The chemistry of ZnWO4 nanoparticle formation†
The need for a change away from classical nucleation and growth models for the description of nanoparticle formation is highlighted. By the use of in situ total X-ray scattering experiments the transformation of an aqueous polyoxometalate precursor mixture to crystalline ZnWO4 nanoparticles under hydrothermal conditions was followed. The precursor solution is shown to consist of specific Tourné-type sandwich complexes. The formation of pristine ZnWO4 within seconds is understood on the basis of local restructuring and three-dimensional reordering preceding the emergence of long range order in ZnWO4 nanoparticles. An observed temperature dependent trend in defect concentration can be rationalized based on the proposed formation mechanism. Following nucleation the individual crystallites were found to grow into prolate morphology with elongation along the unit cell c-direction. Extensive electron microscopy characterization provided evidence for particle growth by oriented attachment; a notion supported by sudden particle size increases observed in the in situ total scattering experiments. A simple continuous hydrothermal flow method was devised to synthesize highly crystalline monoclinic zinc tungstate (ZnWO4) nanoparticles in large scale in less than one minute. The present results highlight the profound influence of structural similarities in local structure between reactants and final materials in determining the specific nucleation of nanostructures and thus explains the potential success of a given synthesis procedure in producing nanocrystals. It demonstrates the need for abolishing outdated nucleation models, which ignore subtle yet highly important system dependent differences in the chemistry of the forming nanocrystals.