“Patchy particles”, where the surface is anisotropically patterned through variation in the surface composition, can assemble into different colloidal crystal structures as well as act as interface stabilizers, heterogeneous reaction catalysts, and targeted drug delivery agents. Patchy nanoparticles (NPs) can be formed by adsorbing two chemically different polymer chains that will spontaneously phase separate. Although there is growing interest in polymer-based patchy nanoparticles, the majority of the studies have been theoretical rather than experimental due to difficulties in preparing significant quantities of nanoparticles with controlled polymer ratios. Likewise, characterization of the phase separation on the nanoparticle surface is challenging. Here we simultaneously overcome the synthesis and characterization hurdles by developing a facile, versatile protocol to produce sufficient quantities of patchy NPs for quantitative solid-state NMR measurements of the patch fractions, degree of phase separation, and morphology. Monodisperse 3.5 nm ZrO2 nanocrystals with polystyrene (PS) and poly­(ethylene oxide) (PEO) ligands, covering the entire possible composition range, were reproducibly prepared through a simple exchange process. This approach has the advantage of well-defined polymer molecular weights and NP sizes, allowing experimental validation of theoretical predictions for nanophase separation in NPs with mixed homopolymer brushes. Upon exposure to a nonselective solvent, the nanoparticles assemble into different morphologies, namely micelles and vesicles, as a function of the PEO:PS ratios.

Spontaneous phase separation in binary mixed ligand shells is a proposed strategy to create patchy nanoparticles. The surface anisotropy, providing directionality along with interfacial properties emerging from both ligands, is highly desirable for targeted drug delivery, catalysis, and other applications. However, characterization of phase separation on the nanoscale remains quite challenging. Here we have adapted solid-state 1 H spin diffusion NMR experiments designed to detect and quantify spatial heterogeneity in polymeric materials to nanoparticles (NPs) functionalized with mixed short ligands. Janus NPs and physical mixtures of homoligand 3.5 nm diameter ZrO 2 NPs, with aromatic (phenylphosphonic acid, PPA) and aliphatic (oleic acid, OA) ligands, were used to calibrate the 1 H spin diffusion experiments. The Janus NPs, prepared by a facile wax/water Pickering emulsion method, and mixed ligand NPs, produced by ligand exchange, both with 1:1 PPA:OA ligand compositions, display strikingly different solvent and particle−particle interactions. 1 H spin diffusion NMR experiments are most consistent with a lamellar surface pattern for the mixed ligand ZrO 2 NPs. Solid-state 1 H spin diffusion NMR is shown to be a valuable additional characterization tool for mixed ligand NPs, as it not only detects the presence of nanoscale phase separation but also allows measurement of the domain sizes and geometries of the surface phase separation.

Thin-film nanocomposite (TFN) membranes have been widely investigated for water treatment applications due to their promising performance in terms of flux, salt rejection, and their antifouling properties. This review article provides an overview of the TFN membrane characterization and performance. It presents different characterization techniques that have been used to analyze these membranes and the nanofillers within them. The techniques comprise structural and elemental analysis, surface and morphology analysis, compositional analysis, and mechanical properties. Additionally, the fundamentals of membrane preparation are also presented, together with a classification of nanofillers that have been used so far. The potential of TFN membranes to address water scarcity and pollution challenges is significant. This review also lists examples of effective TFN membrane applications for water treatment. These include enhanced flux, enhanced salt rejection, antifouling, chlorine resistance, antimicrobial properties, thermal stability, and dye removal. The article concludes with a synopsis of the current status of TFN membranes and future perspectives.