Highly stretchable strain sensors based on Marangoni self-assemblies of graphene and its hybrids with other 2D materials.

Graphene and other two-dimensional materials (2DMs) have been shown to be promising candidates for the development of flexible and highly-sensitive strain sensors. However, the successful implementation of 2DMs in practical applications is slowed down by complex processing and still low sensitivity. Here, we report on a novel development of strain sensors based on Marangoni self-assemblies of graphene and of its hybrids with other 2DMs that can both withstand very large deformation and exhibit highly sensitive piezoresistive behaviour. By exploiting the Marangoni effect, reference films of self-assembled reduced graphene oxide (RGO) are first optimized, and the electromechanical behaviour has been assessed after deposition onto different elastomers demonstrating the potential of producing strain sensors suitable for different fields of application. Hybrid networks have been then prepared by adding hexagonal boron nitride (hBN) and fluorinated graphene (FGr) to the RGO dispersion. The hybrid integration of 2D materials is demonstrated to become a potential solution to increase substantially the sensitivity of the produced resistive strain sensors without compromising the mechanical integrity of the film. In fact, for large quasi-static deformations, a range of gauge factor values up to 2000 were demonstrated, while retaining a stable performance under cyclic deformations.

Highly efficient surface-enhanced Raman scattering substrate formulation by self-assembled gold nanoparticles physisorbed on poly(N-isopropylacrylamide) thermoresponsive hydrogels.

Employing thermoresponsive hydrogels as scaffolding material for noble metal surface loading might be useful for the fabrication of surface-enhanced Raman scattering (SERS) surfaces. Here, we report on a new, reproducible, and simple approach to engineer poly(N-isopropylacrylamide) (PNIPAAm) hydrogel surfaces optimized for physisorption of gold nanoparticles (AuNPs). The advantage of this approach consists of the simple mechanism by which AuNPs are adsorbed on hydrogel templates, without sophisticated chemical treatments for their conjugation with the hydrogel. The resulting PNIPAAm-40 nm AuNP modes demonstrate that this approach gives the capability to tune the interparticle distance and, therefore, to control and modulate SERS affinity upon temperature changing.

Operando Characterization and Molecular Simulations Reveal the Growth Kinetics of Graphene on Liquid Copper During Chemical Vapor Deposition.

In recent years, liquid metal catalysts have emerged as a compelling choice for the controllable, large-scale, and high-quality synthesis of two-dimensional materials. At present, there is little mechanistic understanding of the intricate catalytic process, though, of its governing factors or what renders it superior to growth at the corresponding solid catalysts. Here, we report on a combined experimental and computational study of the kinetics of graphene growth during chemical vapor deposition on a liquid copper catalyst. By monitoring the growing graphene flakes in real time using in situ radiation-mode optical microscopy, we explore the growth morphology and kinetics over a wide range of CH4-to-H2 pressure ratios and deposition temperatures. Constant growth rates of the flakes' radius indicate a growth mode limited by precursor attachment, whereas methane-flux-dependent flake shapes point to limited precursor availability. Large-scale free energy simulations enabled by an efficient machine-learning moment tensor potential trained to density functional theory data provide quantitative barriers for key atomic-scale growth processes. The wealth of experimental and theoretical data can be consistently combined into a microkinetic model that reveals mixed growth kinetics that, in contrast to the situation at solid Cu, is partly controlled by precursor attachment alongside precursor availability. Key mechanistic aspects that directly point toward the improved graphene quality are a largely suppressed carbon dimer attachment due to the facile incorporation of this precursor species into the liquid surface and a low-barrier ring-opening process that self-heals 5-membered rings resulting from remaining dimer attachments.

Chemical Vapour Deposition Graphene-PMMA Nanolaminates for Flexible Gas Barrier.

Successful ways of fully exploiting the excellent structural and multifunctional performance of graphene and related materials are of great scientific and technological interest. New opportunities are provided by the fabrication of a novel class of nanocomposites with a nanolaminate architecture. In this work, by using the iterative lift-off/float-on process combined with wet depositions, we incorporated cm-size graphene monolayers produced via Chemical Vapour Deposition into a poly (methyl methacrylate) (PMMA) matrix with a controlled, alternate-layered structure. The produced nanolaminate shows a significant improvement in mechanical properties, with enhanced stiffness, strength and toughness, with the addition of only 0.06 vol% of graphene. Furthermore, oxygen and carbon dioxide permeability measurements performed at different relative humidity levels, reveal that the addition of graphene leads to significant reduction of permeability, compared to neat PMMA. Overall, we demonstrate that the produced graphene-PMMA nanolaminate surpasses, in terms of gas barrier properties, the traditional discontinuous graphene-particle composites with a similar filler content. Moreover, we found that the gas permeability through the nanocomposites departs from a monotonic decrease as a function of relative humidity, which is instead evident in the case of the pure PMMA nanolaminate. This work suggests the possible use of Chemical Vapour Deposition graphene-polymer nanolaminates as a flexible gas barrier, thus enlarging the spectrum of applications for this novel material.

