skip to main content

Title: Combining pressure and electrochemistry to synthesize superhydrides

Recently, superhydrides have been computationally identified and subsequently synthesized with a variety of metals at very high pressures. In this work, we evaluate the possibility of synthesizing superhydrides by uniquely combining electrochemistry and applied pressure. We perform computational searches using density functional theory and particle swarm optimization calculations over a broad range of pressures and electrode potentials. Using a thermodynamic analysis, we construct pressure–potential phase diagrams and provide an alternate synthesis concept, pressure–potential (P2), to access phases having high hydrogen content. Palladium–hydrogen is a widely studied material system with the highest hydride phase being Pd3H4. Most strikingly for this system, at potentials above hydrogen evolution and ∼ 300 MPa pressure, we find the possibility to make palladium superhydrides (e.g., PdH10). We predict the generalizability of this approach for La-H, Y-H, and Mg-H with 10- to 100-fold reduction in required pressure for stabilizing phases. In addition, theP2strategy allows stabilizing additional phases that cannot be done purely by either pressure or potential and is a general approach that is likely to work for synthesizing other hydrides at modest pressures.

Authors:
; ;
Publication Date:
NSF-PAR ID:
10306374
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
118
Issue:
46
Page Range or eLocation-ID:
Article No. e2110470118
ISSN:
0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Sponsoring Org:
National Science Foundation
More Like this
  1. Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter inH2O-rich setting at high pressures and temperatures (PT) places important limitations on our understanding of this planet type. We have conducted experiments for reactions betweenSiO2andH2O as archetypal materials for rock and ice, respectively, at highPT. We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where theCaCl2-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of (Si1xH4x)O2(x=0.12). At pressures above 60 GPa,H2O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could bemore »the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

    « less
  2. Abstract

    The genericity of Arnold diffusion in the analytic category is an open problem. In this paper, we study this problem in the followinga prioriunstable Hamiltonian system with a time-periodic perturbationHε(p,q,I,φ,t)=h(I)+i=1n±12pi2+Vi(qi)+εH1(p,q,I,φ,t),where(p,q)Rn×Tn,(I,φ)Rd×Tdwithn,d⩾ 1,Viare Morse potentials, andɛis a small non-zero parameter. The unperturbed Hamiltonian is not necessarily convex, and the induced inner dynamics does not need to satisfy a twist condition. Using geometric methods we prove that Arnold diffusion occurs for generic analytic perturbationsH1. Indeed, the set of admissibleH1isCωdense andC3open (a fortiori,Cωopen). Our perturbative technique for the genericity is valid in theCktopology for allk∈ [3, ∞) ∪ {∞,ω}.

  3. Abstract. Triplet excited states of organic matter are formed when colored organicmatter (i.e., brown carbon) absorbs light. While these “triplets” can beimportant photooxidants in atmospheric drops and particles (e.g., theyrapidly oxidize phenols), very little is known about their reactivity towardmany classes of organic compounds in the atmosphere. Here we measure thebimolecular rate constants of the triplet excited state of benzophenone(3BP), a model species, with 17 water-solubleC3C6 alkenes that have either been found in theatmosphere or are reasonable surrogates for identified species. Measured rateconstants (kALK+3BP) vary by a factor of 30 and are in therange of (0.24–7.5) ×109 M−1 s−1. Biogenic alkenesfound in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, andmethyl jasmonate – react rapidly, with rate constants above 1×109 M−1 s−1. Rate constants depend on alkene characteristicssuch as the location of the double bond, stereochemistry, and alkylsubstitution on the double bond. There is a reasonable correlation betweenkALK+3BP and the calculated one-electron oxidation potential(OP) of the alkenes (more »class="inline-formula">R2=0.58); in contrast, rate constants are notcorrelated with bond dissociation enthalpies, bond dissociation freeenergies, or computed energy barriers for hydrogen abstraction. Using the OPrelationship, we estimate aqueous rate constants for a number of unsaturatedisoprene and limonene oxidation products with 3BP: values are inthe range of (0.080–1.7) ×109 M−1 s−1, withgenerally faster values for limonene products. Rate constants with lessreactive triplets, which are probably more environmentally relevant, arelikely roughly 25 times slower. Using our predicted rate constants, alongwith values for other reactions from the literature, we conclude thattriplets are probably minor oxidants for isoprene- and limonene-relatedcompounds in cloudy or foggy atmospheres, except in cases in which the tripletsare very reactive.

    « less
  4. Abstract

    We use ALMA observations of CO(2–1) in 13 massive (M*≳ 1011M) poststarburst galaxies atz∼ 0.6 to constrain the molecular gas content in galaxies shortly after they quench their major star-forming episode. The poststarburst galaxies in this study are selected from the Sloan Digital Sky Survey spectroscopic samples (Data Release 14) based on their spectral shapes, as part of the Studying QUenching at Intermediate-z Galaxies: Gas, anguLarmomentum, and Evolution (SQuIGGLE) program. Early results showed that two poststarburst galaxies host large H2reservoirs despite their low inferred star formation rates (SFRs). Here we expand this analysis to a larger statistical sample of 13 galaxies. Six of the primary targets (45%) are detected, withMH2109M. Given their high stellar masses, this mass limit corresponds to an average gas fraction offH2MH2/M*7%or ∼14% using lower stellar masses estimates derived from analytic, exponentially declining star formation histories. The gas fraction correlates with theDn4000 spectral index, suggesting that the cold gas reservoirs decrease with time since burst, as found in local K+A galaxies. Star formation histories derived from flexible stellar population synthesis modeling support thismore »empirical finding: galaxies that quenched ≲150 Myr prior to observation host detectable CO(2–1) emission, while older poststarburst galaxies are undetected. The large H2reservoirs and low SFRs in the sample imply that the quenching of star formation precedes the disappearance of the cold gas reservoirs. However, within the following 100–200 Myr, theSQuIGGLEgalaxies require the additional and efficient heating or removal of cold gas to bring their low SFRs in line with standard H2scaling relations.

    « less
  5. Abstract

    We report the discovery of MAGAZ3NE J095924+022537, a spectroscopically confirmed protocluster atz=3.36650.0012+0.0009around a spectroscopically confirmedUVJ-quiescent ultramassive galaxy (UMG;M=2.340.34+0.23×1011M) in the COSMOS UltraVISTA field. We present a total of 38 protocluster members (14 spectroscopic and 24 photometric), including the UMG. Notably, and in marked contrast to protoclusters previously reported at this epoch that have been found to contain predominantly star-forming members, we measure an elevated fraction of quiescent galaxies relative to the coeval field (73.316.9+26.7%versus11.64.9+7.1%for galaxies with stellar massM≥ 1011M). This high quenched fraction provides a striking and important counterexample to the seeming ubiquitousness of star-forming galaxies in protoclusters atz> 2 and suggests, rather, that protoclusters exist in a diversity of evolutionary states in the early universe. We discuss the possibility that we might be observing either “early mass quenching” or nonclassical “environmental quenching.” We also present the discovery of MAGAZ3NE J100028+023349, a second spectroscopically confirmed protocluster, at a very similar redshift ofz=3.38010.0281+0.0213. We present a total of 20 protocluster members, 12 of which are photometric and eight spectroscopic including a poststarburst UMG (M=2.950.20+0.21×1011M). Protoclusters MAGAZ3NE J0959more »and MAGAZ3NE J1000 are separated by 18′ on the sky (35 comoving Mpc), in good agreement with predictions from simulations for the size of “Coma”-type cluster progenitors at this epoch. It is highly likely that the two UMGs are the progenitors of Brightest Cluster Galaxies seen in massive virialized clusters at lower redshift.

    « less