Visualization of Tetrahedral Li in the Alkali Layers of Li-Rich Layered Metal Oxides.

Understanding Li+ ion diffusion pathways in Li-rich layered transition metal (TM) oxides is crucial for understanding the sluggish kinetics in anionic O2- redox. Although Li diffusion within the alkali layers undergoes a low-barrier octahedral-tetrahedral-octahedral pathway, it is less clear how Li diffuses in and out of the TM layers, particularly given the complex structural rearrangements that take place during the oxidation of O2-. Here, we develop simultaneous electron ptychography and annular dark field imaging methods to unlock the Li migration pathways in Li1.2Ni0.13Mn0.54Co0.13O2 associated with structural changes in the charge-discharge cycle. At the end of TM oxidation and before the high-voltage O oxidation plateau, we show that the Li migrating out of the TM layers occupies the alkali-layer tetrahedral sites on opposite sides of the TM layers, forming Li-Li dumbbell configurations, consistent with the density functional theory calculations. Also occurring are the TM migration and phase transition from O3 to O1 stacking, leading to unstable tetrahedral Li and the absence of Li contrast in imaging. Upon further Li deintercalation to 4.8 V, most of the tetrahedral Li are removed. After discharging to 2 V, we did not identify the reformation of tetrahedral Li but observed permanently migrated TMs at the alkali-layer sites, disfavoring the Li occupying the tetrahedral sites for diffusion. Our findings suggest a landscape of Li diffusion pathways in Li-rich layered oxides and strategies for minimizing the disruption of Li diffusion.

In-Depth Analysis of the Species and Transformations during Sol Gel-Assisted V2PC Synthesis.

The sol-gel reaction mechanism of 211 MAX phases has proven to be very complex when identifying the intermediate species, chemical processes, and conversions that occur from a mixture of metal salts and gelling agent into a crystalline ternary carbide. With mostly qualitative results in the literature (Cr2GaC, Cr2GeC, and V2GeC), additional analytical techniques, including thermal analysis, powder diffraction, total scattering, and various spectroscopic methods, are necessary to unravel the identity of the chemical compounds and transformations during the reaction. Here, we demonstrate the combination of these techniques to understand the details of the sol-gel synthesis of MAX phase V2PC. The metal phosphate complexes, as well as amorphous/nanocrystalline vanadium phosphate species (V in different oxidation states), are identified at all stages of the reaction and a full schematic of the reaction process is suggested. The early amorphous vanadium species undergo multiple changes of oxidation states while organic species decompose releasing a variety of small molecule gases. Amorphous oxides, analogous to [NH4][VO2][HPO4], V2PO4O, and VO2P2O7 are identified in the dried gel obtained during the early stages of the heating process (300 and 600 °C), respectively. They are carbothermally reduced starting at 900 °C and subsequently react to crystalline V2PC with the excess carbon in the reaction mixture. Through CHN analysis, we obtain an estimate of left-over amorphous carbon in the product which will guide future efforts of minimizing the amount of carbon in sol gel-produced MAX phases which is important for subsequent property studies.

Influence of the Precursor Structure on the Formation of Tungsten Oxide Polymorphs.

Understanding material nucleation processes is crucial for the development of synthesis pathways for tailormade materials. However, we currently have little knowledge of the influence of the precursor solution structure on the formation pathway of materials. We here use in situ total scattering to show how the precursor solution structure influences which crystal structure is formed during the hydrothermal synthesis of tungsten oxides. We investigate the synthesis of tungsten oxide from the two polyoxometalate salts, ammonium metatungstate, and ammonium paratungstate. In both cases, a hexagonal ammonium tungsten bronze (NH4)0.25WO3 is formed as the final product. If the precursor solution contains metatungstate clusters, this phase forms directly in the hydrothermal synthesis. However, if the paratungstate B cluster is present at the time of crystallization, a metastable intermediate phase in the form of a pyrochlore-type tungsten oxide, WO3·0.5H2O, initially forms. The pyrochlore structure then undergoes a phase transformation into the tungsten bronze phase. Our studies thus experimentally show that the precursor cluster structure present at the moment of crystallization directly influences the formed crystalline phase and suggests that the precursor structure just prior to crystallization can be used as a tool for targeting specific crystalline phases of interest.

