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1.
Nat Commun ; 13(1): 7763, 2022 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-36522319

RESUMO

Carbon dioxide capture is essential to achieve net-zero emissions. A hurdle to the design of improved capture materials is the lack of adequate tools to characterise how CO2 adsorbs. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a promising probe of CO2 capture, but it remains challenging to distinguish different adsorption products. Here we perform a comprehensive computational investigation of 22 amine-functionalised metal-organic frameworks and discover that 17O NMR is a powerful probe of CO2 capture chemistry that provides excellent differentiation of ammonium carbamate and carbamic acid species. The computational findings are supported by 17O NMR experiments on a series of CO2-loaded frameworks that clearly identify ammonium carbamate chain formation and provide evidence for a mixed carbamic acid - ammonium carbamate adsorption mode. We further find that carbamic acid formation is more prevalent in this materials class than previously believed. Finally, we show that our methods are readily applicable to other adsorbents, and find support for ammonium carbamate formation in amine-grafted silicas. Our work paves the way for investigations of carbon capture chemistry that can enable materials design.

2.
Research (Wash D C) ; 2022: 9798758, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36111317

RESUMO

Aluminum, as the most abundant metallic elemental content in the Earth's crust, usually exists in the form of alumina (Al2O3). However, the oxidation state of aluminum and the crystal structures of aluminum oxides in the pressure range of planetary interiors are not well established. Here, we predicted two aluminum suboxides (Al2O, AlO) and two superoxides (Al4O7, AlO3) with uncommon stoichiometries at high pressures using first-principle calculations and crystal structure prediction methods. We find that the P4/nmm Al2O becomes stable above ~765 GPa and may survive in the deep mantles or cores of giant planets such as Neptune. Interestingly, the Al2O and AlO are metallic and have electride features, in which some electrons are localized in the interstitials between atoms. We find that Al2O has an electrical conductivity one order of magnitude higher than that of iron under the same pressure-temperature conditions, which may influence the total conductivity of giant planets. Our findings enrich the high-pressure phase diagram of aluminum oxides and improve our understanding of the interior structure of giant planets.

3.
Nature ; 609(7927): 512-516, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-36104556

RESUMO

Water in nanoscale cavities is ubiquitous and of central importance to everyday phenomena in geology and biology. However, the properties of nanoscale water can be substantially different from those of bulk water, as shown, for example, by the anomalously low dielectric constant of water in nanochannels1, near frictionless water flow2 or the possible existence of a square ice phase3. Such properties suggest that nanoconfined water could be engineered for technological applications in nanofluidics4, electrolyte materials5 and water desalination6. Unfortunately, challenges in experimentally characterizing water at the nanoscale and the high cost of first-principles simulations have prevented the molecular-level understanding required to control the behaviour of water. Here we combine a range of computational approaches to enable a first-principles-level investigation of a single layer of water within a graphene-like channel. We find that monolayer water exhibits surprisingly rich and diverse phase behaviour that is highly sensitive to temperature and the van der Waals pressure acting within the nanochannel. In addition to multiple molecular phases with melting temperatures varying non-monotonically by more than 400 kelvins with pressure, we predict a hexatic phase, which is an intermediate between a solid and a liquid, and a superionic phase with a high electrical conductivity exceeding that of battery materials. Notably, this suggests that nanoconfinement could be a promising route towards superionic behaviour under easily accessible conditions.

4.
J Phys Chem Lett ; 13(36): 8447-8454, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-36053162

RESUMO

Through a series of high pressure diamond anvil experiments, we report the synthesis of alkaline earth (Ca, Sr, Ba) tetrahydrides, and investigate their properties through Raman spectroscopy, X-ray diffraction, and density functional theory calculations. The tetrahydrides incorporate both atomic and quasi-molecular hydrogen, and we find that the frequency of the intramolecular stretching mode of the H2δ- units downshifts from Ca to Sr and to Ba upon compression. The experimental results indicate that the larger the host cation, the longer the H2δ- bond. Analysis of the electron localization function (ELF) demonstrates that the lengthening of the H-H bond is caused by the charge transfer from the metal to H2δ- and by the steric effect of the metal host on the H-H bond. This effect is most prominent for BaH4, where the precompression of H2δ- units at 50 GPa results in bond lengths comparable to that of pure H2 above 275 GPa.

