Pressure-Induced Dislocations and Their Influence on Ionic Transport in Li+-Conducting Argyrodites.

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.

Understanding and Controlling Molecular Compositions and Properties in Mixed-Linker Porphyrin Metal-Organic Frameworks.

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.

Estimating the nonideality of eutectic systems containing thermally unstable substances.

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.

Understanding MOF Flexibility: An Analysis Focused on Pillared Layer MOFs as a Model System.

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.

Optically Induced Long-Lived Chirality Memory in the Color-Tunable Chiral Lead-Free Semiconductor (R)/(S)-CHEA4Bi2BrxI10-x (x = 0-10).

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.

The structural complexity of perovskites.

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.

Tuning the High-Pressure Phase Behaviour of Highly Compressible Zeolitic Imidazolate Frameworks: From Discontinuous to Continuous Pore Closure by Linker Substitution.

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 4000 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.

Configurational Entropy Driven High-Pressure Behaviour of a Flexible Metal-Organic Framework (MOF).

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.

Controlling Multiphoton Absorption Efficiency by Chromophore Packing in Metal-Organic Frameworks.

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.

Tuning the Negative Thermal Expansion Behavior of the Metal-Organic Framework Cu3BTC2 by Retrofitting.

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.

Unprecedented High Oxygen Evolution Activity of Electrocatalysts Derived from Surface-Mounted Metal-Organic Frameworks.

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 ∼2.5 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.

Trapping Amorphous Intermediates of Carbonates - A Combined Total Scattering and NMR Study.

Crystallization via metastable phases plays an important role in chemical manufacturing, biomineralization, and protein crystallization, but the kinetic pathways leading from metastable phases to the stable crystalline modifications are not well understood. In particular, the fast crystallization of amorphous intermediates makes a detailed characterization challenging. To circumvent this problem, we devised a system that allows trapping and stabilizing the amorphous intermediates of representative carbonates (calcium, strontium, barium, manganese, and cadmium). The long-term stabilization of these transient species enabled a detailed investigation of their composition, structure, and morphology. Total scattering experiments with high-energy synchrotron radiation revealed a short-range order of several angstroms in all amorphous intermediates. From the synchrotron data, a structural model of amorphous calcium carbonate was derived that indicates a lower coordination number of calcium compared to the crystalline polymorphs. Our study shows that a multistep crystallization pathway via amorphous intermediates is open to many carbonates. We could isolate and characterize these transient species, thereby providing new insights into their crystallization mechanism.

Tuning the Mechanical Response of Metal-Organic Frameworks by Defect Engineering.

The incorporation of defects into crystalline materials provides an important tool to fine-tune properties throughout various fields of materials science. We performed high-pressure powder X-ray diffraction experiments, varying pressures from ambient to 0.4 GPa in 0.025 GPa increments to probe the response of defective UiO-66 to hydrostatic pressure for the first time. We observe an onset of amorphization in defective UiO-66 samples around 0.2 GPa and decreasing bulk modulus as a function of defects. Intriguingly, the observed bulk moduli of defective UiO-66(Zr) samples do not correlate with defect concentration, highlighting the complexity of how defects are spatially incorporated into the framework. Our results demonstrate the large impact of point defects on the structural stability of metal-organic frameworks (MOFs) and pave the way for experiment-guided computational studies on defect engineered MOFs.

Spectroscopic characterization of lithium thiophosphates by XPS and XAS - a model to help monitor interfacial reactions in all-solid-state batteries.

Inspired by reports of redox active interphases in all-solid-state batteries employing fast conducting lithium thiophosphate solid-state electrolytes, we investigated the compositional depolymerization of interconnected PS4 tetrahedra in (Li2S)x(P2S5)100-x glasses (50 < x < 80) by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Based on the observed energy shifts with composition, we present a structural model of the three different bonding types describing the structures of either crystalline or amorphous thiophosphates. This model and reference data characterizes amorphous thiophosphates based on their inter-tetrahedral connectivity and helps to distinguish malign decomposition reactions from reversible redox reactions at the cathode active material/solid-state electrolyte interface. This work highlights the importance of a combined analytical approach and appropriate reference compounds to elucidate the interface reactions in all-solid-state battery systems.

Elaboration of a Highly Porous RuII,II Analogue of HKUST-1.

When the dinuclear RuII,II precursor [Ru2(OOCCH3)4] is employed under redox-inert conditions, a RuII,II analogue of HKUST-1 was successfully prepared and characterized as a phase-pure microcrystalline powder. X-ray absorption near-edge spectroscopy confirms the oxidation state of the Ru centers of the paddle-wheel nodes in the framework. The porosity of 1371 m2/mmol of RuII,II-HKUST-1 exceeds that of the parent compound HKUST1 (1049 m2/ mmol).

Time-Resolved In†Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.

Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X-ray powder diffraction to study the solvothermal formation of isostructural M2 (bdc)2 dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.

Using crystallographic shear to reduce lattice thermal conductivity: high temperature thermoelectric characterization of the spark plasma sintered Magnéli phases WO2.90 and WO2.722.

Engineering of nanoscale structures is a requisite for controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require a conflicting combination of low thermal conductivity and low electrical resistivity. We report the thermoelectric properties of spark plasma sintered Magnéli phases WO2.90 and WO2.722. The crystallographic shear planes, which are a typical feature of the crystal structures of Magnéli-type metal oxides, lead to a remarkably low thermal conductivity for WO2.90. The figures of merit (ZT = 0.13 at 1100 K for WO2.90 and 0.07 at 1100 K for WO2.722) are relatively high for tungsten-oxygen compounds and metal oxides in general. The electrical resistivity of WO2.722 shows a metallic behaviour with temperature, while WO2.90 has the characteristics of a heavily doped semiconductor. The low thermopower of 80 µV K(-1) at 1100 K for WO2.90 is attributed to its high charge carrier concentration. The enhanced thermoelectric performance for WO2.90 compared to WO2.722 originates from its much lower thermal conductivity, due to the presence of crystallographic shear and dislocations in the crystal structure. Our study is a proof of principle for the development of efficient and low-cost thermoelectric materials based on the use of intrinsically nanostructured materials rather than artificially structured layered systems to reduce lattice thermal conductivity.

Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides.

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.

Reduced thermal expansion by surface-mounted nanoparticles in a pillared-layered metal-organic framework.

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.

Solution synthesis of nanoparticular binary transition metal antimonides.

The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were obtained with sizes ranging from 20 and 60 nm. Through careful control of the reaction conditions, single-phase nanoparticular antimonides were synthesized. The nanophases were investigated by powder X-ray diffraction and (high resolution) electron microscopy. The approach is based on activated metal nanoparticles as precursors for the synthesis of the intermetallic compounds. X-ray powder diffraction studies of reaction intermediates allowed monitoring of the reaction kinetics. The small particle size of the reactants ensures short diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis.