Abstract
The in-situ growth of gold nanoparticles (AuNPs) on cellulose nanofibers (CNFs) is a promising novel method to functionalize the CNFs. This work aims to study the synthesis mechanisms of the AuNP/CNF composites and develop the methods to control the particle size and surface coverage of AuNPs grown on CNFs. The growth process was monitored by the spectral analysis in real time, and the morphology of the AuNP/CNF composites was observed by using the electron microscopic techniques. The crystallography of AuNPs grown on CNFs was investigated by using a transmission electron microscopy (TEM). It has been found that the CNFs contribute to reducing the gold (Au) precursors, albeit at a much lower reduction rate than the citrate ions. The Au monomers have been found to strongly attach onto the CNFs to form the nucleation sites for the subsequent growth of AuNPs. The mechanisms underlying the formation of the AuNP/CNF composites have been proposed, with the emphasis on the effects of the CNFs on the growth of Au nanocrystals: the citrate ions play the dominant role in the reduction of Au precursors; the CNFs are able to offer the reduction sites for Au precursors and provide the nucleation sites for the formation of Au nanocrystals, and at the same time, having a prevention effect on the fusion of AuNPs formed on CNFs. Based on the proposed mechanisms, the methods of controlling the growth of AuNPs on CNFs have been developed: the size of AuNPs can be controlled by manipulating either the concentration of citrate ions or the initial pH value of the reaction suspension; the surface coverage of AuNPs on CNFs can be controlled by adjusting either the solid content of the CNFs or the initial pH value of the reaction suspension.
Graphic abstract
Similar content being viewed by others
References
Boufi S, Ferraria AM, Botelho do Rego AM, Battaglini N, Herbst F, Rei Vilar M (2011) Surface functionalisation of cellulose with noble metals nanoparticles through a selective nucleation. Carbohydr Polym 86:1586–1594. https://doi.org/10.1016/j.carbpol.2011.06.067
Chen M, Kang H, Gong Y, Guo J, Zhang H, Liu R (2015) Bacterial cellulose supported gold nanoparticles with excellent catalytic properties. ACS Appl Mater Interfaces 7:21717–21726. https://doi.org/10.1021/acsami.5b07150
Chen R, Zhang L, Li X, Ong L, Soe YG, Sinsua N, Gras SL, Tabor RF, Wang X, Shen W (2017) Trace analysis and chemical identification on cellulose nanofibers-textured SERS substrates using the “coffee ring” effect. ACS Sens. 2:1060–1067. https://doi.org/10.1021/acssensors.7b00403
Engelbrekt C, Jensen PS, Sørensen KH, Ulstrup J, Zhang J (2013) Complexity of gold nanoparticle formation disclosed by dynamics study. J Phys Chem C 117:11818–11828. https://doi.org/10.1021/jp401883h
Espino-Pérez E, Domenek S, Belgacem N, Sillard C, Bras J (2014) Green process for chemical functionalization of nanocellulose with carboxylic acids. Biomacromol 15:4551–4560. https://doi.org/10.1021/bm5013458
Frens G (1973) Controlled nucleation for the regulation of the particle size in monodisperse gold suspension. Nature 241:20–22
Gopiraman M, Deng D, Saravanamoorthy S, Chung I, Kim I (2018) Gold, silver and nickel nanoparticle anchored cellulose nanofiber composites as highly active catalysts for the rapid and selective reduction of nitrophenols in water. RSC Adv 8:3014–3023. https://doi.org/10.1039/C7RA10489H
He H, Chen R, Zhang L, Williams T, Fang X, Shen W (2020) Fabrication of single-crystalline gold nanowires on cellulose nanofibers. J Colloid Interface Sci 562:333–341. https://doi.org/10.1016/j.jcis.2019.11.093
He J, Kunitake T, Nakao A (2003) Facile in situ synthesis of noble metal nanoparticles in porous cellulose fibers. Chem Mater 15:4401–4406. https://doi.org/10.1021/cm034720r
Hong S, Li X (2013) Optimal size of gold nanoparticles for surface-enhanced Raman spectroscopy under different conditions. J Nanomater 2013:1–9. https://doi.org/10.1155/2013/790323
Huang P, Zhao Y, Kuga S, Wu M, Huang Y (2016) A versatile method for producing functionalized cellulose nanofibers and their application. Nanoscale 8:3753–3759. https://doi.org/10.1039/C5NR08179C