5.
Phys Chem Chem Phys ; 24(21): 13033-13039, 2022 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-35583230

RESUMO

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.

6.
Phys Rev Lett ; 128(4): 047001, 2022 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-35148145

RESUMO

Hydrogen-based superconductors provide a route to the long-sought goal of room-temperature superconductivity, but the high pressures required to metallize these materials limit their immediate application. For example, carbonaceous sulfur hydride, the first room-temperature superconductor made in a laboratory, can reach a critical temperature (T_{c}) of 288 K only at the extreme pressure of 267 GPa. The next recognized challenge is the realization of room-temperature superconductivity at significantly lower pressures. Here, we propose a strategy for the rational design of high-temperature superconductors at low pressures by alloying small-radius elements and hydrogen to form ternary H-based superconductors with alloy backbones. We identify a "fluorite-type" backbone in compositions of the form AXH_{8}, which exhibit high-temperature superconductivity at moderate pressures compared with other reported hydrogen-based superconductors. The Fm3[over ¯]m phase of LaBeH_{8}, with a fluorite-type H-Be alloy backbone, is predicted to be thermodynamically stable above 98 GPa, and dynamically stable down to 20 GPa with a high T_{c}∼185 K. This is substantially lower than the synthesis pressure required by the geometrically similar clathrate hydride LaH_{10} (170 GPa). Our approach paves the way for finding high-T_{c} ternary H-based superconductors at conditions close to ambient pressures.

7.
J Chem Phys ; 156(7): 074106, 2022 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-35183078

RESUMO

Titanium dioxide has been extensively studied in the rutile or anatase phase, while its high-pressure phases are less well-understood, despite that many are thought to have interesting optical, mechanical, and electrochemical properties. First-principles methods, such as density functional theory (DFT), are often used to compute the enthalpies of TiO2 phases at 0 K, but they are expensive and, thus, impractical for long time scale and large system-size simulations at finite temperatures. On the other hand, cheap empirical potentials fail to capture the relative stabilities of various polymorphs. To model the thermodynamic behaviors of ambient and high-pressure phases of TiO2, we design an empirical model as a baseline and then train a machine learning potential based on the difference between the DFT data and the empirical model. This so-called Δ-learning potential contains long-range electrostatic interactions and predicts the 0 K enthalpies of stable TiO2 phases that are in good agreement with DFT. We construct a pressure-temperature phase diagram of TiO2 in the range 0 < P < 70 GPa and 100 < T < 1500 K. We then simulate dynamic phase transition processes by compressing anatase at different temperatures. At 300 K, we predominantly observe an anatase-to-baddeleyite transformation at about 20 GPa via a martensitic two-step mechanism with a highly ordered and collective atomic motion. At 2000 K, anatase can transform into cotunnite around 45-55 GPa in a thermally activated and probabilistic manner, accompanied by diffusive movement of oxygen atoms. The pressures computed for these transitions show good agreement with experiments. Our results shed light on how to synthesize and stabilize high-pressure TiO2 phases, and our method is generally applicable to other functional materials with multiple polymorphs.

8.
J Phys Condens Matter ; 34(18)2022 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-34544070

RESUMO

Designing materials with advanced functionalities is the main focus of contemporary solid-state physics and chemistry. Research efforts worldwide are funneled into a few high-end goals, one of the oldest, and most fascinating of which is the search for an ambient temperature superconductor (A-SC). The reason is clear: superconductivity at ambient conditions implies being able to handle, measure and access a single, coherent, macroscopic quantum mechanical state without the limitations associated with cryogenics and pressurization. This would not only open exciting avenues for fundamental research, but also pave the road for a wide range of technological applications, affecting strategic areas such as energy conservation and climate change. In this roadmap we have collected contributions from many of the main actors working on superconductivity, and asked them to share their personal viewpoint on the field. The hope is that this article will serve not only as an instantaneous picture of the status of research, but also as a true roadmap defining the main long-term theoretical and experimental challenges that lie ahead. Interestingly, although the current research in superconductor design is dominated by conventional (phonon-mediated) superconductors, there seems to be a widespread consensus that achieving A-SC may require different pairing mechanisms.In memoriam, to Neil Ashcroft, who inspired us all.

