Quantifying the regime of thermodynamic control for solid-state reactions during ternary metal oxide synthesis.

The success of solid-state synthesis often hinges on the first intermediate phase that forms, which determines the remaining driving force to produce the desired target material. Recent work suggests that when reaction energies are large, thermodynamics primarily dictates the initial product formed, regardless of reactant stoichiometry. Here, we validate this principle and quantify its constraints by performing in situ characterization on 37 pairs of reactants. These experiments reveal a threshold for thermodynamic control in solid-state reactions, whereby initial product formation can be predicted when its driving force exceeds that of all other competing phases by ≥60 milli-electron volt per atom. In contrast, when multiple phases have a comparable driving force to form, the initial product is more often determined by kinetic factors. Analysis of the Materials Project data shows that 15% of possible reactions fall within the regime of thermodynamic control, highlighting the opportunity to predict synthesis pathways from first principles.

Aluminothermic reduction of CeO2: mechanism of an economical route to aluminum-cerium alloys.

Cerium oxide is a low-value byproduct of rare-earth mining yet constitutes the largest fraction of the rare earth elements. The reduction of cerium oxide by liquid aluminum is proposed as an energy- and cost-efficient route to produce high-strength Al-Ce alloys. This work investigated the mechanism of a multi-step reduction reaction to facilitate the industrial adaptation of the process. Differential scanning calorimetry in combination with time-resolved synchrotron diffraction data uncovered the rate-limiting reaction step as the origin of the reported temperature dependence of reduction efficiency. This is the first in situ study of a metallothermic reaction mechanism and will serve as guidance for cost- and energy efficient industrial process control.

Self-Limiting Sub-5 nm Nanodiamonds by Geochemistry-Inspired Synthesis.

Controlling diamond structures with nanometer precision is fundamentally challenging owing to their extreme and far-from-equilibrium synthetic conditions. State-of-the-art techniques, including detonation, chemical vapor deposition, mechanical grinding, and high-pressure-high-temperature synthesis, yield nanodiamond particles with a broad distribution of sizes. Despite many efforts, the direct synthesis of nanodiamonds with precisely controlled diameters remains elusive. Here the geochemistry-inspired synthesis of sub-5 nm nanodiamonds with sub-nanometer size deviation is described. High-pressure-high-temperature treatment of uniform iron carbide nanoparticles embedded in iron oxide matrices yields nanodiamonds with tunable diameters down to 2.13 and 0.22 nm standard deviation. A self-limiting, redox-driven, and diffusion-controlled solid-state reaction mechanism is proposed and supported by in situ X-ray diffraction, ex situ characterizations, and computational modeling. This work provides a unique mechanism for the precise control of nanostructured diamonds under extreme conditions and paves the road for the full realization of their potential in emerging technologies.

Direct Observation of the Pressure-Induced Structural Variation in Gold Nanoclusters and the Correlated Optical Response.

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au25S18, has been directly identified. We found that a 0.1 Å decrease of the Au-Au bond length could induce a blue-shift of 30 nm in the photoluminescence spectra of gold nanoclusters. From theoretical calculations, the origins of the blue-shift and enhanced photoluminescence under pressure are investigated, which are ascribed to molecular orbital symmetry and conformational locking, respectively. The combination of the high-pressure in situ X-ray results with both theoretical and experimental optical spectra provides a direct and generalizable avenue to unveil the underlying structure-property relations for nanoclusters and nanoparticles which cannot be obtained through traditional physical chemistry measurements.

Zirconium Carbide Mediates Coke-Resistant Methane Dry Reforming on Nickel-Zirconium Catalysts.

Graphitic deposits anti-segregate into Ni0 nanoparticles to provide restored CH4 adsorption sites and near-surface/dissolved C atoms, which migrate to the Ni0 /ZrO2 interface and induce local Zrx Cy formation. The resulting oxygen-deficient carbidic phase boundary sites assist in the kinetically enhanced CO2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni-CeZrx Oy catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.