Self-supported Pt-CoO networks combining high specific activity with high surface area for oxygen reduction.

Several concepts for platinum-based catalysts for the oxygen reduction reaction (ORR) are presented that exceed the US Department of Energy targets for Pt-related ORR mass activity. Most concepts achieve their high ORR activity by increasing the Pt specific activity at the expense of a lower electrochemically active surface area (ECSA). In the potential region controlled by kinetics, such a lower ECSA is counterbalanced by the high specific activity. At higher overpotentials, however, which are often applied in real systems, a low ECSA leads to limitations in the reaction rate not by kinetics, but by mass transport. Here we report on self-supported platinum-cobalt oxide networks that combine a high specific activity with a high ECSA. The high ECSA is achieved by a platinum-cobalt oxide bone nanostructure that exhibits unprecedentedly high mass activity for self-supported ORR catalysts. This concept promises a stable fuel-cell operation at high temperature, high current density and low humidification.

Sol Gel-Based Synthesis of the Phosphorus-Containing MAX Phase V2PC.

More than 150 MAX phases are known to date. Their chemical diversity is the result of mixing-and-matching early-to-mid transition metals (M), main group elements (A), and carbon and/or nitrogen (X). The vast majority of the respective carbides and (carbo)nitrides contain group 13 and 14 as the A element, such as Al, Ga, and Si. V2PC is among the least studied members of this family of materials; as a matter of fact, it is only mentioned in two pieces of original literature. The solid-state synthesis is extremely vaguely described and working with elemental phosphorus poses additional synthetic challenges. Here, we confirm these experimental difficulties and present an alternative sol gel-based approach to prepare almost single-phase V2PC. The versatility of the sol gel chemistry is further demonstrated by variation of the gel-building agent moving beyond citric acid as the carbon source. DFT calculations support the experimentally obtained structural parameters and show V2PC is a metal.

Solution Structure, Electronic Energy Levels, and Photophysical Properties of [Eu(MeOH)n-2m(NO3)m]3-m+ Complexes.

The structure of lanthanide(III) ions in solutions high in nitrate has been debated since the early days of lanthanide coordination chemistry. The structure and properties of lanthanides in these solutions are essential in industrial rare-earth separation, as well as in the fundamental solution chemistry of these elements. Pending decades of debate, it was established that nitrate is bidentate and coordinates in the inner sphere, and complexes have been observed with as many as four nitrates coordinated to a single lanthanide(III) center in nonaqueous solutions. We revisit the interactions between nitrate and europium(III) in methanol using optical spectroscopy, X-ray total scattering, and the current understanding of europium(III) photophysics. By a combination of direct and indirect methods to probe the structure, it was found that four distinct species from Eu(MeOH)93+ to [Eu(MeOH)3(NO3)3] are present in solutions containing from 0 to 2 M NO3- ions. It was shown that the changes in transition probabilities together with high-resolution spectra can provide information on speciation and how the minute changes in ligand field affect the microstates. By a comparison to total X-ray scattering, it was concluded that the optical spectra alone allow the constitution and symmetry of the europium(III) species to be determined. Most notably, the minute changes in the all oxygen atom coordination imply significant changes in the optical properties of the europium(III) center.

The effect of weighted averages when determining the speciation and structure-property relationships of europium(iii) dipicolinate complexes.

