Structural complexity in Prussian blue analogues

Abstract

We survey the most important kinds of structural complexity in Prussian blue analogues, their implications for materials function, and how they might be controlled through judicious choice of composition. We...

Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6]

“…By contrast, we expect that the K-ion slide distortion in the vacancy-free K 2 Cu[Fe(CN) 6 ] will be switched off at a critical potassium content because K + ions are removed during charge. 22 , 25 On the basis of the symmetry relationships shown in Figure 3 , one anticipates a transition to the Cccm structure type at such a point, which would explain the two-phase mechanism we observe here.…”

“… 1 , 28 Cooperative tilting of the transition-metal coordination polyhedra is also observed; the particular tilt system is given by the Glazer notation 35 a 0 a 0 c + and is the simplest tilt distortion compatible with the K-ion slides we have observed. 22 , 36 An important feature of this structure is the existence of two symmetry-inequivalent K + sites, a point that is discussed later in this paper. Further details of key bond lengths and coordination environments are given in the SI .…”

“… 25 Formally, this monoclinic structure type is related to the idealized cubic PBA parent structure ( Fm 3̅ m symmetry) by the combined activation of the slide distortion shown in Figure 1 b and a cooperative a 0 a 0 c + octahedral tilt of the framework structure that always seems to accompany it. 22 , 23 The former deformation transforms as the X 5 + irreducible representation (irrep; note that we are using labels relative to the double-perovskite Fm 3̅ m parent with B-site ions located at the cell origin) and the latter as X 3 + ; it is the interplay of these two distortion modes that reduces the PBA symmetry to P 2 1 / n . 22 Replacing Mn 2+ by the Jahn–Teller-active Cu 2+ understandably leads to an additional distortion of the type illustrated in Figure 1 c, which transforms as Γ 3 + .…”

N-Doped hollow Fe0.4Co0.6S2@NC nanoboxes derived from a Prussian blue analogue as a sodium ion anode

“…11 Prussian blue analogues (PBAs) have been the focus of numerous different research areas because of their advantages including inherent open framework structures, high theoretical specific capacity, safety and easy synthesis. 12 Our previous work has focused on studying PBAs as SIB electrodes. 13 It is worth noting that PBAs are excellent candidates for the syn-thesis of new hierarchical or porous functional nanomaterial precursors/templates.…”

2D Network overtakes 3D for photocatalytic hydrogen evolution

“…[1][2][3] 3D Prussian blue analogues (PBAs) have been used extensively in catalytic applications mainly due to their simple synthetic strategy, the robustness of the network structure, and the activity of surface sites. [4][5][6] Despite their intriguing properties, they suffer from extremely low intrinsic HER activity compared to their heterogeneous phosphides and chalcogenides counterparts due to less exposed active surfaces and low conductivity. [7][8][9] Recent efforts to promote a PBA as a proton reduction catalyst are mainly limited to coupling with active semiconductors or decomposition into their corresponding oxides, phosphides, and chalcogenides.…”