Subnanometer CdS clusters self-confined in MFI-type zeolite nanoparticles and thin films.

One-step colloidal synthesis of subnanometer CdS clusters in hydrophobic MFI-type zeolite crystals in the presence of 3-mercaptopropyl-trimethoxysilane (MPS), cadmium precursor, and tetrapropylammonium hydroxide (TPAOH) is performed. MPS is used as the bifunctional agent, as it hydrolyzes fast, cross-links with the silica framework, and provides thiol groups to anchor Cd(2+), and subsequently forms CdS clusters. The MFI crystals with the thiol groups not only function as a nanochamber for the formation of CdS but also prevent further moisture-induced agglomeration of the clusters. Direct evidence for the presence of asymmetric shaped subnanometer CdS clusters aligned in the channels of MFI crystals stabilized in suspensions and films is provided by high resolution transmission electron microscopy (HRTEM), grazing incidence X-ray diffraction (GI-XRD), and photoluminescence spectra (emission < 350 nm). The CdS clusters are stable for months in colloidal suspensions and films without any particular precaution against water. The hydrophobicity of the MFI zeolite and the presence of the organic template in the channels favor the stabilization of small CdS clusters, which are available for further applications.