Whey protein films reinforced with bacterial cellulose nanowhiskers: Improving edible film properties via a circular economy approach.

Edible films were developed using whey protein concentrate (WPC) and a natural bio-polymer, namely bacterial cellulose (BC). BC was produced via fermentation from orange peels and subsequently acid-hydrolyzed to obtain BC nanowhiskers (BCNW) with high crystallinity (XRD analysis). Morphology of BCNW was analyzed by SEM, TEM, and AFM. WPC/BCNW film composites, containing different amounts of BCNW (0.5-15%, w/w) were developed and characterized. WPC/BCNW film composite was analyzed by Raman spectroscopy, indicating the successful incorporation and the homogenous distribution of BCNW into the WPC film matrix. Mechanical characterization showed that BCNW behaved as a reinforcing filler in the WPC film, increasing tensile strength and Young's modulus by 32% and 80%, respectively. In addition, water vapor permeability was reduced by 33.9% upon the addition of 0.5% BCNW. This study presented a sustainable approach towards the production of WPC films with improved tensile and water barrier properties, suggesting its potential application as a packaging material.

Growth and in situ characterization of 2D materials by chemical vapour deposition on liquid metal catalysts: a review.

2D materials (2DMs) have now been established as unique and attractive alternatives to replace current technological materials in a number of applications. Chemical vapour deposition (CVD), is undoubtedly the most renowned technique for thin film synthesis and meets all requirements for automated large-scale production of 2DMs. Currently most CVD methods employ solid metal catalysts (SMCat) for the growth of 2DMs however their use has been found to induce structural defects such as wrinkles, fissures, and grain boundaries among others. On the other hand, liquid metal catalysts (LMCat), constitute a possible alternative for the production of defect-free 2DMs albeit with a small temperature penalty. This review is a comprehensive report of past attempts to employ LMCat for the production of 2DMs with emphasis on graphene growth. Special attention is paid to the underlying mechanisms that govern crystal growth and/or grain consolidation and film coverage. Finally, the advent of online metrology which is particularly effective for monitoring the chemical processes under LMCat conditions is also reviewed and certain directions for future development are drawn.

Effective EMI shielding behaviour of thin graphene/PMMA nanolaminates in the THz range.

The use of graphene in a form of discontinuous flakes in polymer composites limits the full exploitation of the unique properties of graphene, thus requiring high filler loadings for achieving- for example- satisfactory electrical and mechanical properties. Herein centimetre-scale CVD graphene/polymer nanolaminates have been produced by using an iterative 'lift-off/float-on' process and have been found to outperform, for the same graphene content, state-of-the-art flake-based graphene polymer composites in terms of mechanical reinforcement and electrical properties. Most importantly these thin laminate materials show a high electromagnetic interference (EMI) shielding effectiveness, reaching 60 dB for a small thickness of 33 µm, and an absolute EMI shielding effectiveness close to 3·105 dB cm2 g-1 which is amongst the highest values for synthetic, non-metallic materials produced to date.

A theoretical and experimental study on l-tyrosine and citrate mediated sustainable production of near infrared absorbing twisted gold nanorods.

Anisotropic gold nanoparticles displaying plasmon band in the near infrared region can play a crucial role in cancer therapy particularly with techniques such as photothermal therapy (PTT) and photodynamic therapy (PDT). Herein, we report an efficient, sustainable, one pot protocol for the fabrication of an unusual gold anisotropic shape, which we have named as twisted gold nanorods. These particles, though having dimensions in the nanoscale regime comparable to those of gold nanorods, display a continuous flat plasmon band like that of 2-D gold nanowire networks, extended up to the NIR-III (SWIR) range. The proposed strategy is simple and does not require any seed mediation, heating or potential toxic templates or organic solvents. Our process is based on the slow reduction of gold salt in presence of two mild reducing agents viz. l-tyrosine (an amino acid) and trisodium citrate. We observed that when both molecules are present together in particular concentrations, they direct the growth in form of twisted gold nanorods. The mechanism of growth has been described by a Diffusion Limited Aggregation numerical scheme, where it was assumed that both l-tyrosine and the gold ions in solution undergo a stochastic Brownian motion. The predictions of the model matched with the experiments with a good accuracy, indicating that the initial hypothesis is correct. The final structure has been thoroughly characterized in terms of morphology, while SERS and cytotoxic activity have also been demonstrated.

