Precise quantification of nanoparticle surface free energy via colloidal probe atomic force microscopy.

Interfacial interactions of nanoparticles (NPs) in colloids are greatly influenced by the NP surface free energy (SFE). Due to the intrinsic physical and chemical heterogeneity of the NP surface, measuring SFE is nontrivial. The use of direct force measurement methods, such as colloidal probe atomic force microscopy (CP-AFM), have been proven to be effective for the determination of SFE on relatively smooth surfaces, but fail to provide reliable measurements for rough surfaces generated by NPs. Here, we developed a reliable approach to determine the SFE of NPs by adopting Persson's contact theory to include the effect of surface roughness on the measurements in CP-AFM experiments. We obtain the SFE for a range of materials varying in surface roughness and surface chemistry. The reliability of the proposed method is verified by the SFE determination of polystyrene. Subsequently, the SFE of bare and functionalized silica, graphene oxide, and reduced graphene oxide were quantified and validity of the results was demonstrated. The presented method unlocks the potential of CP-AFM as a robust and reliable method of the SFE determination of nanoparticles with a heterogeneous surface, which is challenging to obtain with conventionally implemented experimental techniques.

Fabrication of graphene-based porous materials: traditional and emerging approaches.

The anisotropic nature of 'graphenic' nanosheets enables them to form stable three-dimensional porous materials. The use of these porous structures has been explored in several applications including electronics and batteries, environmental remediation, energy storage, sensors, catalysis, tissue engineering, and many more. As method of fabrication greatly influences the final pore architecture, and chemical and mechanical characteristics and performance of these porous materials, it is essential to identify and address the correlation between property and function. In this review, we report detailed analyses of the different methods of fabricating porous graphene-based structures - with a focus on graphene oxide as the base material - and relate these with the resultant morphologies, mechanical responses, and common applications of use. We discuss the feasibility of the synthesis approaches and relate the GO concentrations used in each methodology against their corresponding pore sizes to identify the areas not explored to date.

Polymer-Free Emulsion-Templated Graphene-Based Sponges for Contaminant Removal.

An emulsion-templated porous material can be formed by polymerizing the continuous phase of high internal phase Pickering emulsions (HIPEs). Although polymerization is a key step to maintain the pore size and integrity of the final sponge, it lowers the effective specific surface area of the final sponge as the continuous phase makes up at least half of the HIPE's volume. Hence, eliminating the need of polymerization not only eases the material processing but also leads to a greater specific surface area. Here, we report a novel strategy in which none of the emulsion phases require polymerization and is therefore a versatile methodology. For this purpose, several oil-in-water Pickering emulsions were prepared using graphene oxide (GO) and cellulose nanocrystals (CNCs) as the stabilizing agents. GO nanosheets are then reduced by mixing the emulsions with an adequate amount of vitamin C as a green reducing agent. Removal of the oil phase via multiple washing and boiling steps results in the formation of the ultimate reduced graphene oxide (rGO)/CNC sponge. The integrity of the structure remains intact and results in the formation of pores that are comparable in size to the droplets because of (i) the strong adhesion of GO and CNC at the oil/water interface in the initial Pickering emulsions and (ii) the strong intermolecular interactions between GO and CNC particles within the water phase. The sponge was then evaluated for its contaminant removal applicability using methylene blue and found to be effective in different water chemistries and outperform previously reported poly(HIPEs) and granular activated carbon. This is the first report on the formation of a polymer-free emulsion-templated sponge, and we believe that this novel nanomaterial paves the road for the fabrication of other emulsion-templated sponges. Although the proposed application in this work is contaminant removal, it could also be utilized in forming electronic devices and sensors because of the incorporation of rGO as a conductive component.

The Significance of Graphene Oxide-Polyacrylamide Interactions on the Stability and Microstructure of Oil-in-Water Emulsions.

The emulsification of oil in water by nanoparticles can be facilitated by the addition of costabilizers, such as polymers and surfactants. The enhanced properties of the resulting emulsions are usually attributed to nanoparticle/costabilizer synergy; however, the mechanism of this synergistic effect and its impacts on emulsion stability and microstructure remain unclear. Here, we study the synergistic interaction of graphene oxide (GO) and a high molecular weight anionic polyacrylamide (PAM) in stabilization of paraffin oil/water emulsion systems. We show that the addition of PAM reduces the amount of GO required to stabilize an emulsion significantly. In order to probe the synergistic effect of GO and PAM, we analytically analyze the oil-free GO and GO-PAM dispersions and directly image their morphology via Cryo-TEM and atomic force microscopy (AFM). X-ray diffraction results confirm the adsorption of PAM molecules onto GO sheets resulting in the formation of ultimate GO-PAM complexes. The adsorption phenomenon is a consequence of hydrogen bonding and acid-base interactions, conceivably leading to a resilient electron-donor-acceptor complex. The microstructure of emulsions is captured with two-color fluorescent microscopy and Cryo-TEM. The acquired images display the localization of GO-PAM complexes at the interface while large amount of GO-PAM flocs coexist at the interface and in between oil droplets. Localization of such complexes and flocs at the interface is found to be responsible for their slow creaming rates compared to their GO counterparts. Mechanical properties of both dispersions and emulsions are studied by shear rheology. Rheological measurements confirm that GO-PAM complexes have a higher desorption energy from the interface resulting in higher critical shear strain of GO-PAM emulsions. The results, with insights into both structure and rheology, form a foundational understanding for integration of other polymers and nanoparticles in emulsion systems, which enables efficient design of these systems for an application of interest.

Stabilization of Oil-in-Water Emulsions with Noninterfacially Adsorbed Particles.

Classical (surfactant stabilized) and Pickering (particle stabilized) type emulsions have been widely studied to elucidate the mechanisms by which emulsion stabilization is achieved. In Pickering emulsions, a key defining factor is that the stabilizing particles reside at the liquid-liquid interface providing a mechanical barrier to droplet coalescence. This interfacial adsorption is achieved through the use of nanoparticles that are partially wet by both liquid phases, often through covalent surface modification of or surfactant adsorption to the nanoparticle surfaces. Herein, we demonstrate particle-induced stabilization of an oil-in-water emulsion with fully water wet nanoparticles (no interfacial adsorption) via synergistic interaction with low concentrations of surfactants. Laser scanning confocal microscopy analysis allows for unique and vital insights into the properties of these emulsions via both three-dimensional imaging and real-time monitoring of particle dynamics at the oil-water interface. Investigation of these "non-Pickering" particle stabilized emulsions suggests that the nonadsorbed particles impart stability to the emulsion primarily via entropic forces imparted by the accumulation of silica nanoparticles in the coherent phase between dispersed oil droplets.