10.
J Phys Chem Lett ; 12(30): 7166-7172, 2021 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-34297555

RESUMO

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.

11.
J Chem Phys ; 154(17): 174111, 2021 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-34241052

RESUMO

Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS.

12.
J Chem Phys ; 154(17): 174702, 2021 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-34241079

RESUMO

Through a series of high-pressure x-ray diffraction experiments combined with in situ laser heating, we explore the pressure-temperature phase diagram of germanium (Ge) at pressures up to 110 GPa and temperatures exceeding 3000 K. In the pressure range of 64-90 GPa, we observe orthorhombic Ge-IV transforming above 1500 K to a previously unobserved high-temperature phase, which we denote as Ge-VIII. This high-temperature phase is characterized by a tetragonal crystal structure, space group I4/mmm. Density functional theory simulations confirm that Ge-IV becomes unstable at high temperatures and that Ge-VIII is highly competitive and dynamically stable at these conditions. The existence of Ge-VIII has profound implications for the pressure-temperature phase diagram, with melting conditions increasing to much higher temperatures than previous extrapolations would imply.

13.
Phys Rev Lett ; 126(22): 225704, 2021 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-34152171

RESUMO

All elements that form diatomic molecules, such as H_{2}, N_{2}, O_{2}, Cl_{2}, Br_{2}, and I_{2}, are destined to become atomic solids under sufficiently high pressure. However, as revealed by many experimental and theoretical studies, these elements show very different propensity and transition paths due to the balance of reduced volume, lone pair electrons, and interatomic bonds. The study of F under pressure can illuminate this intricate behavior since F, owing to its unique position on the periodic table, can be compared with H, with N and O, and also with other halogens. Nevertheless, F remains the only element whose solid structure evolution under pressure has not been thoroughly studied. Using a large-scale crystal structure search method based on first principles calculations, we find that, before reaching an atomic phase, F solid transforms first into a structure consisting of F_{2} molecules and F polymer chains and then into a structure consisting of F polymer chains and F atoms, a distinctive evolution with pressure that has not been seen in any other elements. Both intermediate structures are found to be metallic and become superconducting, a result that adds F to the elemental superconductors.

14.
Proc Natl Acad Sci U S A ; 118(19)2021 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-33931549

RESUMO

The solar system's outer planets, and many of their moons, are dominated by matter from the H-C-N-O chemical space, based on solar system abundances of hydrogen and the planetary ices [Formula: see text]O, [Formula: see text], and [Formula: see text] In the planetary interiors, these ices will experience extreme pressure conditions, around 5 Mbar at the Neptune mantle-core boundary, and it is expected that they undergo phase transitions, decompose, and form entirely new compounds. While temperature will dictate the formation of compounds, ground-state density functional theory allows us to probe the chemical effects resulting from pressure alone. These structural developments in turn determine the planets' interior structures, thermal evolution, and magnetic field generation, among others. Despite its importance, the H-C-N-O system has not been surveyed systematically to explore which compounds emerge at high-pressure conditions, and what governs their stability. Here, we report on and analyze an unbiased crystal structure search among H-C-N-O compounds between 1 and 5 Mbar. We demonstrate that simple chemical rules drive stability in this composition space, which explains why the simplest possible quaternary mixture HCNO-isoelectronic to diamond-emerges as a stable compound and discuss dominant decomposition products of planetary ice mixtures.

15.
J Phys Chem Lett ; 12(20): 4910-4916, 2021 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-34008402

RESUMO

By combining pressures up to 50 GPa and temperatures of 1200 K, we synthesize the novel barium hydride, Ba8H46, stable down to 27 GPa. We use Raman spectroscopy, X-ray diffraction, and first-principles calculations to determine that this compound adopts a highly symmetric Pm3¯n structure with an unusual 534:1 hydrogen-to-barium ratio. This singular stoichiometry corresponds to the well-defined type-I clathrate geometry. This clathrate consists of a Weaire-Phelan hydrogen structure with the barium atoms forming a topologically close-packed phase. In particular, the structure is formed by H20 and H24 clathrate cages showing substantially weakened H-H interactions. Density functional theory (DFT) demonstrates that cubic Pm3¯n Ba8H46 requires dynamical effects to stabilize the H20 and H24 clathrate cages.

