Journal
ACS APPLIED NANO MATERIALS
Volume 4, Issue 1, Pages 503-513Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsanm.0c02819
Keywords
silver nanoparticles; self-assembly; cellulose nanofibrils; layer-by-layer deposition; spray-coating
Funding
- Helmholtz-OCPC program [20191004]
- DESY strategic fund (DSF) Investigation of processes for spraying and spray-coating of hybrid cellulosebased nanostructures
- TUM.solar in the context of the Bavarian Collaborative Research Project Solar Technologies Go Hybrid (SolTech)
- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy [EXC 2089/1-390776260]
- International Research Training Group 2022 Alberta/Technical University of Munich International Graduate School for Environmentally Responsible Functional Hybrid Materials (ATUMS)
- National Natural Science Foundation of China [11905306]
- Fundamental Research Funds for the Central Universities [19lgpy14]
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The study demonstrates the fabrication of AgNP/CNF thin films through layer-by-layer spray-coating method, showing a more uniform distribution and higher surface hydrophilicity compared to SiO2 substrates. This approach provides a convenient and scalable platform for producing AgNP/CNF films with low agglomeration rate.
Silver nanoparticles (AgNPs) and AgNP-based composite materials have attracted growing interest due to their structure-dependent optical, electrical, catalytic, and stimuli-responsive properties. For practical applications, polymeric materials are often combined with AgNPs to provide flexibility and offer a scaffold for homogenous distribution of the AgNPs. However, the control over the assembly process of AgNPs on polymeric substrates remains a big challenge. Herein, we report the fabrication of AgNP/cellulose nanofibril (CNF) thin films via layer-by-layer (LBL) spray-coating. The morphology and self-assembly of AgNPs with increasing number of spray cycles are characterized by atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), and grazing-incidence wide-angle X-ray scattering (GIWAXS). We deduce that an individual AgNP (radius = 15 +/- 3 nm) is composed of multiple nanocrystallites (diameter = 2.4 +/- 0.9 nm). Our results suggest that AgNPs are assembled into large agglomerates on SiO2 substrates during spray-coating, which is disadvantageous for AgNP functionalization. However, the incorporation of CNF substrates contributes to a more uniform distribution of AgNP agglomerates and individual AgNPs by its network structure and by absorbing the partially dissolved AgNP agglomerates. Furthermore, we demonstrate that the spray-coating of the AgNP/CNF mixture results in similar topography and agglomeration patterns of AgNPs compared to depositing AgNPs onto a precoated CNF thin film. Contact-angle measurements and UV/vis spectroscopy suggest that the deposition of AgNPs onto or within CNFs could increase the hydrophilicity of AgNP-containing surfaces and the localized surface plasmon resonance (LSPR) intensity of AgNP compared to AgNPs sprayed on SiO(2 )substrates, suggesting their potential applications in antifouling coatings or label-free biosensors. Thereby, our approach provides a platform for a facile and scalable production of AgNP/CNF films with a low agglomeration rate by two different methods as follows: (1) multistep layer-by-layer (LBL) spray-coating and (2) direct spray-coating of the AgNP/CNF mixture. We also demonstrate the ability of CNFs as a flexible framework for directing the uniform assembly of AgNPs with tailorable wettability and plasmonic properties.
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