Hidden Diversity of Vacancy Networks in Prussian Blue Analogues
Arkadiy Simonov, Trees De Baerdemaeker, Hanna L. B. Boström, María Laura Ríos Gómez, Harry J. Gray, Dmitry Chernyshov, Alexey Bosak, Hans-Beat Bürgi, Andrew L. Goodwin
Prussian blue analogues (PBAs) are a broad and important family of microporous inorganic solids, famous for their gas storage, metal-ion immobilisation, proton conduction, and stimuli-dependent magnetic, electronic and optical properties. The family also includes the widely-used double-metal cyanide (DMC) catalysts and the topical hexacyanoferrate/hexacyanomanganate (HCF/HCM) battery materials. Central to the various physical properties of PBAs is the ability to transport mass reversibly, a process made possible by structural vacancies. Normally presumed random, vacancy arrangements are actually crucially important because they control the connectivity of the micropore network, and hence diffusivity and adsorption profiles. The long-standing obstacle to characterising PBA vacancy networks has always been the relative inaccessibility of single-crystal samples. Here we report the growth of single crystals of a range of PBAs. By measuring and interpreting their X-ray diffuse scattering patterns, we identify for the first time a striking diversity of non-random vacancy arrangements that is hidden from conventional crystallographic analysis of powder samples. Moreover, we show that this unexpected phase complexity can be understood in terms of a remarkably simple microscopic model based on local rules of electroneutrality and centrosymmetry. The hidden phase boundaries that emerge demarcate vacancy-network polymorphs with profoundly different micropore characteristics. Our results establish a clear foundation for correlated defect engineering in PBAs as a means of controlling storage capacity, anisotropy, and transport efficiency.
We experimentally show that the magnetocaloric properties of molecule-based Prussian blue analogues can be adjusted by controlling during the synthesis the amount of intrinsic vacancies. For Cs_xNi^II_4[Cr^III(CN)_6]_(8+x)/3}, we find indeed that the ferromagnetic phase transition induces significantly large magnetic entropy changes, whose maxima shift from 68 K to 95 K by varying the number of [Cr^III(CN)_6]^3- vacancies, offering an unique tunability of the magnetocaloric effect in this complex.
We report on the magnetocaloric properties of two molecule-based hexacyanochromate Prussian blue analogs, nominally CsNi[Cr(CN)_6](H_2O) and Cr_3[Cr(CN)_6]_2x12(H_2O). The former orders ferromagnetically below Tc=90 K, whereas the latter is a ferrimagnet below Tc=230 K. For both, we find significantly large magnetic entropy changes DSm associated to the magnetic phase transitions. Notably, our studies represent the first attempt to look at molecule-based materials in terms of the magnetocaloric effect for temperatures well above the liquid helium range.
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 focus on six particular aspects: octahedral tilts, A-site `slides', Jahn--Teller distortions, A-site species and occupancy, hexacyanometallate vacancies, and framework hydration. The promising K-ion cathode material K$_x$Mn[Fe(CN)$_6$]$_y$ serves as a recurrent example that illustrates many of these different types of complexity. Our article concludes with a discussion of how the interplay…
Magnetic order in the thermally quenched photomagnetic Prussian blue analogue coordination polymer K0.27Co[Fe(CN)6]0.73[D2O6]0.27 1.42D2O has been studied down to 4 K with unpolarized and polarized neutron powder diffraction as a function of applied magnetic field. Analysis of the data allows the onsite coherent magnetization of the Co and Fe spins to be established. Specifically, magnetic fields of 1 T and 4 T induce moments parallel to the applied field, and the sample behaves as a ferromagnet with a wandering axis.