Lanthanide(iii) coordination chemistry in solution is inherently complicated by the lack of directional interactions and rapid ligand exchange. The latter can be eliminated in kinetically inert complexes, but remains a challenge in complexes between lanthanide(iii) ions and smaller ligands. As multiple conformations and partial decomplexation is an issue even with multidentate ligands, it will influence the observed solution properties of complexes of smaller ligands common in the field of f-elements coordination chemistry such as acetylacetonates and dipicolinates. Here, europium(iii) complexes with one, two and three dipicolinates were investigated in a series of 13 samples, where the composition was varied from 0 to 3 equivalents of dipicolinate. While the results did show the formation of three distinct europium(iii) dipicolinate complexes confirming the literature data on the system, clear discrepancies in speciation related properties were evident when comparing the results from absorption and luminescence spectroscopy. It was concluded that the difference is due to the difference in time constant of the two experiments. Furthermore, it is shown that the information obtained from luminescence arises from a weigthed average, and with discepancies between the observed and actual concentration exceeding 25%, it is advised that the weighted averages are taken into consideration when reporting on solution properties of lanthanide(iii) complexes. From the resolved optical spectra of [Eu(H2O)9]3+, [Eu(DPA)(H2O)6]+, [Eu(DPA)2(H2O)3]-, and [Eu(DPA)3]3-, the excited energy levels and transition probabilities are determined, and it was concluded that both transition probabilities and ligand field effects on the microstates are different in all four species.

Structural characterization and magnetic properties of chromium jarosite KCr3(OD)6(SO4)2.

Potassium chromium jarosite, KCr3(OH)6(SO4)2 (Cr-jarosite), is considered a promising candidate to display spin liquid behavior due to the strong magnetic frustration imposed by the crystal structure. However, the ground state magnetic properties have been debated, since Cr-jarosite is notoriously non-stoichiometric. Our study reports the magnetic properties for deuterated KCr3(OD)6(SO4)2 on chemically well-defined samples, which have been characteried by a combination of powder X-ray diffraction, neutron diffraction, solid state NMR spectroscopy, and scanning electron microscopy with energy dispersive spectroscopy. Eight polycrystalline samples, which all contained only 1-3% Cr vacancies were obtained. However, significant substitution (2-27%) of potassium with H2O and/or H3O+ was observed and resulted in pronounced stacking disorder along the c-axis. A clear second-order transition to an antiferromagnetically ordered phase at TN = 3.8(1) K with a small net moment of 0.03 µB per Cr3+-ion was obtained from vibrating sample magnetometry and temperature dependent neutron diffraction. The moment is attributed to spin canting caused by the Dzyaloshinskii-Moriya interaction. Thus, our experimental results imply that even ideal potassium chromium jarosite will exhibit magnetic order below 4 K and therefore it does not qualify as a true spin liquid material.

POMFinder: identifying polyoxometallate cluster structures from pair distribution function data using explainable machine learning.

Characterization of a material structure with pair distribution function (PDF) analysis typically involves refining a structure model against an experimental data set, but finding or constructing a suitable atomic model for PDF modelling can be an extremely labour-intensive task, requiring carefully browsing through large numbers of possible models. Presented here is POMFinder, a machine learning (ML) classifier that rapidly screens a database of structures, here polyoxometallate (POM) clusters, to identify candidate structures for PDF data modelling. The approach is shown to identify suitable POMs from experimental data, including in situ data collected with fast acquisition times. This automated approach has significant potential for identifying suitable models for structure refinement to extract quantitative structural parameters in materials chemistry research. POMFinder is open source and user friendly, making it accessible to those without prior ML knowledge. It is also demonstrated that POMFinder offers a promising modelling framework for combined modelling of multiple scattering techniques.

Atomic structural changes in the formation of transition metal tungstates: the role of polyoxometalate structures in material crystallization.