Anomalous thermal transport under high pressure in boron arsenide.

High pressure represents extreme environments and provides opportunities for materials discovery1-8. Thermal transport under high hydrostatic pressure has been investigated for more than 100 years and all measurements of crystals so far have indicated a monotonically increasing lattice thermal conductivity. Here we report in situ thermal transport measurements in the newly discovered semiconductor crystal boron arsenide, and observe an anomalous pressure dependence of the thermal conductivity. We use ultrafast optics, Raman spectroscopy and inelastic X-ray scattering measurements to examine the phonon bandstructure evolution of the optical and acoustic branches, as well as thermal conductivity under varied temperatures and pressures up to 32 gigapascals. Using atomistic theory, we attribute the anomalous high-pressure behaviour to competitive heat conduction channels from interactive high-order anharmonicity physics inherent to the unique phonon bandstructure. Our study verifies ab initio theory calculations and we show that the phonon dynamics-resulting from competing three-phonon and four-phonon scattering processes-are beyond those expected from classical models and seen in common materials. This work uses high-pressure spectroscopy combined with atomistic theory as a powerful approach to probe complex phonon physics and provide fundamental insights for understanding microscopic energy transport in materials of extreme properties.

Atomic-Scale Insights into Nickel Exsolution on LaNiO3 Catalysts via In Situ Electron Microscopy.

Using a combination of in situ bulk and surface characterization techniques, we provide atomic-scale insight into the complex surface and bulk dynamics of a LaNiO3 perovskite material during heating in vacuo. Driven by the outstanding activity LaNiO3 in the methane dry reforming reaction (DRM), attributable to the decomposition of LaNiO3 during DRM operation into a Ni//La2O3 composite, we reveal the Ni exsolution dynamics both on a local and global scale by in situ electron microscopy, in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy. To reduce the complexity and disentangle thermal from self-activation and reaction-induced effects, we embarked on a heating experiment in vacuo under comparable experimental conditions in all methods. Associated with the Ni exsolution, the remaining perovskite grains suffer a drastic shrinkage of the grain volume and compression of the structure. Ni particles mainly evolve at grain boundaries and stacking faults. Sophisticated structure analysis of the elemental composition by electron-energy loss mapping allows us to disentangle the distribution of the different structures resulting from LaNiO3 decomposition on a local scale. Important for explaining the DRM activity, our results indicate that most of the Ni moieties are oxidized and that the formation of NiO occurs preferentially at grain edges, resulting from the reaction of the exsolved Ni particles with oxygen released from the perovskite lattice during decomposition via a spillover process from the perovskite to the Ni particles. Correlating electron microscopy and X-ray diffraction data allows us to establish a sequential two-step process in the decomposition of LaNiO3 via a Ruddlesden-Popper La2NiO4 intermediate structure. Exemplified for the archetypical LaNiO3 perovskite material, our results underscore the importance of focusing on both surface and bulk characterization for a thorough understanding of the catalyst dynamics and set the stage for a generalized concept in the understanding of state-of-the art catalyst materials on an atomic level.

Mapping completeness.

Tchon & Makal [IUCrJ (2021), 8, 1006-1017] use numerical simulations to explore the dependence of data completeness on crystal orientation, X-ray energy and diamond anvil cell geometry for high-pressure diffraction experiments. Their completeness heat maps for different Laue classes can be used to guide optimization of high-pressure single-crystal diffraction experiments.

Steering the methanol steam reforming reactivity of intermetallic Cu-In compounds by redox activation: stability vs. formation of an intermetallic compound-oxide interface.

