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The influence of the microstructure on the ionic conductivity and cell performance is a topic of broad scientific interest in solid-state batteries. The current understanding is that interfacial decomposition reactions during cycling induce local strain at the interfaces between solid electrolytes and the anode/cathode, as well as within the electrode composites. Characterizing the effects of internal strain on ion transport is particularly important, given the significant local chemomechanical effects caused by volumetric changes of the active materials during cycling. Here, we show the effects of internal strain on the bulk ionic transport of the argyrodite Li6PS5Br. Internal strain is reproducibly induced by applying pressures with values up to 10 GPa. An internal permanent strain is observed in the material, indicating long-range strain fields typical for dislocations. With increasing dislocation densities, an increase in the lithium ionic conductivity can be observed that extends into improved ionic transport in solid-state battery electrode composites. This work shows the potential of strain engineering as an additional approach for tuning ion conductors without changing the composition of the material itself.
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Porphyrin-based metal-organic frameworks (MOFs) are attractive materials for photo- and thermally activated catalysis due to their unique structural features related to the porphyrin moiety, guest-accessible porosity, and high chemical tunability. In this study, we report the synthetic incorporation of nonplanar ß-ethyl-functionalized porphyrin linkers into the framework structure of PCN-222, obtaining a solid-solution series of materials with different modified linker contents. Comprehensive analysis by a combination of characterization techniques, such as NMR, UV-vis and IR spectroscopy, powder X-ray diffraction, and N2 sorption analysis, allows for the confirmation of linker incorporation. A detailed structural analysis of intrinsic material properties, such as the thermal response of the different materials, underlines the complexity of synthesizing and understanding such materials. This study presents a blueprint for synthesizing and analyzing porphyrin-based mixed-linker MOF systems and highlights the hurdles of characterizing such materials.
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Eutectic systems design requires an in-depth understanding of their solid-liquid equilibria (SLE). Modeling SLE in eutectic systems has as prerequisites, the melting properties and activity coefficients of components in the liquid phase. Thus, due to the unavailable melting properties of thermally unstable substances, it is impossible to estimate their activity coefficients from experimental SLE data and model the SLE phase diagram of their eutectic systems. Here, we evaluate the activity coefficients of thermally unstable constituents in the liquid phase, which were calculated independent of their melting properties by correlating the SLE data of their cocrystals. Differential scanning calorimetry and powder x-ray diffraction were employed to obtain the SLE phase diagram of three eutectic systems, i.e., tetramethylammonium chloride/catechol, tetraethylammonium chloride/catechol, and betaine/catechol systems, and identify the formation of nine cocrystals. The non-random, two-liquid equation was used to calculate the activity coefficients of the components in the liquid phase. The substantial negative deviation from ideality in the three studied systems indicated strong hydrogen bonding interactions in the liquid solution. Furthermore, modeling ion-ion interactions in eutectic systems containing ionic constituents is of utmost importance for understanding their nonideality.
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Flexible porous frameworks are at the forefront of materials research. A unique feature is their ability to open and close their pores in an adaptive manner induced by chemical and physical stimuli. Such enzyme-like selective recognition offers a wide range of functions ranging from gas storage and separation to sensing, actuation, mechanical energy storage and catalysis. However, the factors affecting switchability are poorly understood. In particular, the role of building blocks, as well as secondary factors (crystal size, defects, cooperativity) and the role of host-guest interactions, profit from systematic investigations of an idealized model by advanced analytical techniques and simulations. The review describes an integrated approach targeting the deliberate design of pillared layer metal-organic frameworks as idealized model materials for the analysis of critical factors affecting framework dynamics and summarizes the resulting progress in their understanding and application.