Material nucleation processes are poorly understood; nevertheless, an atomistic understanding of material formation would aid in the design of material synthesis methods. Here, we apply in situ X-ray total scattering experiments with pair distribution function (PDF) analysis to study the hydrothermal synthesis of wolframite-type MWO4 (M : Mn, Fe, Co, Ni). The data obtained allow the mapping of the material formation pathway in detail. We first show that upon mixing of the aqueous precursors, a crystalline precursor containing [W8O27]6- clusters forms for the MnWO4 synthesis, while amorphous pastes form for the FeWO4, CoWO4 and NiWO4 syntheses. The structure of the amorphous precursors was studied in detail with PDF analysis. Using database structure mining and an automated modelling strategy by applying machine learning, we show that the amorphous precursor structure can be described through polyoxometalate chemistry. A skewed sandwich cluster containing Keggin fragments describes the PDF of the precursor structure well, and the analysis shows that the precursor for FeWO4 is more ordered than that of CoWO4 and NiWO4. Upon heating, the crystalline MnWO4 precursor quickly converts directly to crystalline MnWO4, while the amorphous precursors transform into a disordered intermediate phase before the crystalline tungstates appear. Our data show that the more disordered the precursor is, the longer the reaction time required to form crystalline products, and disorder in the precursor phase appears to be a barrier for crystallization. More generally, we see that polyoxometalate chemistry is useful when describing the initial wet-chemical formation of mixed metal oxides.

Detailed Analysis of the Synthesis and Structure of MAX Phase (Mo0.75V0.25)5AlC4 and Its MXene Sibling (Mo0.75V0.25)5C4.

MAX phases with the general formula Mn+1AXn are layered carbides, nitrides, and carbonitrides with varying stacking sequence of layers of M6X octahedra and the A element depending on n. While "211" MAXphases (n = 1) are very common, MAX phases with higher n, especially n ≥ 3, have hardly been prepared. This work addresses open questions regarding the synthesis conditions, structure, and chemical composition of the "514" MAX phase. In contrast to literature reports, no oxide is needed to form the MAX phase, yet multiple heating steps at 1,600 °C are required. Using high-resolution X-ray diffraction, the structure of (Mo1-xVx)5AlC4 is thoroughly investigated, and Rietveld refinement suggests P-6c2 as the most fitting space group. SEM/EDS and XPS show that the chemical composition of the MAX phase is (Mo0.75V0.25)5AlC4. It was also exfoliated into its MXene sibling (Mo0.75V0.25)5C4 using two different techniques (using HF and an HF/HCl mixture) that lead to different surface terminations as shown by XPS/HAXPES measurements. Initial investigations of the electrocatalytic properties of both MXene versions show that, depending on the etchant, (Mo0.75V0.25)5C4 can reduce hydrogen at 10 mA cm-2 with an overpotential of 166 mV (HF only) or 425 mV (HF/HCl) after cycling the samples, which makes them a potential candidate as an HER catalyst.

Breaking with the Principles of Coreduction to Form Stoichiometric Intermetallic PdCu Nanoparticles.

Intermetallic nanoparticles (NPs) have shown enhanced catalytic properties as compared to their disordered alloy counterparts. To advance their use in green energy, it is crucial to understand what controls the formation of intermetallic NPs over alloy structures. By carefully selecting the additives used in NP synthesis, it is here shown that monodisperse, intermetallic PdCu NPs can be synthesized in a controllable manner. Introducing the additives iron(III) chloride and ascorbic acid, both morphological and structural control can be achieved. Combined, these additives provide a synergetic effect resulting in precursor reduction and defect-free growth; ultimately leading to monodisperse, single-crystalline, intermetallic PdCu NPs. Using in situ X-ray total scattering, a hitherto unknown transformation pathway is reported that diverges from the commonly reported coreduction disorder-order transformation. A Cu-rich structure initially forms, which upon the incorporation of Pd(0) and atomic ordering forms intermetallic PdCu NPs. These findings underpin that formation of stoichiometric intermetallic NPs is not limited by standard reduction potential matching and coreduction mechanisms, but is instead driven by changes in the local chemistry. Ultimately, using the local chemistry as a handle to tune the NP structure might open new opportunities to expand the library of intermetallic NPs by exploiting synthesis by design.

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles.