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound-oxide interface, we selected the Cu-In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu-In compounds - Cu7In3, Cu2In and Cu11In9 - were studied both in an untreated and redox-activated state resulting from alternating oxidation-reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes. The inherent activity under batch MSR conditions is highest for Cu2In, corroborating the results of a Cu2In/In2O3 sample accessed through reactive metal-support interaction. Under flow MSR operation, Cu7In3 displays considerable deactivation, while Cu2In and Cu11In9 feature stable performance at simultaneously high CO2 selectivity. The missing significant self-activation is most evident in the operando thermogravimetric experiments, where no oxidation is detected for any of the intermetallic compounds. In situ X-ray diffraction allowed us to monitor the partial decomposition and redox activation of the Cu-In intermetallic compounds into Cu0.9In0.1/In2O3 (from Cu7In3), Cu7In3/In2O3 (from Cu2In) and Cu7In3/Cu0.9In0.1/In2O3 (from Cu11In9) interfaces with superior MSR performance compared to the untreated samples. Although the catalytic profiles appear surprisingly similar, the latter interface with the highest indium content exhibits the least deactivation, which we explain by formation of stabilizing In2O3 patches under MSR conditions.

Eye movement alterations in presymptomatic C9orf72 expansion gene carriers.

OBJECTIVE: The clinical manifestation of amyotrophic lateral sclerosis (ALS) is characterized by motor neuron degeneration, whereas frontotemporal dementia (FTD) patients show alterations of behavior and cognition. Both share repeat expansions in C9orf72 as the most prevalent genetic cause. Before disease-defining symptoms onset, structural and functional changes at cortical level may emerge in C9orf72 carriers. Here, we characterized oculomotor parameters and their association to neuropsychological domains in apparently asymptomatic individuals with mutations in ALS/FTD genes. PATIENTS AND METHODS: Forty-eight carriers of ALS genes, without any clinical symptoms underwent video-oculographic examination, including 22 subjects with C9orf72 mutation, 17 with SOD1, and 9 with other ALS associated gene mutations (n = 3 KIF5A; n = 3 FUS/FUS + TBK1; n = 1 NEK1; n = 1 SETX; n = 1 TDP43). A total of 17 subjects underwent a follow-up measurement. Data were compared to 54 age- and gender-matched healthy controls. Additionally, mutation carriers performed a neuropsychological assessment. RESULTS: In comparison to controls, the presymptomatic subjects performed significantly worse in executive oculomotor tasks such as the ability to perform correct anti-saccades. A gene mutation subgroup analysis showed that dysfunctions in C9orf72 carriers were much more pronounced than in SOD1 carriers. The anti-saccade error rate of ALS mutation carriers was associated with cognitive deficits: this correlation was increased in subjects with C9orf72 mutation, whereas SOD1 carriers showed no associations. CONCLUSION: In C9orf72 carriers, executive eye movement dysfunctions, especially the increased anti-saccade error rate, were associated with cognitive impairment and unrelated to time. These oculomotor impairments are in support of developmental deficits in these mutations, especially in prefrontal areas.

Exploring microstructures in lower mantle mineral assemblages with synchrotron x-rays.

Understanding dynamics across phase transformations and the spatial distribution of minerals in the lower mantle is crucial for a comprehensive model of the evolution of the Earth's interior. Using the multigrain crystallography technique (MGC) with synchrotron x-rays at pressures of 30 GPa in a laser-heated diamond anvil cell to study the formation of bridgmanite [(Mg,Fe)SiO3] and ferropericlase [(Mg,Fe)O], we report an interconnected network of a smaller grained ferropericlase, a configuration that has been implicated in slab stagnation and plume deflection in the upper part of the lower mantle. Furthermore, we isolated individual crystal orientations with grain-scale resolution, provide estimates on stress evolutions on the grain scale, and report {110} twinning in an iron-depleted bridgmanite, a mechanism that appears to aid stress relaxation during grain growth and likely contributes to the lack of any appreciable seismic anisotropy in the upper portion of the lower mantle.

Stress-Induced Structural Transformations in Au Nanocrystals.