This paper summarizes 0 GPa to 0.6 GPa neutron diffraction measurements of a nickel hexacyanochromate coordination polymer (NiCrPB) that has the face-centered cubic, Prussian blue structure. Deuterated powders of NiCrPB contain ~100 nm sided cubic particles. The application of a large magnetic field shows the ambient pressure, saturated magnetic structure. Pressures of less than 1 GPa have previously been shown to decrease the magnetic susceptibility by as much as half, and we find modifications to the nuclear crystal structure at these pressures that we quantify. Bridging cyanide molecules is…
Octahedral tilting is key to the structure and functionality of perovskites. Here we show how these distortions manifest in the related Prussian blue analogues (PBAs): cyanide versions of double perovskites with formula A$_x$M[M$^{\prime}$(CN)$_6$]$_{1-y}\Box _y\cdot n$H$_2$O (A = alkali metal, M and M$^{\prime}$ = transition metals, $\Box$ = vacancy/defect). Tilts are favoured by high values of $x$ if A = Na or K, whereas the transition metals play a less important role. External hydrostatic pressure can induce tilt transitions nearly irrespective of the stoichiometry, whereas thermal transit…
The cubic Prussian Blue (PB) analog, Zn3 [Fe(CN)6]2, has been studied by X-ray powder diffraction and inelastic neutron scattering (INS). X-ray data collected at 300 and 84 K revealed negative thermal expansion (NTE) behaviour for this material. The NTE coefficient was found to be -31.1 x 10-6 K-1. The neutron vibrational spectrum for Zn3[Fe(CN)6]2.xH2O, was studied in detail. The INS spectrum showed well-defined, well-separated bands corresponding to the stretching of and deformation modes of the Fe and Zn octahedra, all below 800 cm-1.
Mixed Orbital Ground States of Fe2+ in Prussian Blues
Mössbauer Effect Data Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences（中国科学院大连化学物理研究所）；School of Engineering, The University of Tokyo（东京大学工学部）
Nanoparticles of rubidium cobalt hexacyanoferrate (Rb$_j$Co$_k$[Fe(CN)$_6$]$_l \cdot n$H$_2$O) were synthesized using different concentrations of the polyvinylpyrrolidone (PVP) to produce four different batches of particles with characteristic diameters ranging from 3 to 13 nm. Upon illumination with white light at 5 K, the magnetization of these particles increases. The long-range ferrimagnetic ordering temperatures and the coercive fields evolve with nanoparticle size. At 2 K, particles with diameters less than approximately 10 nm provide a Curie-like magnetic signal.
Different types of ordering phenomena may occur during phase transitions, described within the universal framework of the Landau theory through the evolution of one, or several, symmetry-breaking order parameter h. In addition, many systems undergo phase transitions related to an electronic instability, in the absence of a symmetry-breaking and eventually described through the evolution of a totally symmetric order parameter q linearly coupled to volume change. Analyzing the coupling of a non-symmetry-breaking electronic instability, responsible for volume strain, to symmetry-breaking phenomen…
We present dynamical properties of spin crossover compounds with photomagnetization, proposing a new model in which the spin-crossover phenomena and magnetic ordering are incorporated in a unified way. By using this model, the novel characteristics observed in Prussian blue analogs are qualitatively well reproduced. We investigate the time evolution of the magnetization and high spin fraction taking into account multi-time scales in a master equation approach for the magnetic relaxation, the lattice (electronic) relaxation, and the photoexcitation process. In particular, processes with differe…
Cubic heterostructured (BA) particles of Prussian blue analogues, composed of a shell of ferromagnetic K_{0.3}Ni[Cr(CN)_6]_{0.8} \cdot 1.3H_2O (A), Tc ~ 70 K, surrounding a bulk core of photoactive ferrimagnetic Rb_{0.4}Co[Fe(CN)_6]_{0.8} \cdot 1.2H_2O (B), Tc ~20 K, have been studied. Below Tc ~ 70 K, these samples exhibit a persistent photoinduced decrease in low-field magnetization, and these results resemble data from other core-shell particles and analogous ABA heterostructured films. This net decrease suggests that the photoinduced lattice expansion in the B layer generates a strain-indu…
