A "copolymer-co-morphology" conception for shape-controlled synthesis of Prussian blue analogues and as-derived spinel oxidesElectronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07193c

The morphologically and compositionally controlled synthesis of coordination polymers and spinel oxides is highly desirable for realizing new advanced nanomaterial functionalities. Here we develop a novel and scalable strategy, containing a "copolymer-co-morphology" conception, to shape-controlled synthesis of various types of Prussian blue analogues (PBAs). Three series of PBAs M y Fe 1− y [Co(CN) 6 ] 0.67 · n H 2 O (M y Fe 1− y -Co, M = Co, Mn and Zn) with well-controlled morphology have been successfully prepared through this strategy. Using Mn y Fe 1− y -Co PBAs as the model, by increasing the relative content of Mn, flexible modulation of the morphology could be easily realized. In addition, a series of porous Mn x Fe 1.8− x Co 1.2 O 4 nano-dices with well-inherited morphologies and defined cation distribution could be obtained through a simple thermal treatment of the PBAs. All these results demonstrate the good universality of this novel strategy. When evaluated as an electrocatalyst, the octahedral-site Mn III /Mn IV content in Mn x Fe 1.8− x Co 1.2 O 4 , mainly determined by sensitive 57 Fe Mössbauer in combination with X-ray photoelectron spectroscopic techniques, was discovered to be directly correlated with the oxygen reduction/evolution reaction (ORR/OER) activity. The morphologically and compositionally controlled synthesis of coordination polymers and spinel oxides is highly desirable for realizing new advanced nanomaterial functionalities.