Crystal Face Dominated Fabrication of Prussian Blue Analogue with Oriented Growth and Naturally Nonpreferred Unsaturated Coordination Center.

ABSTRACT

Defects, such as unsaturated coordination centers and vacancies, can fundamentally change materials' inherent properties and growth habits. The development of defect engineering has promoted the application of many technologies, but it is still a great challenge to selectively manufacture defect sites in existing material systems. It is shown here that in situ site-directed tailoring of metal sites in Prussian blue analogs (PBA) can be achieved according to the reducibility differences of different metal atoms, forming naturally nonpreferred unsaturated coordination centers. Meanwhile, the in situ capture of small reducing molecule can realize site-directed tailoring of crystal facets during crystal growth and results in oriented 1D growth. As an oxygen evolution reaction catalyst, the resulted PBA with the nonpreferred unsaturated coordination centers shows a low overpotential of 239 mV at 10 mA cm-2 in alkali, superior to the original PBAs and the previously reported defective PBA derivatives, which can be ascribed to the unsaturated coordination active center and the unique 1D structure. This work opens up opportunities for producing naturally nonpreferred unsaturated coordination center in nanomaterials for broad applications.