3COO)2·2H2O. Acta Crystallogr A 6:720–723

    Article  CAS  Google Scholar 

  • Wang HH, Xie CS, Zeng DW (2005) ZnO microspheres self-assembled by hexagonal nanoplates. Chem Lett 34:260–261

    Article  CAS  Google Scholar 

  • Wang X, Kong XG, Yu Y, Zhang H (2007) Synthesis and characterization of water-soluble and bifunctional ZnO–Au nanocomposites. J Phys Chem C 111:3836–3841

    Article  CAS  Google Scholar 

  • Wang Y, Li YH, Zhou ZZ, Zu XH, Deng YL (2011) Evolution of the zinc compound nanostructures in zinc acetate single-source solution. J Nanopart Res 13:5193–5202

    Article  CAS  Google Scholar 

  • Wu JJ, Zhao N, Zhang XL, Xu J (2012) Cellulose/silver nanoparticles composite microspheres: eco-friendly synthesis and catalytic application. Cellulose 19:1239–1249

    Article  CAS  Google Scholar 

  • Yang ZM, Zhang P, Ding YH, Jiang Y, Long ZL, Dai WL (2011) Facile synthesis of Ag/ZnO heterostructures assisted by UV irradiation: highly photocatalytic property and enhanced photostability. Mater Res Bull 46:1625–1631

    Article  CAS  Google Scholar 

  • Yang GW, Wang BL, Guo WY, Wang Q, Liu YM, Miao CC, Bu ZH (2013) Hydrothermal growth of low-density ZnO microrod arrays on nonseeded FTO substrates. Mater Lett 90:34–36

    Article  CAS  Google Scholar 

  • Zhang YY, Mu J (2007) One-pot synthesis, photoluminescence, and photocatalysis of Ag/ZnO composites. J Colloid Interface Sci 309:478–484

    Article  CAS  Google Scholar 

  • Zhang DF, Zeng FB (2012) Visible light-activated cadmium-doped ZnO nanostructured photocatalyst for the treatment of methylene blue dye. J Mater Sci 47:2155–2161

    Article  CAS  Google Scholar 

  • Zheng Y, Zheng L, Zhan Y, Lin X, Zheng Q, Wei K (2007) Ag/ZnO heterostructure nanocrystals: synthesis, characterization, and photocatalysis. Inorg Chem 46:6980–6986

    Article  CAS  Google Scholar 

  • Zheng YH, Chen CQ, Zhan YY, Lin XY, Zheng Q, Wei KM, Zhu JF (2008) Photocatalytic activity of Ag/ZnO heterostructure nanocatalyst: correlation between structure and property. J Phys Chem C 112:10773–10777

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by Operational Program Research and Development for Innovations co-funded by the European Regional Development Fund (ERDF) and national budget of Czech Republic, within the project Centre of Polymer Systems (reg. no. CZ.1.05/2.1.00/03.0111). The authors from Zlin also acknowledge the support of Operational Program Education for Competitiveness co-funded by the European Social Fund (ESF) and national budget of Czech Republic, within the framework of project Advanced Theoretical and Experimental Studies of Polymer Systems (reg. no. CZ.1.07/2.3.00/20.0104). The work of L.M. was supported by the Internal Grant Agency of Tomas Bata University in Zlin, contract grant no. IGA/FT/2014/008. This work was financially supported by the project Materials Research Centre at FCH BUT-Sustainability and Development, REG LO1211, with financial support from the National Programme for Sustainability I (Ministry of Education, Youth and Sports).

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  1. Centre of Polymer Systems, University Institute, Tomas Bata University in Zlin, Nad Ovcirnou 3685, 760 01, Zlin, Czech Republic

    Pavel Bazant, Ivo Kuritka & Lukas Munster

  2. Faculty of Chemistry, Centre for Materials Research CZ.1.05/2.1.00/01.0012, Brno University of Technology, Purkyňova 464/118, 61200, Brno, Czech Republic

    Lukas Kalina

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  1. Pavel Bazant
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Correspondence to Ivo Kuritka.

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Bazant, P., Kuritka, I., Munster, L. et al. Microwave solvothermal decoration of the cellulose surface by nanostructured hybrid Ag/ZnO particles: a joint XPS, XRD and SEM study. Cellulose 22, 1275–1293 (2015). https://doi.org/10.1007/s10570-015-0561-y

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