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Hybrid organic-inorganic networks that incorporate chiral molecules have attracted great attention due to their potential in semiconductor lighting applications and optical communication. Here, we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free structures with an edge-sharing octahedral motif, to synthesize chiral lead-free (R)/(S)-CHEA4Bi2BrxI10-x crystals and thin films. Using single-crystal X-ray diffraction measurements and density functional theory calculations, we identify crystal and electronic band structures. We investigate the materials' optical properties and find circular dichroism, which we tune by the bromide-iodide ratio over a wide wavelength range, from 300 to 500 nm. We further employ transient absorption spectroscopy and time-correlated single photon counting to investigate charge carrier dynamics, which show long-lived excitations with optically induced chirality memory up to tens of nanosecond timescales. Our demonstration of chirality memory in a color-tunable chiral lead-free semiconductor opens a new avenue for the discovery of high-performance, lead-free spintronic materials with chiroptical functionalities.
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The four compounds A3MO4H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb3MoO4D, Cs3MoO4D and Cs3WO4D crystallize in the antiperovskite-like K3SO4F-structure type, while Rb3WO4D adopts a different orthorhombic structure. 2H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb3WO4H shows a unique, peculiar valence band structure dominated by hydride states.
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A recent research direction related to ABX3 perovskites is the use of molecules on the A and/or X-site, a development that has proved fruitful for photovoltaics, (improper) ferroelectrics and barocalorics. Replacing atoms by molecules increases the chemical space for the synthesis of materials with new properties, conceptually translating chemical, synthetic freedom to novel opportunities in material design. Here an information theory-based rating scheme is applied to obtain structural complexities across various perovskite classes. It is shown that chemical diversity is synonymous with increased structural complexity which scales with the size of the pseudocubic ReO3-type network and available distortion schemes. The results agree with chemical intuition and show that structural complexities serve as a valuable tool for identifying complex distortion schemes in perovskites such as octahedral tilts and shifts with unusual propagation vectors and deformations of the coordination network.
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The high-pressure behaviour of flexible zeolitic imidazolate frameworks (ZIFs) of the ZIF-62 family with the chemical composition M(im)2-x (bim)x is presented (M2+ =Zn2+ , Co2+ ; im- =imidazolate; bim- =benzimidazolate, 0.02≤x≤0.37). High-pressure powder X-ray diffraction shows that the materials contract reversibly from an open pore (op) to a closed pore (cp) phase under a hydrostatic pressure of up to 4000â bar. Sequentially increasing the bim- fraction (x) reinforces the framework, leading to an increased threshold pressure for the op-to-cp phase transition, while the total volume contraction across the transition decreases. Most importantly, the typical discontinuous op-to-cp transition (first order) changes to an unusual continuous transition (second order) for x≥0.35. This allows finetuning of the void volume and the pore size of the material continuously by adjusting the pressure, thus opening new possibilities for MOFs in pressure-switchable devices, membranes, and actuators.
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Control of thermal expansion (TE) is important to improve material longevity in applications with repeated temperature changes or fluctuations. The TE behavior of metal-organic frameworks (MOFs) is increasingly well understood, while the impact of surface-mounted nanoparticles (NPs) on the TE properties of MOFs remains unexplored despite large promises of NP@MOF composites in catalysis and adsorbate diffusion control. Here we study the influence of surface-mounted platinum nanoparticles on the TE properties of Pt@MOF (Pt@Zn2(DP-bdc)2dabco; DP-bdc2-=2,5-dipropoxy-1,4-benzenedicarboxylate, dabco=1,4-diazabicyclo[2.2.2]octane). We show that TE is largely retained at low platinum loadings, while high loading results in significantly reduced TE at higher temperatures compared to the pure MOF. These findings support the chemical intuition that surface-mounted particles restrict deformation of the MOF support and suggest that composite materials exhibit superior TE properties thereby excluding thermal stress as limiting factor for their potential application in temperature swing processes or catalysis.
