Design And Catalytic Performance Of Anisotropic Prussian Blue Analogue Based On Ion Doping

Prussian blue analogue(PBA)materials have shown application value in areas including drug delivery,energy storage,and catalysis due to the high porosity,large specific surface area,and regulatable structure.Studies have shown that the morphology and size of prussian blue analogue are important factors in fine-tuning the properties of materials.The synthesis of prussian blue analogue often unitize surfactants or templates to confine the growth of prussian blue analogue,while the shape of prussian blue analogues are generally limited to relatively simple configurations(e.g.,spheres or polyhedrons).To date,the morphological control of prussian blue analogue still remains as challenge.This paper reports a special zigzag crystal("Z"-PBA)synthesized by ion doping,which has a uniform thickness(～60 nm)of walls in three dimensions for the first time.NiCo(Fe)-PBA was obtained by doping[Fe(CN)6]3-in NiCo-PBA cube,and then the "Z"-PBA is obtained by preferentially etching the two opposite angles of the NiCo(Fe)-PBA by the ammonia.Mechanistic studies show that the heterogeneous growth of Fe3+and Fe2+(the redox reaction of Fe3+)leads to an inhomogeneous phase distribution is formed in NiCo(Fe)-PBA.Since the bonding between Ni2+and-N≡C-Fe3+would broke more easily,anisotropic etching of ammonia occurs.This open zigzag structure provides a larger specific surface area and more active sites to activate peroxymonosulfate(PMS)to degrade bisphenol ABased on this strategy,we synthesized a nanocage structure of a mixture of prussian blue analogues and oxide by changing the dopant ions.By doping ions,we first synthesize cubic nanostructured MnFeCo-PBA,and then MnFeCo-PBA and ammonia undergo corrosion reaction at normal temperature and pressure.Due to inhomogeneous phase distribution,the original cube was etched into a pyramid-shaped nanocage structure on the inner surface,which retains some prussian blue analogues structure,while the inner and outer surfaces are covered by 1-2 nm nanosheets.These nanosheets were characterized to be manganese oxides.This forms a composite of prussian blue analogues and oxide.Further investigation revealed that it showed high efficiency and high stability on catalytic degradation of bisphenol A.The above experiments show that the prussian blue analogues with inhomogeneous phase distribution can be obtained by introducing doping ions into the single-phase prussian blue analogues.Then prussian blue analogues or composite material of prussian blue analogues with unique morphology can be obtained after the anisotropic etching by ammonia.Due to its high specific surface area and more active sites,it can effectively improve the efficiency of catalytic degradation of bisphenol A.The current research results are expected to provide new ideas for further fine-tuning the structure and properties of prussian blue analogues and encourage the development of new water environmental restoration materials.