Nanocrystals can exist in multiply twinned structures like icosahedron or single crystalline structures like cuboctahedron. Transformations between these structures can proceed through diffusion or displacive motion. Experimental studies on nanocrystal structural transformations have focused on high-temperature diffusion-mediated processes. Limited experimental evidence of displacive motion exists. We report structural transformation of 6 nm Au nanocrystals under nonhydrostatic pressure of 7.7 GPa in a diamond anvil cell that is driven by displacive motion. X-ray diffraction and transmission electron microscopy were used to detect the structural transformation from multiply twinned to single crystalline. Single crystalline nanocrystals were recovered after unloading, then quickly reverted to the multiply twinned state after dispersion in toluene. The dynamics of recovery was captured using TEM which showed surface recrystallization and rapid twin boundary motion. Molecular dynamics simulations showed that twin boundaries are unstable due to defects nucleated from the interior of the nanocrystal.

Potential Control of Oxygen Non-Stoichiometry in Cerium Oxide and Phase Transition Away from Equilibrium.

Cerium oxide (ceria, CeO2) is a technologically important material for energy conversion applications. Its activities strongly depend on redox states and oxygen vacancy concentration. Understanding the functionality of chemical active species and behavior of oxygen vacancy during operation, especially in high-temperature solid-state electrochemical cells, is the key to advance future material design. Herein, the structure evolution of ceria is spatially resolved using bulk-sensitive operando X-ray diffraction and spectroscopy techniques. During water electrolysis, ceria undergoes reduction, and its oxygen non-stoichiometry shows a dependence on the electrochemical current. Cerium local bonding environments vary concurrently to accommodate oxygen vacancy formation, resulting in changes in Ce-O coordination number and Ce3+/Ce4+ redox couple. When reduced enough, a crystallographic phase transition occurs from α to an α' phase with more oxygen vacancies. Nevertheless, the transition behavior is intriguingly different from the one predicted in the standard phase diagram of ceria. This paper demonstrates a feasible means to control oxygen non-stoichiometry in ceria via electrochemical potential. It also sheds light on the mechanism of phase transitions induced by electrochemical potential. For electrochemical systems, effects from a large-scale electrical environment should be taken into consideration, besides effective oxygen partial pressure and temperature.

Nucleation of Dislocations in 3.9 nm Nanocrystals at High Pressure.

As circuitry approaches single nanometer length scales, it has become important to predict the stability of single nanometer-sized metals. The behavior of metals at larger scales can be predicted based on the behavior of dislocations, but it is unclear if dislocations can form and be sustained at single nanometer dimensions. Here, we report the formation of dislocations within individual 3.9 nm Au nanocrystals under nonhydrostatic pressure in a diamond anvil cell. We used a combination of x-ray diffraction, optical absorbance spectroscopy, and molecular dynamics simulation to characterize the defects that are formed, which were found to be surface-nucleated partial dislocations. These results indicate that dislocations are still active at single nanometer length scales and can lead to permanent plasticity.

High-pressure strengthening in ultrafine-grained metals.

The Hall-Petch relationship, according to which the strength of a metal increases as the grain size decreases, has been reported to break down at a critical grain size of around 10 to 15 nanometres1,2. As the grain size decreases beyond this point, the dominant mechanism of deformation switches from a dislocation-mediated process to grain boundary sliding, leading to material softening. In one previous approach, stabilization of grain boundaries through relaxation and molybdenum segregation was used to prevent this softening effect in nickel-molybdenum alloys with grain sizes below 10 nanometres3. Here we track in situ the yield stress and deformation texturing of pure nickel samples of various average grain sizes using a diamond anvil cell coupled with radial X-ray diffraction. Our high-pressure experiments reveal continuous strengthening in samples with grain sizes from 200 nanometres down to 3 nanometres, with the strengthening enhanced (rather than reduced) at grain sizes smaller than 20 nanometres. We achieve a yield strength of approximately 4.2 gigapascals in our 3-nanometre-grain-size samples, ten times stronger than that of a commercial nickel material. A maximum flow stress of 10.2 gigapascals is obtained in nickel of grain size 3 nanometres for the pressure range studied here. We see similar patterns of compression strengthening in gold and palladium samples down to the smallest grain sizes. Simulations and transmission electron microscopy reveal that the high strength observed in nickel of grain size 3 nanometres is caused by the superposition of strengthening mechanisms: both partial and full dislocation hardening plus suppression of grain boundary plasticity. These insights contribute to the ongoing search for ultrastrong metals via materials engineering.

New Estimator for Gravitational Lensing Using Galaxy and Intensity Mapping Surveys.

We introduce the galaxy intensity mapping cross-correlation estimator (GIMCO), which is a new tomographic estimator for the gravitational lensing potential, based on a combination of intensity mapping (IM) and galaxy number counts. The estimator can be written schematically as IM(z_{f})×galaxy(z_{b})-galaxy(z_{f})×IM(z_{b}) for a pair of distinct redshifts (z_{f},z_{b}); this combination allows to greatly reduce the contamination by density-density correlations, thus isolating the lensing signal. As an estimator constructed only from cross-correlations, it is additionally less susceptible to systematic effects. We show that the new estimator strongly suppresses cosmic variance and consequently improves the signal-to-noise ratio (SNR) for the detection of lensing, especially on linear scales and intermediate redshifts. For cosmic variance dominated surveys, the SNR of our estimator is a factor of 30 larger than the SNR obtained from the correlation of galaxy number counts only. Shot noise and interferometer noise reduce the SNR. For the specific example of the dark energy survey (DES) cross-correlated with the hydrogen intensity mapping and real time analysis experiment (HIRAX), the SNR is around four, whereas for Euclid cross-correlated with HIRAX it reaches 52. This corresponds to an improvement of a factor of 4-5 compared to the SNR from DES alone. For Euclid cross-correlated with HIRAX the improvement with respect to Euclid alone strongly depends on the redshift. We find that the improvement is particularly important for redshifts below 1.6, where it reaches a factor of 5. This makes our estimator especially valuable to test dark energy and modified gravity, that are expected to leave an impact at low and intermediate redshifts.

Longitudinal brain atrophy distribution in advanced Parkinson's disease: What makes the difference in "cognitive status" converters?

We investigated the brain atrophy distribution pattern and rate of regional atrophy change in Parkinson's disease (PD) in association with the cognitive status to identify the morphological characteristics of conversion to mild cognitive impairment (MCI) and dementia (PDD). T1-weighted longitudinal 3T MRI data (up to four follow-up assessments) from neuropsychologically well-characterized advanced PD patients (n = 172, 8.9 years disease duration) and healthy elderly controls (n = 85) enrolled in the LANDSCAPE study were longitudinally analyzed using a linear mixed effect model and atlas-based volumetry and cortical thickness measures. At baseline, PD patients presented with cerebral atrophy and cortical thinning including striatum, temporoparietal regions, and primary/premotor cortex. The atrophy was already observed in "cognitively normal" PD patients (PD-N) and was considerably more pronounced in cognitively impaired PD patients. Linear mixed effect modeling revealed almost similar rates of atrophy change in PD and controls. The group comparison at baseline between those PD-N whose cognitive performance remained stable (n = 42) and those PD-N patients who converted to MCI/PDD ("converter" cPD-N, n = 26) indicated suggested cortical thinning in the anterior cingulate cortex in cPD-N patients which was correlated with cognitive performance. Our results suggest that cortical brain atrophy has been already expanded in advanced PD patients without overt cognitive deficits while atrophy progression in late disease did not differ from "normal" aging regardless of the cognitive status. It appears that cortical atrophy begins early and progresses already in the initial disease stages emphasizing the need for therapeutic interventions already at disease onset.

Olfactory screening of Parkinson's Disease patients and healthy subjects in China and Germany: A study of cross-cultural adaptation of the Sniffin' Sticks 12-identification test.

BACKGROUND: Olfactory testing is a useful tool in the differential diagnosis of Parkinson's Disease (PD). Although fast and easy to use, the high intercultural variability of odor detection limits the world-wide use of the most common test sets. OBJECTIVE: The aim of this study was to test one of the most commonly used olfactory tests (Sniffin' Sticks 12-identification test) in an adapted version for a Chinese population of healthy subjects and PD patients. METHODS: For this purpose, cohorts of 39 Chinese and 41 German PD patients as well as 70 Chinese and 100 German healthy subjects have been examined both with the original and the adapted version of the Sniffin' Sticks test, the latter being designed according to the regional culture. RESULTS: The adapted Chinese version of the Sniffin' Sticks 12 identification test proved to discriminate Chinese PD patients from controls with a high specificity but relatively low sensitivity. Yet not all odor exchanges would have been necessary as the original odors including liquorice and coffee showed an equally high identification rate in the Chinese and German cohorts. CONCLUSIONS: The results showed that the newly adapted test could be used as a screening test for PD related olfactory dysfunction in a Chinese population. However further investigation will be necessary to optimize the selection of odors for the Chinese version of the test.

Structural brain signature of cognitive decline in Parkinson's disease: DTI-based evidence from the LANDSCAPE study.

BACKGROUND: The nonmotor symptom spectrum of Parkinson's disease (PD) includes progressive cognitive decline mainly in late stages of the disease. The aim of this study was to map the patterns of altered structural connectivity of patients with PD with different cognitive profiles ranging from cognitively unimpaired to PD-associated dementia. METHODS: Diffusion tensor imaging and neuropsychological data from the observational multicentre LANDSCAPE study were analyzed. A total of 134 patients with PD with normal cognitive function (56 PD-N), mild cognitive impairment (67 PD-MCI), and dementia (11 PD-D) as well as 72 healthy controls were subjected to whole-brain-based fractional anisotropy mapping and covariance analysis with cognitive performance measures. RESULTS: Structural data indicated subtle changes in the corpus callosum and thalamic radiation in PD-N, whereas severe white matter impairment was observed in both PD-MCI and PD-D patients including anterior and inferior fronto-occipital, uncinate, insular cortices, superior longitudinal fasciculi, corona radiata, and the body of the corpus callosum. These regional alterations were demonstrated for PD-MCI and were more pronounced in PD-D. The pattern of involved regions was significantly correlated with the Consortium to Establish a Registry for Alzheimer's Disease (CERAD) total score. CONCLUSIONS: The findings in PD-N suggest impaired cross-hemispherical white matter connectivity that can apparently be compensated for. More pronounced involvement of the corpus callosum as demonstrated for PD-MCI together with affection of fronto-parieto-temporal structural connectivity seems to lead to gradual disruption of cognition-related cortico-cortical networks and to be associated with the onset of overt cognitive deficits. The increase of regional white matter damage appears to be associated with the development of PD-associated dementia.

Implementation and application of the peak scaling method for temperature measurement in the laser heated diamond anvil cell.

A new design for a double-sided high-pressure diamond anvil cell laser heating set-up is described. The prototype is deployed at beamline 12.2.2 of the Advanced Light Source at Lawrence Berkeley National Lab. Our compact design features shortened mechanical lever arms, which results in more stable imaging optics, and thus more user friendly and more reliable temperature measurements based on pyrometry. A modification of the peak scaling method was implemented for pyrometry, including an iterative method to determine the absolute peak temperature, thus allowing for quasi-real time temperature mapping of the actual hotspot within a laser-heated diamond anvil cell without any assumptions on shape, size, and symmetry of the hotspot and without any assumptions to the relationship between fitted temperature and peak temperature. This is important since we show that the relationship between peak temperature and temperature obtained by fitting the Planck function against the thermal emission spectrum averaged over the entire hotspot is not constant but depends on variable fitting parameters (in particular, the size and position of the fitting window). The accuracy of the method is confirmed through measuring melting points of metal wires at ambient pressure. Having absolute temperature maps in real time allows for more differentiated analyses of laser heating experiments. We present such an example of the pressure variations within a heated hotspot of AgI at a loaded base pressure of 3.8 GPa.