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Molecular perovskites, i.e. ABX3 coordination polymers with a perovskite structure, are a chemically diverse material platform for studying fundamental and applied materials properties such as barocalorics and improper ferroelectrics. Compared to inorganic perovskites, the use of molecular ions on the A- and X-site of molecular perovskites leads to new geometric and structural degrees of freedom. In this work we introduce the concept of tilt and shift polymorphism, categorising irreversible perovskite-to-perovskite phase transitions in molecular perovskites. As a model example we study the new molecular perovskite series [(nPr)3(CH3)N]M(C2N3)3 with M = Mn2+, Co2+, Ni2+, and nPr = n-propyl, where different polymorphs crystallise in the perovskite structure but with different tilt systems depending on the synthetic conditions. Tilt and shift polymorphism is a direct ramification of the use of molecular building units in molecular perovskites and as such is unknown for inorganic perovskites. Given the role of polymorphism in materials science, medicine and mineralogy, and more generally the relation between physicochemical properties and structure, the concept introduced herein represents an important step in classifying the crystal chemistry of molecular perovskites and in maturing the field.
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Ciencia de los Materiales , Compuestos de Calcio , Óxidos , TitanioRESUMEN
The information content of a crystal structure as conceived by information theory has recently proved an intriguing approach to calculate the complexity of a crystal structure within a consistent concept. Given the relatively young nature of the field, theory development is still at the core of ongoing research efforts. This work provides an update to the current theory, enabling the complexity analysis of crystal structures with partial occupancies as frequently found in disordered systems. To encourage wider application and further theory development, the updated formulas are incorporated into crystIT (crystal structure and information theory), an open-source Python-based program that allows for calculating various complexity measures of crystal structures based on a standardized *.cif file.
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Crystalline coordination polymers are a chemically diverse material platform that provide control over network geometry and chemical interactions, harbouring a wealth of phenomena of large scientific and technological relevance. The underlying structure together with chemical interactions play a crucial role, factors that together determine the underlying free energy surface of a material, i.e. its physicochemical properties. Here we discuss selected phenomena and research examples related to structural flexibility, identifying the underlying free energy landscape in coordination polymers as a scientific discipline unifying component that can help to further support cross-communication between different research areas. We finish by advocating the roles of concept-based thinking, interdisciplinarity and a progressive attitude in advancing the field in the near future.
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Flexible metal-organic frameworks (MOFs) show large structural flexibility as a function of temperature or (gas)pressure variation, a fascinating property of high technological and scientific relevance. The targeted design of flexible MOFs demands control over the macroscopic thermodynamics as determined by microscopic chemical interactions and remains an open challenge. Herein we apply high-pressure powder X-ray diffraction and molecular dynamics simulations to gain insight into the microscopic chemical factors that determine the high-pressure macroscopic thermodynamics of two flexible pillared-layer MOFs. For the first time we identify configurational entropy that originates from side-chain modifications of the linker as the key factor determining the thermodynamics in a flexible MOF. The study shows that configurational entropy is an important yet largely overlooked parameter, providing an intriguing perspective of how to chemically access the underlying free energy landscape in MOFs.
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ABX3 perovskite coordination networks are a rapidly growing sub-class of crystalline coordination networks. At present, synthetic efforts in the field are dominated by the use of commercially available building blocks, leaving the potential for tuning properties via targeted compositional changes largely untouched. Here we apply a rational crystal engineering approach, using 6-azaspiro[5.5]undecane ([ASU]+) as A-site cation for the synthesis of the polar perovskite [ASU][Cd(C2N3)3].
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Hydrogen bonds are of great scientific interest, determining the free energy landscape and hence chemical and physical properties of many materials systems, for example, the hybrid organic-inorganic perovskites. Although these interactions are critical, understanding them is difficult in complex, multicomponent systems; hydrogen halides are ideal as simple binary model compounds for understanding the role of hydrogen bonding in physical properties like phase transitions. Here we investigate the orthorhombic low-temperature phase and the cubic high-temperature phase in HX (X = F, Cl, Br, or I) systems to understand how different hydrogen-halide bonds influence free energy profiles. We show that hydrogen fluoride has a qualitatively different behavior due to strong hydrogen bonding and hence a very different vibrational entropy. Heavier halides are in contrast rather similar in their physical properties; however, dispersion interactions play a more crucial role in these. These results have implications for the rational design of materials with hydrogen-halide bonds and tuning material properties in systems like mixed anion CH3NH3PbX3 perovskites.
