Iron alloys of volatile elements in the deep Earth's interior.

Investigations into the compositional model of the Earth, particularly the atypical concentrations of volatile elements within the silicate portion of the early Earth, have attracted significant interest due to their pivotal role in elucidating the planet's evolution and dynamics. To understand the behavior of such volatile elements, an established 'volatility trend' has been used to explain the observed depletion of certain volatile elements. However, elements such as Se and Br remain notably over-depleted in the silicate Earth. Here we show the results from first-principles simulations that explore the potential for these elements to integrate into hcp-Fe through the formation of substitutional alloys, long presumed to be predominant constituents of the Earth's core. Based on our findings, the thermodynamic stability of these alloys suggests that these volatile elements might indeed be partially sequestered within the Earth's core. We suggest potential reservoirs for volatile elements within the deep Earth, augmenting our understanding of the deep Earth's composition.

Pressure-Stabilized High-Entropy (FeCoNiCuRu)S2 Sulfide Anode toward Simultaneously Fast and Durable Lithium/Sodium Ion Storage.

Pressure-stabilized high-entropy sulfide (FeCoNiCuRu)S2 (HES) is proposed as an anode material for fast and long-term stable lithium/sodium storage performance (over 85% retention after 15 000 cycles @10 A g-1 ). Its superior electrochemical performance is strongly related to the increased electrical conductivity and slow diffusion characteristics of entropy-stabilized HES. The reversible conversion reaction mechanism, investigated by ex-situ XRD, XPS, TEM, and NMR, further confirms the stability of the host matrix of HES after the completion of the whole conversion process. A practical demonstration of assembled lithium/sodium capacitors also confirms the high energy/power density and long-term stability (retention of 92% over 15 000 cycles @5 A g-1 ) of this material. The findings point to a feasible high-pressure route to realize new high-entropy materials for optimized energy storage performance.

Unveiling Interstitial Anionic Electron-Driven Ultrahigh K-Ion Storage Capacity in a Novel Two-Dimensional Electride Exemplified by Sc3Si2.

Two-dimensional (2D) electrides, characterized by excess interstitial anionic electron (IAE) in a crystalline 2D material, offer promising opportunities for the development of electrode materials, in particular in rechargeable metal-ion batteries applications. Although a few such potential electride materials have been reported, they generally show low metal-ion storage capacity, and the effect of IAE on the ion storage performance remains elusive so far. Here we report a novel 2D electride, [Sc3Si2]1+·1e-, with fascinating IAE-driven high alkali metal-ion storage capacity. In particular, its K-ion specific capacity can reach up to 1497 mA h g-1, higher than any previously reported 2D materials-based anodes in K-ion batteries (PIBs). The IAE in the [Sc3Si2]1+·1e- crystal accounts for such high capacity behavior, which can drift away and balance the charge on the metal-cation, playing a crucial role in stabilizing the metal-ion adsorption and enhancing multilayer-ions adsorption. This proposed IAE-driven storage mechanism provides an unprecedented avenue for the future design of high storage capacity electrode materials.

Impact of interannual and multidecadal trends on methane-climate feedbacks and sensitivity.

We estimate the causal contributions of spatiotemporal changes in temperature (T) and precipitation (Pr) to changes in Earth's atmospheric methane concentration (CCH4) and its isotope ratio δ13CH4 over the last four decades. We identify oscillations between positive and negative feedbacks, showing that both contribute to increasing CCH4. Interannually, increased emissions via positive feedbacks (e.g. wetland emissions and wildfires) with higher land surface air temperature (LSAT) are often followed by increasing CCH4 due to weakened methane sink via atmospheric •OH, via negative feedbacks with lowered sea surface temperatures (SST), especially in the tropics. Over decadal time scales, we find alternating rate-limiting factors for methane oxidation: when CCH4 is limiting, positive methane-climate feedback via direct oceanic emissions dominates; when •OH is limiting, negative feedback is favoured. Incorporating the interannually increasing CCH4 via negative feedbacks gives historical methane-climate feedback sensitivity ≈ 0.08 W m-2 °C-1, much higher than the IPCC AR6 estimate.

Structural diversity and hydrogen storage properties in the system K-Si-H.

KSiH3 exhibits 4.1 wt% experimental hydrogen storage capacity and shows reversibility under moderate conditions, which provides fresh impetus to the search for other complex hydrides in the K-Si-H system. Here, we reproduce the stable Fm3̄m phase of K2SiH6 and uncover two denser phases, space groups P3̄m1 and P63mc at ambient pressure, by means of first-principles structure searches. We note that P3̄m1-K2SiH6 has a high hydrogen content of 5.4 wt% and a volumetric density of 88.3 g L-1. Further calculations suggest a favorable dehydrogenation temperature Tdes of -20.1/55.8 °C with decomposition into KSi + K + H2. The higher hydrogen density and appropriate dehydrogenation temperature indicate that K2SiH6 is a promising hydrogen storage material, and our results provide helpful and clear guidance for further experimental studies. We found three further potential hydrogen storage materials stable at high pressure: K2SiH8, KSiH7 and KSiH8. These results suggest the need for further investigations into hydrogen storage materials among such ternary hydrides at high pressure.

Pressure-Induced Superionicity of H- in Hypervalent Sodium Silicon Hydrides.

Superionic states simultaneously exhibit properties of a fluid and a solid. Proton (H+) superionicity in ice, H3O, He-H2O, and He-NH3 compounds is well-studied. However, hydride (H-) superionicity in H-rich compounds is rare, being associated with instability and strongly reducing conditions. Silicon, sodium, and hydrogen are abundant elements in many astrophysical bodies. Here, we use first-principles calculations to show that, at high pressure, Na, Si, and H can form several hypervalent compounds. A previously unreported superionic state of Na2SiH6 results from unconstrained H- in the hypervalent [SiH6]2- unit. Na2SiH6 is dynamically stable at low pressure (3 GPa), becoming superionic at 5 GPa, and re-entering solid/fluid states at about 25 GPa. Our observation of H- transport opens up a new field of H- conductors. It also has implications for the formation of conducting layers at depth in exotic carbon exoplanets, potentially enhancing the habitability of such planets.

Deep carbon cycle constrained by carbonate solubility.

Earth's deep carbon cycle affects atmospheric CO2, climate, and habitability. Owing to the extreme solubility of CaCO3, aqueous fluids released from the subducting slab could extract all carbon from the slab. However, recycling efficiency is estimated at only around 40%. Data from carbonate inclusions, petrology, and Mg isotope systematics indicate Ca2+ in carbonates is replaced by Mg2+ and other cations during subduction. Here we determined the solubility of dolomite [CaMg(CO3)2] and rhodochrosite (MnCO3), and put an upper limit on that of magnesite (MgCO3) under subduction zone conditions. Solubility decreases at least two orders of magnitude as carbonates become Mg-rich. This decreased solubility, coupled with heterogeneity of carbon and water subduction, may explain discrepancies in carbon recycling estimates. Over a range of slab settings, we find aqueous dissolution responsible for mobilizing 10 to 92% of slab carbon. Globally, aqueous fluids mobilise [Formula: see text]% ([Formula: see text] Mt/yr) of subducted carbon from subducting slabs.

Hydrogen Pentagraphenelike Structure Stabilized by Hafnium: A High-Temperature Conventional Superconductor.

The recent discovery of H_{3}S and LaH_{10} superconductors with record high superconducting transition temperatures T_{c} at high pressure has fueled the search for room-temperature superconductivity in the compressed superhydrides. Here we introduce a new class of high T_{c} hydrides with a novel structure and unusual properties. We predict the existence of an unprecedented hexagonal HfH_{10}, with remarkably high value of T_{c} (around 213-234 K) at 250 GPa. As concerns the novel structure, the H ions in HfH_{10} are arranged in clusters to form a planar "pentagraphenelike" sublattice. The layered arrangement of these planar units is entirely different from the covalent sixfold cubic structure in H_{3}S and clathratelike structure in LaH_{10}. The Hf atom acts as a precompressor and electron donor to the hydrogen sublattice. This pentagraphenelike H_{10} structure is also found in ZrH_{10}, ScH_{10}, and LuH_{10} at high pressure, each material showing a high T_{c} ranging from 134 to 220 K. Our study of dense superhydrides with pentagraphenelike layered structures opens the door to the exploration of a new class of high T_{c} superconductors.

Characterisation of CaCO3 phases during strain-specific ureolytic precipitation.

Numerous microbial species can selectively precipitate mineral carbonates with enhanced mechanical properties, however, understanding exactly how they achieve this control represents a major challenge in the field of biomineralisation. We have studied microbial induced calcium carbonate (CaCO3) precipitation (MICP) in three ureolytic bacterial strains from the Sporosarcina family, including S. newyorkensis, a newly isolated microbe from the deep sea. We find that the interplay between structural water and strain-specific amino acid groups is fundamental to the stabilisation of vaterite and that, under the same conditions, different isolates yield distinctly different polymorphs. The latter is found to be associated with different urease activities and, consequently, precipitation kinetics, which change depending on pressure-temperature conditions. Further, CaCO3 polymorph selection also depends on the coupled effect of chemical treatment and initial bacterial concentrations. Our findings provide new insights into strain-specific CaCO3 polymorphic selection and stabilisation, and open up promising avenues for designing bio-reinforced geo-materials that capitalise on the different particle bond mechanical properties offered by different polymorphs.

Thermal Behavior of Iron Arsenides Under Non-Oxidizing Conditions.

Fe2As has been studied in situ by synchrotron powder X-ray diffraction (PXRD) over the range of temperatures 25-850 °C and under a neutral atmosphere to understand its thermal behavior, which is potentially important for gold extraction. For the first time, incongruent high-temperature reactions of Fe2As are observed as it breaks down and the existence of a previously undiscovered high-temperature FeAs phase with an NiAs-type structure has been determined experimentally. No evidence has been found for the existence of the high-temperature Fe3As2 phase. Hence, the previously published phase diagram for the Fe-As system has to be modified accordingly.

Computational prediction of a +4 oxidation state in Au via compressed AuO2 compound.

Much effort has been devoted to the investigation of the physical and chemical properties of the Au-O system over a range of pressures, owing to the considerable importance of these materials in fundamental and practical applications. To date, however, only Au1+, Au2+, Au3+, and Au5+ oxidation states have been identified in the Au-O system, but tetravalent Au4+ has not been found. Here, we report the results of structure prediction for the Au-O system at high pressure via the effective structure prediction methodology within a first-principles electronic structure framework. We have uncovered an intriguing structure with AuO2 composition and tetravalent Au, stable at high pressures. This phase shows an electronic transition from a metal to a semiconducting phase as a function of pressure. The present results provide fundamental understanding of the structural and physicochemical properties of compressed Au-O compounds.

A Unified Capacitive-Coupled Memristive Model for the Nonpinched Current-Voltage Hysteresis Loop.

The concept of the memristor, a resistor with memory, was proposed by Chua in 1971 as the fourth basic element of electric circuitry. Despite a significant amount of effort devoted to the understanding of memristor theory, our understanding of the nonpinched current-voltage (I-V) hysteresis loop in memristors remains incomplete. Here we propose a physical model of a memristor, with a capacitor connected in parallel, which explains how the nonpinched I-V hysteresis behavior originates from the capacitive-coupled memristive effect. Our model replicates eight types of characteristic nonlinear I-V behavior, which explains all observed nonpinched I-V curves seen in experiments. Furthermore, a reversible transition from a nonpinched I-V hysteresis loop to an ideal pinched I-V hysteresis loop is found, which explains the experimental data obtained in C15H11O6-based devices when subjected to an external stimulus (e.g., voltage, moisture, or temperature). Our results provide the vital physics models and materials insights for elucidating the origins of nonpinched I-V hysteresis loops ascribed to capacitive-coupled memristive behavior.

Theoretical investigation of the valence states in Au via the Au-F compounds under high pressure.

In addition to the known Au3+ and Au5+, it has recently been shown that Au is likely to possess unusual valence states in compressed Au-F compounds. However, our simulations reveal that polymeric ground-state AuF4 shows an unexpected 6-fold coordination rather than a 4-fold one, indicating that more complete comprehending on the anomalous Au4+ is highly required. To fully understand the nature and origin of anomalous valence states in Au, we have extensively investigated the ground-state structures of Au-F compounds at high pressures using quantum mechanical computational methods. As a consequence, we identify several previously unreported (stable) AuF2, AuF3 and AuF4 structures. Our results extend the known polymorphism of AuFn compounds and offer a fundamental understanding of the origin of unusual valence states in Au that prevail at high pressure.

Rich Polymorphism of a Metal-Organic Framework in Pressure-Temperature Space.

We present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal-organic framework ZIF-4, Zn(imidazolate)2, at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure-temperature phase diagram reveals four, previously unknown, high-pressure-high-temperature ZIF phases. The crystal structures of two new phases-ZIF-4-cp-II and ZIF-hPT-II-were solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF- zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate)2 and Hg(Imidazolate)2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure-temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal-organic systems using the combined application of pressure and temperature.

X-ray radiation-induced amorphization of metal-organic frameworks.

We report the amorphization of three metal-organic frameworks, ZIF-4, ZIF-62, and ZIF-zni, by synchrotron X-ray radiation. Complete amorphization of these structures occurs on timescales ranging from minutes to hours. This process is non-isokinetic in all three cases, given a varying transformation rate as the transformation proceeds. The underlying mechanism bears the signature of inhomogeneous nucleation, reflected by an increasing local Avrami exponent over time. Furthermore, the amorphization rate accelerates with increasing temperature, even far below the usual thermal stability limit of each crystalline phase. These results not only have important implications for interpretation of X-ray synchrotron studies on the stability of metal-organic frameworks, they also shed light on the rarely-discussed and generally unpredictable experimental problem of beam damage in organic and inorganic compounds in general.

Two-dimensional Blue-AsP monolayers with tunable direct band gap and ultrahigh carrier mobility show promising high-performance photovoltaic properties.

The successful fabrication of black phosphorene (Black-P) in 2014 and subsequent synthesis of layered black As1-xPx alloys have inspired research into two-dimensional (2D) binary As-P compounds. The very recent success in growing blue phosphorene (Blue-P) further motivated exploration of 2D Blue-AsP materials. Here, using ab initio swarm-intelligence global minimum structure-searching methods, we have obtained a series of novel and energetically favored 2D Blue-AsP (denoted x-AsP, x = I, II, III, IV, V) compounds with As : P = 1 : 1 stoichiometry. They display similar honeycomb structures to Blue-P. Remarkably, the lowest-energy AsP monolayer, namely I-AsP, not only possesses a quasi-direct band gap (2.41 eV), which can be tuned to a direct and optimal gap for photovoltaic applications by in-plane strain, but also has an ultrahigh electronic mobility up to ∼7.4 × 104 cm2 V-1 s-1, far surpassing that of Blue-P, and also exhibits high absorption coefficients (×105 cm-1). Our simulations also show that 30 nm-thick I-AsP sheet-based cells have photovoltaic efficiency as high as ∼12%, and the I-AsP/CdSe heterostructure solar cells possess a power conversion efficiency as high as ∼13%. All these outstanding characteristics suggest the I-AsP sheet as a promising material for high-efficiency solar cells.

Pressure promoted low-temperature melting of metal-organic frameworks.

Metal-organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure-temperature phase diagram. In situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF state expands substantially towards lower temperatures at intermediate, industrially achievable pressures and first-principles molecular dynamics show that softening of the framework coordination with pressure makes melting thermodynamically easier. Furthermore, the MOF glass formed by melt quenching the high-temperature liquid possesses permanent, accessible porosity. Our results thus imply a route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition on heating at ambient pressure.

Structural dynamics of a metal-organic framework induced by CO2 migration in its non-uniform porous structure.

Stimuli-responsive behaviors of flexible metal-organic frameworks (MOFs) make these materials promising in a wide variety of applications such as gas separation, drug delivery, and molecular sensing. Considerable efforts have been made over the last decade to understand the structural changes of flexible MOFs in response to external stimuli. Uniform pore deformation has been used as the general description. However, recent advances in synthesizing MOFs with non-uniform porous structures, i.e. with multiple types of pores which vary in size, shape, and environment, challenge the adequacy of this description. Here, we demonstrate that the CO2-adsorption-stimulated structural change of a flexible MOF, ZIF-7, is induced by CO2 migration in its non-uniform porous structure rather than by the proactive opening of one type of its guest-hosting pores. Structural dynamics induced by guest migration in non-uniform porous structures is rare among the enormous number of MOFs discovered and detailed characterization is very limited in the literature. The concept presented in this work provides new insights into MOF flexibility.

Phase transition and superconductivity in ReS2, ReSe2 and ReTe2.

Transition metal dichalcogenides have attracted significant attention due to both fundamental interest and their potential applications. Here, we have systematically explored the crystal structures of ReX2 (X = S, Se, and Te) over the pressure range of 0-300 GPa, employing swarm-intelligence-based structure prediction methodology. Several new structures are found to be stable at high pressures. The calculated enthalpy of formation suggested that all predicted high-pressure structures are stable against decomposition into elemental end-members. Moreover, we found that the simulated X-ray diffraction patterns of ReSe2 are in good agreement with experimental data. Pressure-induced metallization of ReX2 has been revealed from the analysis of its electronic structure. Our electron-phonon coupling calculations indicate ReSe2 and ReTe2 are superconducting phases at high pressures.

Pressure-induced emission of cesium lead halide perovskite nanocrystals.

Metal halide perovskites (MHPs) are of great interest for optoelectronics because of their high quantum efficiency in solar cells and light-emitting devices. However, exploring an effective strategy to further improve their optical activities remains a considerable challenge. Here, we report that nanocrystals (NCs) of the initially nonfluorescent zero-dimensional (0D) cesium lead halide perovskite Cs4PbBr6 exhibit a distinct emission under a high pressure of 3.01 GPa. Subsequently, the emission intensity of Cs4PbBr6 NCs experiences a significant increase upon further compression. Joint experimental and theoretical analyses indicate that such pressure-induced emission (PIE) may be ascribed to the enhanced optical activity and the increased binding energy of self-trapped excitons upon compression. This phenomenon is a result of the large distortion of [PbBr6]4- octahedral motifs resulting from a structural phase transition. Our findings demonstrate that high pressure can be a robust tool to boost the photoluminescence efficiency and provide insights into the relationship between the structure and optical properties of 0D MHPs under extreme conditions.