Oxide inverse opals (IOs) with their high surface area and open porosity are promising candidates for catalyst support applications. Supports with confined mesoporous domains are of added value to heterogeneous catalysis. However, the fabrication of IOs with mesoporous or sub-macroporous voids (<100 nm) continues to be a challenge, and the diffusion of tracers in quasi-mesoporous IOs is yet to be adequately studied. In order to address these two problems, we synthesized ZnO IOs films with tunable pore sizes using chemical bath deposition and template-based approach. By decreasing the size of polystyrene (PS) template particles towards the mesoporous range, ZnO IOs with 50 nm-sized pores and open porosity were synthesized. The effect of the template-removal method on the pore geometry (spherical vs. gyroidal) was studied. The infiltration depth in the template was determined, and the factors influencing infiltration were assessed. The crystallinity and photonic stop-band of the IOs were studied using X-Ray diffraction and UV-Vis, respectively. The infiltration of tracer molecules (Alexa Fluor 488) in multilayered quasi-mesoporous ZnO IOs was confirmed via confocal laser scanning microscopy, while fluorescence correlation spectroscopy analysis revealed two distinct diffusion times in IOs assigned to diffusion through the pores (fast) and adsorption on the pore walls (slow).

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth.