High-pressure Transformations Research Articles

2D Co-N-C catalysts derived by 1D CoxZn1-xO hexagonal microrods for oxygen reduction reaction

A novel and feasible strategy to construct 2D Co-N-C catalyst from one-dimensional (1D) CoxZn1-xO microrod is reported. In the strategy, 1D CoxZn1-xO microrods are firstly transformed into CoxZn1-xO@CoZn-ZIF hexagonal core-shell microrods by regulating the reaction conditions of high-pressure vapor-solid transformation, and subsequently pyrolyzed at high temperature to form Co-N-C hexagonal microtubes, which are finally fractured along its edges under the action of thermal stress, evolving gradually to Co-N-C nanosheets. Besides, by investigating the effects of Co doping contents, a catalyst with optimal chemical and structural properties and more highly accessible Co-N4 active sites has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in alkaline media. Among them, Co0.3-N-C NS exhibits superior ORR performance (Eon=1.01 V, E1/2 = 0.87 V), durability and tolerance to methanol than those of commercial Pt/C catalysts (Eon=0.99 V, E1/2 = 0.85 V) in alkaline media.

Direct imaging of shock wave splitting in diamond at Mbar pressure

Understanding the behavior of matter at extreme pressures of the order of a megabar (Mbar) is essential to gain insight into various physical phenomena at macroscales—the formation of planets, young stars, and the cores of super-Earths, and at microscales—damage to ceramic materials and high-pressure plastic transformation and phase transitions in solids. Under dynamic compression of solids up to Mbar pressures, even a solid with high strength exhibits plastic properties, causing the induced shock wave to split in two: an elastic precursor and a plastic shock wave. This phenomenon is described by theoretical models based on indirect measurements of material response. The advent of x-ray free-electron lasers (XFELs) has made it possible to use their ultrashort pulses for direct observations of the propagation of shock waves in solid materials by the method of phase-contrast radiography. However, there is still a lack of comprehensive data for verification of theoretical models of different solids. Here, we present the results of an experiment in which the evolution of the coupled elastic–plastic wave structure in diamond was directly observed and studied with submicrometer spatial resolution, using the unique capabilities of the x-ray free-electron laser (XFEL). The direct measurements allowed, for the first time, the fitting and validation of the 2D failure model for diamond in the range of several Mbar. Our experimental approach opens new possibilities for the direct verification and construction of equations of state of matter in the ultra-high-stress range, which are relevant to solving a variety of problems in high-energy-density physics.

More words but less investment: Rookie CEOs and firms’ digital transformations

In digital economy, firm’s digital transformation is an important means of achieving high-quality development. Adopting career concerns theory, we examine rookie CEOs’ impact on firms’ digital transformations, using Chinese A-share listed firms from 2007 to 2019. (1) Rookie CEOs disclose more digital transformation information, but invest less in substantial transformation, i.e., “more words but less investment”. (2) Under high performance pressure and difficult digital transformation, rookie CEOs are more likely to adopt the above strategy. (3) Internal and external governance mechanisms help effectively monitor and mitigate such behaviors. (4) The above strategy helps CEOs decrease short-term, but not long-term, dismissal probabilities. Our findings elucidate firms’ digital transformation practices and the decision styles of CEOs with different experience levels.

Toward better understanding of the high-pressure structural transformation in beryllium by the statistical moment method.

Beryllium is a vital alkaline-earth metal for plasma physics, space science, and nuclear technology. Unfortunately, its accurate phase diagram is clouded by many controversial results, even though solid beryllium can only exist with hcp or bcc crystalline structures. Herein, we offer a simple quantum-statistical solution to the above problem. Our core idea is to develop the moment expansion technique to determine the Helmholtz free energy under extreme conditions. This strategy helps elucidate the underlying correlation among symmetric characteristics, vibrational excitations, and physical stabilities. In particular, our analyses reveal that the appearance of anharmonic effects forcefully straightens up the hcp-bcc boundary. This phenomenon explains why it has been difficult to detect bcc signatures via diamond-anvil-cell measurements. Besides, we modify the work-heat equivalence principle to quickly obtain the high-pressure melting profile from the room-temperature equation of state. The hcp-bcc-liquid triple point of beryllium is found at 165 GPa and 4559 K. Our theoretical findings agree excellently with cutting-edge ab initio simulations adopting the phonon quasiparticle method and the thermodynamic integration. Finally, we consider the principal Hugoniot curve and its secondary branches to explore the behaviors of beryllium under shock compression. Our predictions would be advantageous for designing inertial-confinement-fusion experiments.

Phase relations, thermal conductivity and elastic properties of ZrO2 and HfO2 polymorphs at high pressures and temperatures.

In the present study, P-T phase diagrams of ZrO2 and HfO2 for a wide pressure range of 0-150 GPa at 0-2500 K were calculated for the first time using density functional theory with the method of lattice dynamics within the quasi-harmonic approximation. We calculated P-T conditions for a full sequence of high-pressure transformations, P21/c → Pbca → Pnma → P6̄2m, for both compounds. At low temperatures, these transformations for ZrO2 are obtained at 7.6 GPa (P21/c → Pbca), 13.4 GPa (Pbca → Pnma), and 143 GPa (Pnma → P6̄2m), while for HfO2 similar polymorphic transitions are obtained at 9 GPa (P21/c → Pbca), 16 GPa (Pbca → Pnma), and 126 GPa (Pnma → P6̄2m), correspondingly. At high temperatures, for both ZrO2 and HfO2 the P21/c and Pbca structures transform into the P42/nmc modification. In addition, the thermal conductivity and elastic properties of the ZrO2 and HfO2 polymorphs were calculated and compared with the available experimental and theoretical data.

Structural Evolution of D 5h (1)-C90 under High Pressure: A Mediate Allotrope of Nanocarbon from Zero-Dimensional Fullerene to One-Dimensional Nanotube

The hybridization of fullerene and nanotube structures in newly isolated C90 with the D 5h symmetric group (D 5h (1)-C90) provides an ideal model as a mediating allotrope of nanocarbon from zero-dimensional (0D) fullerene to one-dimensional nanotube. Raman and infrared spectroscopy combined with classical molecular dynamics simulation were used to investigate the structural evolution of D 5h (1)-C90 at ambient and high pressure up to 35.1 GPa. Interestingly, the high-pressure transformations of D 5h (1)-C90 exhibit the features of both fullerene and nanotube. At around 2.5 GPa, the D 5h (1)-C90 molecule in the crystal undergoes an orientational transition to a restricted rotation. At 6.6 GPa, the tubular hexagonal part occurs and transforms into a dumbbell-like structure at higher pressure. The material starts to amorphize above 13.9 GPa, and the transition is reversible until the pressure exceeds 25 GPa. The amorphization is probably correlated with both the intermolecular bonding and the morphology change. Our results enrich our understanding of structural changes in nanocarbon from 0D to 1D.

High-pressure transformations of CaC2O5 - a full structural trend from double [CO3] triangles through the isolated group of [CO4] tetrahedra to framework and layered structures.

Over the past few years, the concept of carbonates, as the salts of MCO3 or composition with [CO3] triangles in the crystal structures, was sufficiently extended. In addition to carbonates, crystal structures with stoichiometry M3CO5, M2CO4 and MC2O5 were predicted and successfully synthesized. In the present study, based on density functional theory and crystal structure prediction algorithms, we found a novel structure of CaC2O5, namely Ca-pyrocarbonate with monoclinic symmetry Cc, which is one of the possible agents of the global carbon cycle. This structure is characterized by the isolated [C2O5] groups consisting of two [CO3] triangles connected through a common oxygen atom. The thermodynamic stability field of Ca-pyrocarbonate with respect to the decomposition reaction into calcium carbonate and carbon dioxide begins at a pressure of 10 GPa. As the pressure increases to 21 GPa, the structure of Ca-pyrocarbonate transforms into the recently synthesized tetragonal modification I4̄2d, in the structure of which carbon is in the sp3-hybridized state and [CO4] tetrahedra form isolated pyramidal [C4O10] anionic groups. At 59 GPa in the temperature range of 0-2500 K, CaC2O5-I4̄2d undergoes a phase transition to CaC2O5-Fdd2, with the framework structure of [CO4] tetrahedra. On further compression to about 80 GPa, the framework structure transforms into layered ones, C2 and Pc. In addition, we estimated the thermodynamic stability of CaC2O5 with respect to the minerals of the Earth's mantle. We found that CaC2O5 can coexist with bridgmanite up to pressures of 54 GPa at 300 K, where it reacts with the formation of a Ca-perovskite, magnesite, and solid CO2-V.

High-pressure vapor-solid transformation of 2D template to derive 2D Co–N–C electrocatalysts for oxygen reduction reaction

Two-dimensional (2D) cobalt zeolitic imidazolate frameworks (ZIF-67) have attracted significant research interests to synthesize cobalt and nitrogen co-doped carbon-based (Co–N–C) catalyst for oxygen reduction reaction (ORR). However, most of the current synthetic approaches of 2D ZIF-67 are energy-intensive, environmentally hazardous and low-yield. Herein, a feasible and efficient ‘morphology-retaining method via a high-pressure vapor-solid reaction’ are reported to synthesize 2D ZIF-67 nanosheets by using 2D cobalt carbonate hydroxide template. In the strategy, the high-pressure vapor caused by sublimation of 2-Melm and the pores formed from effusion of CO2 during transformation ensure the complete transformation from 2D template to 2D ZIF-67. The corresponding 2D Co–N–C catalyst exhibits comparable ORR electrocatalytic activity and better stability than Pt/C in alkaline media. The present method is expected to offer a feasible and universal way to efficiently synthesize 2D M–N–C catalysts.

Atomistic insights on the pressure-induced multi-layer graphene to diamond-like structure transformation

Recent results suggest a pressure-induced transformation of bilayer graphene to a diamond-like structure. Intriguingly, the reported transformation is absent or incomplete in multi-layer graphene beyond two layers, implying the suppression of the transformation by an unclear mechanism. In this work, we use reactive molecular dynamics simulations to describe the pressure-induced structural evolution of multi-layer graphene with two to six layers to pressures up to 200 GPa. The results show that bilayer graphene transforms into a diamond-like film, i.e., more than 75% sp3 hybridized atoms. In contrast, three- to six-layer graphene with AB layer stacking fail to form a diamond-like film up to 200 GPa. Bond formation analysis indicates that the transformation or its suppression is related to the generation of a bond chain structure across layers, connecting sp3 hybridized atoms. The result suggests that the ABA layer stacking is directly related to the hindering of the chain structure formation and the suppression of the transformation. Surprisingly, the bond-chain-structure transformation mechanism is effective in three-layer graphene with ABC layer stacking, as well as five-layer graphene with ABCAB layer stacking. That suggests that stacking faults are effective catalysts for the high-pressure transformation of multi-layer graphene to diamond.

High-pressure transformations in liquid rubidium

An electronic-driven liquid-liquid phase transition in rubidium is revealed by picosecond acoustic measurements combined with ab initio calculations. Picosecond acoustics were used to measure the melting line up to 10 GPa, finding the maximum in the melting curve at 7 GPa and 555 K. We observe the onset of a continuous liquid-liquid phase transition beginning around the melting maxima through until 16 GPa. Sound velocity shows a softening similar to that reported for liquid caesium, caused by a change in the bulk modulus during a crossover from the low-density to the high-density liquid. Guided by the ab initio calculations, we relate the changes in the thermoelastic properties to the progressive localization of the valence electrons in the pressure range of 6--16 GPa. At high pressure rubidium forms an electride liquid quantified by the appearance of interstitial quasiatoms localized in the valence electron density.

Dendritic reidite from the Chesapeake Bay impact horizon, Ocean Drilling Program Site 1073 (offshore northeastern USA): A fingerprint of distal ejecta?

Abstract High-pressure minerals provide records of processes not normally preserved in Earth’s crust. Reidite, a quenchable polymorph of zircon, forms at pressures >20 GPa during shock compression. However, there is no broad consensus among empirical, experimental, and theoretical studies on the nature of the polymorphic transformation. Here we decipher a multistage history of reidite growth recorded in a zircon grain in distal impact ejecta (offshore northeastern United States) from the ca. 35 Ma Chesapeake Bay impact event which, remarkably, experienced near-complete conversion (89%) to reidite. The grain displays two distinctive reidite habits: (1) intersecting sets of planar lamellae that are dark in cathodoluminescence (CL); and (2) dendritic epitaxial overgrowths on the lamellae that are luminescent in CL. While the former is similar to that described in literature, the latter has not been previously reported. A two-stage growth model is proposed for reidite formation at >40 GPa in Chesapeake Bay impact ejecta: formation of lamellar reidite by shearing during shock compression, followed by dendrite growth, also at high pressure, via recrystallization. The dendritic reidite is interpreted to nucleate on lamellae and replace damaged zircon adjacent to lamellae, which may be amorphous ZrSiO4 or possibly an intermediate phase, all before quenching. These results provide new insights on the microstructural evolution of the high-pressure polymorphic transformation over the microseconds-long interval of reidite stability during meteorite impact. Given the formation conditions, dendritic reidite may be a unique indicator of distal ejecta.

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.

Can We Predict the Pressure Induced Phase Transition of Urea? Application of Quantum Molecular Dynamics.

Crystalline urea undergoes polymorphic phase transition induced by high pressure. Form I, which is the most stable form at normal conditions and Form IV, which is the most stable form at 3.10 GPa, not only crystallize in various crystal systems but also differ significantly in the unit cell dimensions. The aim of this study was to determine if it is possible to predict polymorphic phase transitions by optimizing Form I at high pressure and Form IV at low pressure. To achieve this aim, a large number of periodic density functional theory (DFT) calculations were performed using CASTEP. After geometry optimization of Form IV at 0 GPa Form I was obtained, performing energy minimization of Form I at high pressure did not result in Form IV. However, employing quantum molecular isothermal–isobaric (NPT) dynamics calculations enabled to accurately predict this high-pressure transformation. This study shows the potential of different approaches in predicting the polymorphic phase transition and points to the key factors that are necessary to achieve the success.

Extraterrestrial, shock-formed, cage-like nanostructured carbonaceous materials

AbstractShock caused by impacts can convert carbonaceous material to diamond. During this transition, new materials can form that depend on the structure of the starting carbonaceous materials and the shock conditions. Here we report the discovery of cage-like nanostructured carbonaceous materials, including carbon nano-onions and bucky-diamonds, formed through extraterrestrial impacts in the Gujba (CBa) meteorite. The nano-onions are fullerene-type materials and range from 5 to 20 nm; the majority shows a graphitic core-shell structure, and some are characterized by fully curved, onion-like graphitic shells. The core is either filled with carbonaceous material or empty. We show the first, natural, 4 nm sized bucky-diamond, which is a type of carbon nano-onion consisting of multilayer graphitic shells surrounding a diamond core. We propose that the nano-onions formed during shock metamorphism, either the shock or the release wave, of the pre-existing primitive carbonaceous material that included nanodiamonds, poorly ordered graphitic material, and amorphous carbonaceous nanospheres. Bucky-diamonds could have formed either through the high-pressure transformation of nano-onions, or as an intermediate material in the high-temperature transformation of nanodiamond to nano-onion. Impact processing of planetary materials was and is a common process in our solar system, and by extension, throughout extrasolar planetary bodies. Together with our previous discovery of interstratified graphite-diamond in Gujba, our new findings extend the range of nano-structured carbonaceous materials formed in nature. Shock-formed nano-onions and bucky-diamonds are fullerene-type structures, and as such they could contribute to the astronomical 217.5 nm absorption feature.

Granular zircon from Vredefort granophyre (South Africa) confirms the deep injection model for impact melt in large impact structures

Abstract The Vredefort impact structure, South Africa, is a 2.02 Ga deeply eroded meteorite scar that provides an opportunity to study large impact craters at their lower stratigraphic levels. A series of anomalous granophyre dikes in the core of the structure are believed to be composed of an impact melt, which intruded downwards from the crater floor, exploiting fractures in basement rocks. However, the melt emplacement mechanisms and timing are not constrained. The granophyre dikes contain supracrustal xenoliths captured at higher levels, presently eroded. By studying these clasts and shocked minerals within, we can better understand the nature of dikes, magnitude of impact melt movement, conditions that affected target rocks near the impacted surface, and erosional rates. We report “former reidite in granular neoblastic” (FRIGN) zircon within a granite clast enclosed in the granophyre. High-pressure zircon transformation to reidite (ZrSiO4) and reversion to zircon resulted in zircon grains composed of fine neoblasts (∼0.5–3 µm) with two or three orthogonal orientations. Our finding provides new independent constraints on the emplacement history of Vredefort granophyre dikes. Based on the environment, where other FRIGN zircons are found (impact glasses and melts), the clast was possibly captured near the top of the impact melt sheet and transported to the lowermost levels of the structure, traveling some 8–10 km. Our finding not only provides the highest-pressure shock estimates thus far discovered in the Vredefort structure (≥30 GPa), but also shows that microscopic evidence of high shock pressures can be found within large eroded craters at their lowest stratigraphic levels.

Nanoscale constraints on the shock-induced transformation of zircon to reidite

In a hypervelocity impact event, the temperatures and pressures generated by the shock waves far exceed the values produced by endogenic processes. The shock-induced processes can modify the distribution of trace elements in zircon grains located in target rocks, potentially affecting the geochemical reliability of zircon, but also providing an opportunity to better understand the mechanisms of shock deformation. The formation of reidite lamellae by the shock-induced phase change of zircon has previously been proposed to be a diffusionless, martensitic transformation, with no associated atomic mobility over nanometre length scales. However, nanoscale characterization of the zircon–reidite interface and a low-angle boundary within the reidite by atom probe tomography, transmission electron microscopy and correlative analytical techniques, shows localised enrichment of particular trace elements (Y, Al, Ca, Be, Mg, Mn, and Ti). These observations indicate the presence of additional short-range diffusional components to explain the local compositional variations observed at the nanoscale for the high-pressure transformation of zircon to reidite lamellae. A new model for this transformation is proposed that consists of two stages: 1) the early stage of the impact event where the shock waves induce defects in the zircon grain and trigger a phase transformation, resulting in trace element segregation by interface migration; and 2) the recovery stage where the trace elements and shock induced defects migrate to areas of lower energy.

Perspective: High pressure transformations in nanomaterials and opportunities in material design

Pressure and temperature phase transitions of nanomaterials often differ significantly from those of their bulk parents, offering novel approaches for the engineering of original materials. The importance or even the dominance of surface atoms in the nanoworld enhances the effects of environment, geometry, and intercalation. In the present article, we explore the current knowledge of these effects, as evidenced in the high pressure phase diagrams of nanomaterials such as nanocrystals, carbon nanotubes, fullerites, graphene, and other 2D systems, as well as nanoporous structures like clathrates or zeolites. Recent advances and future challenges in the use of extreme thermodynamic conditions to develop new functional nanomaterials, composites, or devices will be reviewed, along with the specificities of the experimental environment required for these investigations.

High-Pressure Transformations and the Resonance Structure of Thiourea

High pressure increases intermolecular interactions in the crystal environment and affects the molecular dimensions of thiourea, CS(NH2)2, consistently with changing contributions of the thione and zwitterionic mesomers. The ambient-pressure phase V (space-group Pnma, Z = 4) at 0.34 GPa transforms to phase VI, of the same space-group symmetry, but with the larger unit-cell trifold (Z = 12). Another pressure-induced transition to phase VII was previously postulated for thiourea at 0.54 GPa; however, no associated structural transformations were identified. Our high-pressure single-crystal X-ray diffraction study reveals that following the transition at 0.34 GPa the lattice parameters and crystal structure strongly and monotonically change to about 0.65 GPa while the crystal symmetry is retained.

New clues from Earth’s most elusive impact crater: Evidence of reidite in Australasian tektites from Thailand

Abstract Australasian tektites are enigmatic drops of siliceous impact melt found in an ∼8000 × ∼13,000 km strewn field over Southeast Asia and Australia, including sites in both the Indian and Pacific oceans. These tektites formed only 790,000 yr ago from an impact crater estimated to be 40–100 km in diameter; yet remarkably, the young and presumably large structure remains undiscovered. Here we report new evidence of a rare high-pressure phase in Australasian tektites that further constrains the location of the source crater. The former presence of reidite, a high-pressure polymorph of zircon, was detected in granular zircon grains within Muong Nong–type tektites from Thailand. The zircon grains are surrounded by tektite glass and are composed of micrometer-sized neoblasts that contain inclusions of ZrO2. Each grain consists of neoblasts in three distinct crystallographic orientations as measured by electron backscatter diffraction, where all [001] directions are orthogonal and aligned with one <110> direction from the other two orientations. The systematic orientation relationships among zircon neoblasts are a hallmark of the high-pressure polymorphic transformation to reidite and subsequent reversion to zircon. The preserved microstructures and dissociation of zircon to ZrO2 and SiO2 require a pressure >30 GPa and a temperature >1673 °C, which represent the most extreme conditions thus far reported for Australasian Muong Nong–type tektites. The data presented here place further constraints on the distribution of high-pressure phases in Australasian tektites, including coesite and now reidite, to an area centered over Southeast Asia, which appears to be the most likely location of the source crater.

A new high-pressure form of Mg2SiO4 highlighting diffusionless phase transitions of olivine

High-pressure polymorphism of olivine (α-phase of Mg2SiO4) is of particular interest for geophysicists aiming to understand the structure and dynamics of the Earth’s interior because of olivine’s prominent abundance in the upper mantle. Therefore, natural and synthetic olivine polymorphs have been actively studied in the past half century. Here, we report a new high-pressure polymorph, the ε*-phase, which was discovered in a heavily shocked meteorite. It occurs as nanoscale lamellae and has a topotaxial relationship with the host ringwoodite (γ-phase of Mg2SiO4). Olivine in the host rock entrapped in a shock-induced melt vein initially transformed into polycrystalline ringwoodite through a nucleation and growth mechanism. The ringwoodite grains then coherently converted into the ε*-phase by shear transformation during subsequent pressure release. This intermediate metastable phase can be formed by all Mg2SiO4 polymorphs via a shear transformation mechanism. Here, we propose high-pressure transformations of olivine that are enhanced by diffusionless processes, not only in shocked meteorites but also in thick and cold lithosphere subducting into the deep Earth.