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl3 or H2OsCl6), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1-2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

Formation and growth mechanism for niobium oxide nanoparticles: atomistic insight from in situ X-ray total scattering.

Understanding the mechanisms for nanoparticle nucleation and growth is crucial for the development of tailormade nanomaterials. Here, we use X-ray total scattering and Pair Distribution Function analysis to follow the formation and growth of niobium oxide nanoparticles. We study the solvothermal synthesis from niobium chloride in benzyl alcohol, and through investigations of the influence of reaction temperature, a formation pathway can be suggested. Upon dissolution of niobium chloride in benzyl alcohol, octahedral [NbCl6-xOx] complexes form through exchange of chloride ligands. Heating of the solution results in polymerization, where larger clusters built from multiple edge-sharing [NbCl6-xOx] octahedra assemble. This leads to the formation of a nucleation cluster with the ReO3 type structure, which grows to form nanoparticles of the Wadsley-Roth type H-Nb2O5 structure, which in the bulk phase usually only forms at high temperature. Upon further growth, structural defects appear, and the presence of shear-planes in the structure appears highly dependent on nanoparticle size.

Size-induced amorphous structure in tungsten oxide nanoparticles.

The properties of functional materials are intrinsically linked to their atomic structure. When going to the nanoscale, size-induced structural changes in atomic structure often occur, however these are rarely well-understood. Here, we systematically investigate the atomic structure of tungsten oxide nanoparticles as a function of the nanoparticle size and observe drastic changes when the particles are smaller than 5 nm, where the particles are amorphous. The tungsten oxide nanoparticles are synthesized by thermal decomposition of ammonium metatungstate hydrate in oleylamine and by varying the ammonium metatungstate hydrate concentration, the nanoparticle size, shape and structure can be controlled. At low concentrations, nanoparticles with a diameter of 2-4 nm form and adopt an amorphous structure that locally resembles the structure of polyoxometalate clusters. When the concentration is increased the nanoparticles become elongated and form nanocrystalline rods up to 50 nm in length. The study thus reveals a size-dependent amorphous structure when going to the nanoscale and provides further knowledge on how metal oxide crystal structures change at extreme length scales.

Insights from In Situ Studies on the Early Stages of Platinum Nanoparticle Formation.

Understanding the formation of nanomaterials down to the atomic level is key to rational design of advanced materials. Despite their widespread use and intensive study over the years, the detailed formation mechanism of platinum (Pt) nanoparticles remains challenging to explore and rationalize. Here, various in situ characterization techniques, and in particular X-ray total scattering with pair distribution function (PDF) analysis, are used to follow the structural and chemical changes taking place during a surfactant-free synthesis of Pt nanoparticles in alkaline methanol. Polynuclear structures form at the beginning of the synthesis, and Pt-Pt pair distances are identified before any nanoparticles are generated. The structural motifs best describing the species formed change with time, e.g., from [PtCl5-PtCl5] and [PtCl6-Pt2Cl6-PtCl6] to [Pt2Cl10-Pt3Cl8-Pt2Cl10]. The formation of these polynuclear structures with Pt-Pt coordination before the formation of the nanoparticles is suggested to account for the fast nucleation observed in the synthesis.

Size Induced Structural Changes in Molybdenum Oxide Nanoparticles.

Nanosizing of metal oxide particles is a common strategy for improving materials properties; however, small particles often take structures different from the bulk material. MoO2 nanoparticles show a structure that is distinct from the bulk distorted rutile structure and which has not yet been determined. Here, we present a model for nanostructured MoO2 obtained through detailed atomic pair distribution function analysis combined with high-resolution electron microscopy. Defects occur in the arrangement of [MoO6] octahedra, in both large (40-100 nm) nanoparticles, where the overall distorted rutile structure is preserved, and in small nanoparticles (<5 nm), where a new nanostructure is formed. The study provides a piece in the puzzle of understanding the structure/properties relationship of molybdenum oxides and further our understanding of the origin of structural changes taking place upon nanosizing in oxide materials.