Polyethylene (PE) is the most widely used plastic, known for its high mechanical strength and affordability, rendering it responsible for ~70% of packaging waste and contributing to microplastic pollution. The cleavage of the carbon chain can induce the conversion of PE wastes into low-molecular-weight hydrocarbons, such as petroleum oils, waxes, and natural gases, but the thermal degradation of PE is challenging and requires high temperatures exceeding 400 °C due to its lack of specific chemical groups. Herein, we prepare metal/zeolite nanocatalysts by incorporating small-sized nickel nanoparticles into zeolite to lower the degradation temperature of PE. With the use of nanocatalysts, the degradation temperature can be lowered to 350 °C under hydrogen conditions, compared to the 400 °C required for non-catalytic pyrolysis. The metal components of the catalysts facilitate hydrogen adsorption, while the zeolite components stabilize the intermediate radicals or carbocations formed during the degradation process. The successful pyrolysis of PE at low temperatures yields valuable low-molecular-weight oil products, offering a promising pathway for the upcycling of PE into higher value-added products.
The co-assembly of block copolymers (BCPs) and inorganic nanoparticles (NPs) under emulsion confinement allows facile access to hybrid polymeric colloids with controlled hierarchical structures. Here, the effect of inorganic NPs on the structure of the hybrid BCP particles and the local distribution of NPs are studied, with a particular focus on comparing Au and Fe3O4 NPs. To focus on the effect of the NP core, Au and Fe3O4 NPs stabilized with oleyl ligands were synthesized, having a comparable diameter and grafting density. The confined co-assembly of symmetric polystyrene-b-poly(1,4-butadiene) (PS-b-PB) BCPs and NPs in evaporative emulsions resulted in particles with various morphologies including striped ellipsoids, onion-like particles, and their intermediates. The major difference in PS-b-PB/Au and PS-b-PB/Fe3O4 particles was found in the distribution of NPs inside the particles that affected the overall particle morphology. Au NPs were selectively localized inside PB domains with random distributions regardless of the particle morphology. Above the critical volume fraction, however, Au NPs induced the morphological transition of onion-like particles into ellipsoids by acting as an NP surfactant. For PS-b-PB/Fe3O4 ellipsoids, Fe3O4 NPs clustered and segregated to the particle/surrounding interface of the ellipsoids even at a low volume fraction, while Fe3O4 NPs were selectively localized in the middle of PB domains in a string-like pattern for PS-b-PB/Fe3O4 onion-like particles.
The molecular weights and chain rigidities of block copolymers can strongly influence their self-assembly behavior, particularly when the block copolymers are under confinement. We investigate the self-assembly of bottlebrush block copolymers (BBCPs) confined in evaporative emulsions with varying molecular weights. A series of symmetric BBCPs, where polystyrene (PS) and polylactide (PLA) side-chains are grafted onto a polynorbornene (PNB) backbone, are synthesized with varying degrees of polymerization of the PNB (NPNB) ranging from 100 to 300. Morphological transitions from onion-like concentric particles to striped ellipsoids occur as the NPNB of the BBCP increases above 200, which is also predicted from coarse-grained simulations of BBCP-containing droplets by an implicit solvent model. This transition is understood by the combined effects of (i) an elevated entropic penalty associated with bending lamella domains of large molecular weight BBCP particles and (ii) the favorable parallel alignment of the backbone chains at the free surface. Furthermore, the morphological evolutions of onion-like and ellipsoidal particles are compared. Unlike the onion-like BBCP particles, ellipsoidal BBCP particles are formed by the axial development of ring-like lamella domains on the particle surface, followed by the radial propagation into the particle center. Finally, the shape anisotropies of the ellipsoidal BBCP particles are analyzed as a function of particle size. These BBCP particles demonstrate promising potential for various applications that require tunable rheological, optical, and responsive properties.
Shape-anisotropic polymeric colloids having chemically distinct compartments are promising materials, however, introducing site-specific surface functionality to block copolymer (BCP) particles has not yet been actively investigated. The current contribution demonstrates the selective surface functionalization of nanostructured, ellipsoidal polystyrene-b-polybutadiene (PS-b-PB) particle and investigate their effects on the particle shape. Photo-induced thiol-ene click reaction was used as a selective functionalization chemistry for modifying the PB block, which was achieved by controlling the feed ratio of functional thiols to the double bonds in PB. Importantly, the controlled particle elongation was observed as a function of the degree of PB functionalization. Such an increase in the aspect ratio is attributed to the (i) increased incompatibility of the PS and modified PB block and (ii) the reduced surface tension between the particles and surrounding aqueous medium, both of which contributes to the further elongation of ellipsoids. Further tunability of the elongation behavior of ellipsoids was further demonstrated by controlling the particle size and chemical structure of functional thiols, showing the versatility of this approach for controlling the particle shape. Finally, the utility of surface functionality was demonstrated by the facile complexation of fluorescent dye on the modified surface of the particle via favorable interaction, which showed stable fluorescence and colloidal dispersity.
Confined assembly of block copolymers (BCPs) is receiving increasing attention due to the ability to create unconventional morphologies that cannot be observed in the corresponding bulk systems. This effect is further driven by the simplicity and versatility of these procedures for controlling the shape of particles prepared by 3D soft confinement of BCPs in emulsions. By taking advantage of a mobile emulsion interface, the one-step formation of nonspherical BCP particles through spontaneous deformation is possible with design principles and theoretical models for controlling shape/nanostructure now being established. This Viewpoint highlights strategies for shape tuning of BCP particles, currently accessible shapes, their controllability, and potential application. The emergence of 3D soft confinement of BCPs and related theory is overviewed with a focus on current strategies, types of nonspherical shapes achieved, and structure-property relationships for nonspherical BCP particles. Finally, the applications and future perspectives for these materials are discussed.
