Silicon-Doped Graphene Oxide Quantum Dots as Efficient Nanoconjugates for Multifunctional Nanocomposites

M. Ghasemlou, E. L.H. Mayes, B. J. Murdoch, P. H. Le, C. Dekiwadia, A. Aburto-Medina, F. Daver, E. P. Ivanova and B. Adhikari

ACS Applied Materials and Interfaces 14,7161 (2022)
Graphene oxide quantum dots (GOQDs) hold great promise as a new class of high-performance carbonaceous nanomaterials due to their numerous functional properties, such as tunable photoluminescence (PL), excellent thermal and chemical stability, and superior biocompatibility. In this study, we developed a facile, one-pot, and effective strategy to engineer the interface of GOQDs through covalent doping with silicon. The successful covalent attachment of the silane dopant with pendant vinyl groups to the edges of the GOQDs was confirmed by an in-depth investigation of the structural and morphological characteristics. The Si-GOQD nanoconjugates had an average dimension of ∼8 nm, with a graphite-structured core and amorphous carbon on their shell. We further used the infrared nanoimaging based on scattering-type scanning near-field optical microscopy to unveil the spectral near-field response of GOQD samples and to measure the nanoscale IR response of its network; we then demonstrated their distinct domains with strongly enhanced near fields. The doping of Si atoms into the sp2-hybridized graphitic framework of GOQDs also led to tailored PL emissions. We then sought to explore the potential applications of Si-GOQDs on the surface of plastic films where poly(dimethylsiloxane) (PDMS) served as a bridge to tightly anchor the Si-GOQDs to the surface. The bi-layered coated films which were built with co-assembly of Si-GOQDs and PDMS contributed to suppressing the transmission of water molecules due to the generation of compact and less accessible passing sites, achieving a nearly twofold reduction in water permeability compared to the single-layered coated films. The nanoindentation and PeakForce quantitative nanomechanical mapping showed that Si-GOQD-coated substrates were softer and more deformable than those coated only with PDMS. The co-assembly of PDMS and Si-GOQDs yielded films that were less stiff than those made from PDMS alone. Our findings provided conceptual insights into the importance of nanoscale surface engineering of GOQDs in conferring excellent dispersibility and enhancing the performance of nanocomposite films.