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The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) - retrofitting - has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.
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Coordination polymers show great potential for the tailored design of advanced photonic applications by employing crystal chemistry concepts. One challenge for achieving a rational design of nonlinear optically active MOF materials is deriving fundamental structure-property relations of the interplay between the photonic properties and the spatial arrangements of optically active chromophores within the network. We here investigate two-photon-absorption (TPA)-induced photoluminescence of two new MOFs based on a donor-acceptor tetraphenylphenylenediamine (tPPD) chromophore linker (H4TPBD) and Zn(II) and Cd(II) as metal centers. The TPA efficiencies are controlled by the network topologies, degree of interpenetration, packing densities, and the specific spatial arrangement of the chromophores. The effects can be rationalized within the framework of established excited-state theories of molecular crystals. The results presented here demonstrate the key effect of chromophore orientation on the nonlinear optical properties of crystalline network compounds and allow for establishing quantitative design principles for efficient TPA materials.
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The modular building principle of metal-organic frameworks (MOFs) presents an excellent platform to explore and establish structure-property relations that tie microscopic to macroscopic properties. Negative thermal expansion (NTE) is a common phenomenon in MOFs and is often ascribed to collective motions that can move through the structure at sufficiently low energies. Here, we show that the introduction of additional linkages in a parent framework, retrofitting, is an effective approach to access lattice dynamics experimentally, in turn providing researchers with a tool to alter the NTE behavior in MOFs. By introducing TCNQ (7,7,8,8-tetracyanoquinodimethane) into the prototypical MOF Cu3BTC2 (BTC = 1,3,5-benzenetricarboxylate; HKUST-1), NTE can be tuned between αV = -15.3 × 10-6 K-1 (Cu3BTC2) and αV = -8.4 × 10-6 K-1 (1.0TCNQ@Cu3BTC2). We ascribe this phenomenon to a general stiffening of the framework as a function of TCNQ loading due to additional network connectivity, which is confirmed by computational modeling and far-infrared spectroscopy. Our findings imply that retrofitting is generally applicable to MOFs with open metal sites, opening yet another way to fine-tune properties in this versatile class of materials.
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Flexible metal-organic frameworks (MOFs) exhibit large potential as next-generation materials in areas such as gas sensing, gas separation and mechanical damping. By using a mixed metal approach, we report how the stimuli reponsive phase transition of flexible pillared-layered MOFs can be tuned over a wide range. Different Cu2+ to Zn2+ metal ratios are incorporated into the materials by using a simple solvothermal approach. The properties of the obtained materials are probed by differential scanning calorimetry and CO2 sorption measurements, revealing stimuli responsive behaviour as a function of metal ratio. Pair distribution functions derived from X-ray total scattering experiments suggest a distortion of the M2 paddlewheel as a function of the Cu content. We rationalize these phenomena by the different distortion energies of Cu2+ and Zn2+ ions to deviate from the square pyramidal structure of the relaxed paddlewheel node. Our work follows on from the large interest in tuning and understanding the materials properties of flexible MOFs, highlighting the large number of parameters that can be used for the targeted manipulation and design of properties of these fascinating materials.
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The oxygen evolution reaction (OER) is a key process for renewable energy storage. However, developing non-noble metal OER electrocatalysts with high activity, long durability and scalability remains a major challenge. Herein, high OER activity and stability in alkaline solution were discovered for mixed nickel/cobalt hydroxide electrocatalysts, which were derived in one-step procedure from oriented surface-mounted metal-organic framework (SURMOF) thin films that had been directly grown layer-by-layer on macro- and microelectrode substrates. The obtained mass activity of â¼2.5 mA·µg-1 at the defined overpotential of 300 mV is 1 order of magnitude higher than that of the benchmarked IrO2 electrocatalyst and at least 3.5 times higher than the mass activity of any state-of-the-art NiFe-, FeCoW-, or NiCo-based electrocatalysts reported in the literature. The excellent morphology of the SURMOF-derived ultrathin electrocatalyst coating led to a high exposure of the most active Ni- and Co-based sites.