Lim IS, Zhong C (2007) Molecularly-mediated assembly of gold nanoparticles. Gold Bull 40:59–66. https://doi.org/10.1007/BF03215294
Lin C, Tao K, Hua D, Ma Z, Zhou S (2013) Size effect of gold nanoparticles in catalytic reduction of p-nitrophenol with NaBH4. Molecules 18:12609–12620. https://doi.org/10.3390/molecules181012609
Njoki PN, Lim IS, Mott D, Park H, Khan B, Mishra S, Sujakumar R, Luo J, Zhong C (2007) Size correlation of optical and spectroscopic properties for gold nanoparticles. J Phys Chem C 111:14664–14669. https://doi.org/10.1021/jp074902z
Reguera J, Langer J, Jiménez de Aberasturi D, Liz-Marzán LM (2017) Anisotropic metal nanoparticles for surface enhanced Raman scattering. Chem Soc Rev 46:3866–3885. https://doi.org/10.1039/C7CS00158D
Schulz F, Homolka T, Bastús NG, Puntes V, Weller H, Vossmeyer T (2014) Little adjustments significantly improve the Turkevich synthesis of gold nanoparticles. Langmuir 30:10779–10784. https://doi.org/10.1021/la503209b
Shan M, Liu C, Shi L, Zhang L, Lin Y, Zhang S, Zhu Z, Wang X, Zhuang X (2019) In situ synthesis of Au nanoparticles on viscose cellulose sponges for antibacterial activities. Polymers 11:1281. https://doi.org/10.3390/polym11081281
Shirahata N, Yonezawa T, Matsushita Y, Masuda Y, Koumoto K (2008) Fusion and growth behavior of gold nanoparticles stabilized by allylmercaptane. Macromol Symp 270:82–87. https://doi.org/10.1002/masy.200851010
Suchomel P, Kvitek L, Prucek R, Panacek A, Halder A, Vajda S, Zboril R (2018) Simple size-controlled synthesis of Au nanoparticles and their size-dependent catalytic activity. Sci Rep 8:4589. https://doi.org/10.1038/s41598-018-22976-5
Wu H, Tsai H, Hung Y, Lao K, Liao C, Chung P, Huang J, Chen I, Huang M (2011) A comparative study of gold nanocubes, octahedra, and rhombic dodecahedra as highly sensitive SERS substrates. Inorg Chem 50:8106–8111. https://doi.org/10.1021/ic200504n
Wu X, Lu C, Zhou Z, Yuan G, Xiong R, Zhang X (2014) Green synthesis and formation mechanism of cellulose nanocrystal-supported gold nanoparticles with enhanced catalytic performance. Environ Sci Nano 1:71–79. https://doi.org/10.1039/C3EN00066D
Wuithschick M, Birnbaum A, Witte S, Sztucki M, Vainio U, Pinna N, Rademann K, Emmerling F, Kraehnert R, Polte J (2015) Turkevich in new robes: key questions answered for the most common gold nanoparticle synthesis. ACS Nano 9:7052–7071. https://doi.org/10.1021/acsnano.5b01579
Zhang T, Wang W, Zhang D, Zhang X, Ma Y, Zhou Y, Qi L (2010) Biotemplated synthesis of gold nanoparticle-bacteria cellulose nanofiber nanocomposites and their application in biosensing. Adv Funct Mater 20:1152–1160. https://doi.org/10.1002/adfm.200902104
Zhang L, Li X, Ong L, Tabor RF, Bowen BA, Fernando AI, Nilghaz A, Garnier G, Gras SL, Wang X, Shen W (2015a) Cellulose nanofibre textured SERS substrate. Colloids Surf A 468:309–314. https://doi.org/10.1016/j.colsurfa.2014.12.056
Zhang L, Tsuzuki T, Wang X (2015b) Preparation of cellulose nanofiber from softwood pulp by ball milling. Cellulose 22:1729–1741. https://doi.org/10.1007/s10570-015-0582-6
Zhou X, Zhao Z, He Y, Ye Y, Zhou J, Zhang J, Ouyang Q, Tang B, Wang X (2018) Photoinduced synthesis of gold nanoparticle-bacterial cellulose nanocomposite and its application for in-situ detection of trace concentration of dyes in textile and paper. Cellulose 25:3941–3953. https://doi.org/10.1007/s10570-018-1850-z
Acknowledgments
Hui He and Ruoyang Chen acknowledge the Monash Graduate Education (MGE) and the Faculty of Engineering for scholarships. Liyuan Zhang and Wei Shen acknowledge the Monash Institute of Medical Engineering (MIME) for research funds, the Australian Research Council for the funds support through Research Hub for Energy Efficient Separation (IH170100009) Project, the Innovation Connection Grants (ICG000457 and ICG000830) and Research Grants from Wuhan Textile University.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare no competing financial interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
He, H., Chen, R., Zhang, L. et al. Growth of gold nanoparticles on cellulose nanofibers. Cellulose 27, 5041–5053 (2020). https://doi.org/10.1007/s10570-020-03142-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-020-03142-5