Spatially Controlled Occlusion of Polymer‐Stabilized Gold Nanoparticles within ZnO

Abstract

In principle, incorporating nanoparticles into growing crystals offers an attractive and highly convenient route for the production of a wide range of novel nanocomposites. Herein we describe an efficient aqueous route that enables the spatially controlled occlusion of gold nanoparticles (AuNPs) within ZnO crystals at up to 20 % by mass. Depending on the precise synthesis protocol, these AuNPs can be (i) solely located within a central region, (ii) uniformly distributed throughout the ZnO host crystal or (iii) confined to a surface layer. Remarkably, such efficient occlusion is mediated by a non‐ionic water‐soluble polymer, poly(glycerol monomethacrylate)70 (G70), which is chemically grafted to the AuNPs; pendent cis‐diol side groups on this steric stabilizer bind Zn2+ cations, which promotes nanoparticle interaction with the growing ZnO crystals. Finally, uniform occlusion of G70‐AuNPs within this inorganic host leads to faster UV‐induced photodegradation of a model dye.

Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals

“…The occlusion of additives ranging from small molecules, 7 , 32 , 53 , 54 to polymers, 34 , 55 , 56 to organic and inorganic nanoparticles, 4 , 5 , 8 , 18 , 22 , 24 , 26 , 28 in single crystals provides a unique strategy for creating new materials with tailor-made properties. However, to fully profit from this approach, it is necessary to control the composition and structure of these nanocomposites.…”

“…This approach has been demonstrated for the occlusion of nanoparticles including magnetite (Fe 3 O 4 ), gold and organic nano-objects in calcite and ZnO. 24 – 28 Nanoparticle aggregation is less significant in organic solvents, such that successful occlusion has been achieved of Pt nanoparticles in MOFs 29 and PbS particles in methylammonium lead iodide perovskites. 4 , 30…”

Rationally designed anionic diblock copolymer worm gels are useful model systems for calcite occlusion studies

“…In principle, this new class of model anionic nanoparticles, which exhibit precisely controlled size (for spheres), adjustable morphology and tunable anionic surface character (particularly for case 1), should provide new insights for biomineralization studies. 50,[52][53][54][55][56][57][58][59] For example, an extensive study of the occlusion of the spherical micelles discussed in case 1 and 2 above within Figure 10. Storage modulus (G') and loss modulus (G'') versus temperature curves obtained by rheological studies of a series of 20% w/w worm gels of varying composition.…”

Efficient occlusion of oil droplets within calcite crystals

“…[1][2][3] Over the past decade, a range of synthetic protocols have been developed for the incorporation of various guest species (e.g. nanoparticles [4][5][6][7][8][9] or organic molecules [10][11][12][13][14] ) within host crystals. In principle, efficient additive occlusion should enable the preparation of a range of new nanocomposite crystals [15][16][17][18][19][20][21][22] and, at least in some cases, also enhance our understanding of biomineralization.…”