Occlusion of Diblock Copolymer-Modified Gold Nanoparticles Generates Diabolo-Shaped Au@ZnO Nanocomposite Crystals with Enhanced Photocatalytic Properties

Abstract

Double-hydrophilic diblock copolymers have been extensively used as additives to tune the growth of inorganic crystals in aqueous media. However, there have been no reports of how double-hydrophilic diblock copolymer-decorated nanoparticles influence the morphology, structure, and properties of such crystals. Herein, a well-defined poly­(ammonium 2-sulfatoethyl methacrylate)-poly­(glycerol monomethacrylate) diblock copolymer is prepared by reversible addition-fragmentation chain transfer polymerization and then adsorbed onto the surface of gold nanoparticles via its dithiobenzoate end-group to form sterically stabilized nanoparticles. The growth of zinc oxide (ZnO) crystals in the presence of such nanoparticles leads to their occlusion, producing Au@ZnO nanocomposite crystals with a remarkable diabolo morphology. Furthermore, such Au@ZnO crystals enable the rapid photocatalytic degradation of a model organic dye (rhodamine B) when subjected to visible light irradiation. This study opens up a new avenue for the design of diblock copolymer-stabilized nanoparticles to enable the construction of organic–inorganic nanocomposite crystals that exhibit emergent properties.

Metal–Organic Frameworks@Calcite Composite Crystals

“…This is most probably because the PMAA packing density at the surface of UiO-66-PMAA is relatively low and the growth of calcite crystal can readily penetrate into the PMAA layer, resulting in intimate contact between the guest MOF crystals and the host calcite. Indeed, a similar finding was reported in prior studies, where polymer-modified gold nanoparticles are in close contact with the host zinc oxide matrix without the detection of the polymeric layer in between. , …”

“…Indeed, a similar finding was reported in prior studies, where polymer-modified gold nanoparticles are in close contact with the host zinc oxide matrix without the detection of the polymeric layer in between. 47,48 High-resolution TEM enables the lattice fringes of these two components to be visualized. Figure 2e,f showed that the host calcite matrix is a single crystal whereas the UiO-66-PMAA is polycrystalline since the lattice fringes of the latter are ordered only in short ranges.…”

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure

“…are essential for successful nanoparticle incorporation. – Moreover, the polymer chain length has to be long enough so as to provide sufficient binding sites to drive nanoparticle incorporation and the chain density ideally should be optimized. , When these parameters are satisfied, nanoparticle incorporation can be realized. Undoubtably, surface modification of the guest nanoparticles is tedious, time-consuming and sometimes irreproducible. – In the present study, the PMAA 84 -P­(St- alt -NMI) 100 nanoparticles played a key role in promoting the incorporation of CNPs into calcite crystals. Such anionic polymeric nanoparticles bridge the MSNs-NH 2 and the growing calcite.…”

Research progress of stimuli-responsive ZnO-based nanomaterials in biomedical applications

“…), [41][42][43] recombination (metal, non-metal, etc. ), [44][45][46] hybridization (MOFs, UCNPs, etc. ), 47,48 coupling narrow band gap materials 49 and developing oxygen vacancies, 50 thereby broadening the light absorption range.…”