Fine and Hyperfine Interactions with Multi-level Spin Relaxation of the purified Giese-Salt in Veterinary Medicine: Prussian Blue Compound Ammonium-Ferric-Hexacyano-Ferrate
University of Veterinary Medicine Hannover Foundation（汉诺威兽医大学基金会）；Leibniz University Hannover（汉诺威莱布尼茨大学）；Technische Universität Berlin（柏林工业大学）；Technische Universität Dresden（德累斯顿工业大学）；TU Bergakademie Freiberg（弗赖贝格矿业技术大学）
The combination of spin transitions and magnetic ordering provides an interesting structure of phase transitions in Prussian blue analogues (PBAs). To understand the structure of stable and metastable states of Co-Fe PBA, it is necessary to clarify free energy as a function of magnetization and the fraction of the high-temperature component. Including the magnetic interaction between high-temperature states, we study the magnetic phase transition of Co-Fe PBA in addition to spin transitions. Here, we take into account the degeneracy changes due to charge transfer between Co and Fe atoms accomp…
Emerging concepts for neuromorphic computing, bioelectronics, and brain-computer interfacing inspire new research avenues aimed at understanding the relationship between oxidation state and conductivity in unexplored materials. Here, we present ruthenium Prussian blue analogue (RuPBA), a mixed valence coordination compound with an open framework structure and ability to conduct both ionic and electronic charge, for flexible artificial synapses that reversibly switch conductance by more than four orders of magnitude based on electrochemically tunable oxidation state. Retention of programmed sta…
We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions MII3[(M')III(CN)6]2.nH2O and MII2[FeII(CN)6].nH2O, where MII = Mn, Fe, Co, Ni, Cu and Zn, (M')III = Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150oC (123 K) and room-temperature. The vast majority of the studied PBAs w…
Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge t…
Nanoscale resistive switching in electrodeposited MOF Prussian blue analogs driven by K-ion intercalation probed by C-AFM
Université catholique de Louvain (UCLouvain)（天主教鲁汶大学）；University of Applied Sciences Zwickau（茨维考应用技术大学）；Universidad de Granada（格拉纳达大学）；Universitat de Valencia（瓦伦西亚大学）
Water, vacancies, and competing exchange interactions in Prussian blue analogues: a neutron diffraction study of field and dehydration-driven magnetic transitions
Université Paris-Saclay（巴黎萨克雷大学）；CNRS（法国国家科学研究中心）；Laboratoire de Physique des Solides（固体物理实验室）；Synchrotron SOLEIL（Soleil 同步辐射中心）；Institut Néel（内耳研究所）；Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）；Institut Laue-Langevin（朗之万-劳厄研究所）；ICMMO（无机化学、分子材料和有机材料研究所）；Institut universitaire de France (IUF)（法国高等研究院）
The Origin of Enhanced Conductivity and Structure Change in Defective Li4Ti5O12 or Blue-LTO : a study combined theoretical and experimental perspectives
We investigate the optical properties of silicon-vacancy (SiV) and germanium-vacancy (GeV) color centers in nanodiamonds under hydrostatic pressure up to 180 GPa. The nanodiamonds were synthetized by Si or Ge-doped plasma assisted chemical vapor deposition and, for our experiment, pressurized in a diamond anvil cell. Under hydrostatic pressure we observe blue-shifts of the SiV and GeV zero-phonon lines by 17 THz (70 meV) and 78 THz (320 meV), respectively. These measured pressure induced shifts are in good agreement with ab initio calculations that take into account the lattice compression bas…
Magneto-optical properties of the neutral silicon-vacancy center in diamond under extreme isotropic strain fields
Wigner Research Centre for Physics（维格纳物理研究中心）；Eötvös Loránd University（罗兰大学）；Budapest University of Technology and Economics, Institute of Physics, Department of Atomics Physics（布达佩斯技术与经济大学物理学院原子物理系）