16.
Nano Lett ; 21(7): 2745-2751, 2021 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-33788564

RESUMO

The formation of nanoscale phases at grain boundaries in polycrystalline materials has attracted much attention, since it offers a route toward targeted and controlled design of interface properties. However, understanding structure-property relationships at these complex interfacial defects is hampered by the great challenge of accurately determining their atomic structure. Here, we combine advanced electron microscopy together with ab initio random structure searching to determine the atomic structure of an experimentally fabricated Σ13 (221) [11̅0] grain boundary in rutile TiO2. Through careful analysis of the atomic structure and complementary electron energy-loss spectroscopy analysis we identify the existence of a unique nanoscale phase at the grain boundary with striking similarities to the bulk anatase crystal structure. Our results show a path to embed nanoscale anatase into rutile TiO2 and showcase how the atomic structure of even complex internal interfaces can be accurately determined using a combined theoretical and experimental approach.

17.
J Phys Chem A ; 125(7): 1650-1660, 2021 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-33586978

RESUMO

The properties of a material depend on how its atoms are arranged, and predicting these arrangements from first principles is a longstanding challenge. Orbital-free density functional theory provides a quantum-mechanical model based solely on the electron density, not individual wave functions. The resulting speedups make it attractive for random structure searching, whereby random configurations of atoms are relaxed to local minima in the energy landscape. We use this strategy to map the low-energy crystal structures of Li, Na, Mg, and Al at zero pressure. For Li and Na, our searching finds numerous close-packed polytypes of almost-equal energy, consistent with previous efforts to understand their low-temperature forms. For Mg and Al, the searching identifies the expected ground state structures unambiguously, in addition to revealing other low-energy structures. This new role for orbital-free density functional theory-particularly as continued advances make it accurate for more of the periodic table-will expedite crystal structure prediction over wide ranges of compositions and pressures.

18.
Nat Mater ; 20(6): 841-850, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33479526

RESUMO

Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/ß-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.

19.
J Phys Chem Lett ; 12(3): 1046-1051, 2021 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-33470818

RESUMO

Half-Heusler thermoelectric materials are potential candidates for high thermoelectric efficiency. We report high-pressure thermoelectric and structural property measurements, density functional theory calculations on the half-Heusler material TiNiSn, and an increase of 15% in the relative dimensionless figure of merit, ZT, around 3 GPa. Thermal and electrical properties were measured utilizing a specialized sample cell assembly designed for the Paris-Edinburgh large-volume press to a maximum pressure of 3.5 GPa. High-pressure structural measurements performed up to 50 GPa in a diamond-anvil cell indicated the emergence of a new high-pressure phase around 20 GPa. A first-principles structure search performed using an ab initio random structure search approach identified the high-pressure phase as an orthorhombic type, in good agreement with the experimental results.

20.
J Am Chem Soc ; 143(1): 214-222, 2021 01 13.
Artigo em Inglês | MEDLINE | ID: mdl-33372790

RESUMO

Incorporating bismuth, the heaviest element stable to radioactive decay, into new materials enables the creation of emergent properties such as permanent magnetism, superconductivity, and nontrivial topology. Understanding the factors that drive Bi reactivity is critical for the realization of these properties. Using pressure as a tunable synthetic vector, we can access unexplored regions of phase space to foster reactivity between elements that do not react under ambient conditions. Furthermore, combining computational and experimental methods for materials discovery at high-pressures provides broader insight into the thermodynamic landscape than can be achieved through experiment alone, informing our understanding of the dominant chemical factors governing structure formation. Herein, we report our combined computational and experimental exploration of the Mo-Bi system, for which no binary intermetallic structures were previously known. Using the ab initio random structure searching (AIRSS) approach, we identified multiple synthetic targets between 0-50 GPa. High-pressure in situ powder X-ray diffraction experiments performed in diamond anvil cells confirmed that Mo-Bi mixtures exhibit rich chemistry upon the application of pressure, including experimental realization of the computationally predicted CuAl2-type MoBi2 structure at 35.8(5) GPa. Electronic structure and phonon dispersion calculations on MoBi2 revealed a correlation between valence electron count and bonding in high-pressure transition metal-Bi structures as well as identified two dynamically stable ambient pressure polymorphs. Our study demonstrates the power of the combined computational-experimental approach in capturing high-pressure reactivity for efficient materials discovery.

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