Real-Time Multiscale Monitoring and Tailoring of Graphene Growth on Liquid Copper.

The synthesis of large, defect-free two-dimensional materials (2DMs) such as graphene is a major challenge toward industrial applications. Chemical vapor deposition (CVD) on liquid metal catalysts (LMCats) is a recently developed process for the fast synthesis of high-quality single crystals of 2DMs. However, up to now, the lack of in situ techniques enabling direct feedback on the growth has limited our understanding of the process dynamics and primarily led to empirical growth recipes. Thus, an in situ multiscale monitoring of the 2DMs structure, coupled with a real-time control of the growth parameters, is necessary for efficient synthesis. Here we report real-time monitoring of graphene growth on liquid copper (at 1370 K under atmospheric pressure CVD conditions) via four complementary in situ methods: synchrotron X-ray diffraction and reflectivity, Raman spectroscopy, and radiation-mode optical microscopy. This has allowed us to control graphene growth parameters such as shape, dispersion, and the hexagonal supra-organization with very high accuracy. Furthermore, the switch from continuous polycrystalline film to the growth of millimeter-sized defect-free single crystals could also be accomplished. The presented results have far-reaching consequences for studying and tailoring 2D material formation processes on LMCats under CVD growth conditions. Finally, the experimental observations are supported by multiscale modeling that has thrown light into the underlying mechanisms of graphene growth.

Quantitative analysis via Surface Enhanced Raman Scattering from Ag nano-colloids utilizing an oscillating cell and right-angle collection geometry.

We examine the application of an oscillating cell in combination with right-angle Raman scattered light collection geometry for quantitative Surface Enhanced (Resonance) Raman Scattering (SER(R)S) measurements from nano-colloidal noble metal solutions. This excitation/collection Raman configuration allows specific SERS and SERRS signatures of aqueous solutions of mitoxantrone, an antitumor drug, to be easily resolved at (sub)-ng/mL and (sub)-pg/mL concentration levels. A partial least-squares (PLS) chemometric algorithm was applied to predict the concentration of 25 microL of aqueous solutions of mitoxantrone added in 0.5 mL of a silver colloidal solution in a test tube attached to the oscillating cell. For SERS (514.5 nm) measurements, this was performed over the range from 0 to 13 ng/mL with a correlation coefficient R(2) of 98.5% and RMS error of prediction equal to 0.5 ng/mL. SERRS (632.8 nm) measurements performed over a range of 0 to 7 pg/mL gave R(2) = 98.92% and RMSE = 0.2 pg/mL.

Mosaic pattern formation in exfoliated graphene by mechanical deformation.

Graphene is susceptible to morphological instabilities such as wrinkles and folds, which result from the imposition of thermo-mechanical stresses upon cooling from high temperatures and/ or under biaxial loading. A particular pattern encountered in CVD graphene is that of mosaic formation. Although it is understood that this pattern results from the severe biaxial compression upon cooling from high temperatures, it has not been possible to create such a complex pattern at room temperature by mechanical loading. Herein, we have managed by means of lateral wrinkling induced by tension and Euler buckling resulting from uniaxial compression upon unloading, to create such patterns in exfoliated graphene. We also show that these patterns can be used as channels for trapping or administering fluids at interstitial space between graphene and its support. This opens a whole dearth of new applications in the area of nano-fluidics but also in photo-electronics and sensor technologies.

Tuning gold nanoparticles interfaces by specific peptide interaction for surface enhanced Raman spectroscopy (SERS) and separation applications.

Surface functionalization and control over nanostructured interfaces represents a key aspect in nanoscience and nanobiotechnology. Nanoplasmonic structures for analyte detection typically require sophisticated nanofabrication techniques, as well as bioactivated nanostructures that need multistep conjugations for chemical ligation. An alternative to such complex processes is to rely on specific biomolecules adsorption for decoration or self-assembly of nanoparticles at solid/liquid interface. In principle, small biomolecules with specific binding properties to nanostructures could control the assembly without modifying the nanoparticle chemistry, pH of the solution or salt concentration. Importantly, such an approach could be direct, robust, and reversible. In this work, we report about the use of a specific peptide for direct and reversible adsorption on gold nanoparticles with tuned interfacial properties just by simply adjusting the ratio between the numbers of peptide molecules to the number of gold nanoparticles. This easy, direct and reversible assembly of gold nanoparticles mediated by the specific peptide makes this platform ideal for small-volume samples and low concentrations detection using surface enhanced Raman Spectroscopy, as well as for the capture or separation of biomolecules in complex mix.