skip to main content


Title: Reaction between Hydrogen and Ferrous/Ferric Oxides at High Pressures and High Temperatures—Implications for Sub-Neptunes and Super-Earths
Abstract

Sub-Neptune exoplanets may have thick hydrogen envelopes and therefore develop a high-pressure interface between hydrogen and the underlying silicates/metals. Some sub-Neptunes may convert to super-Earths via massive gas loss. If hydrogen chemically reacts with oxides and metals at high pressures and temperatures (PT), it could impact the structure and composition of the cores and atmospheres of sub-Neptunes and super-Earths. While H2gas is a strong reducing agent at low pressures, the behavior of hydrogen is unknown at thePTexpected for sub-Neptunes’ interiors, where hydrogen is a dense supercritical fluid. Here we report experimental results of reactions between ferrous/ferric oxides and hydrogen at 20–40 GPa and 1000–4000 K utilizing the pulsed laser-heated diamond-anvil cell combined with synchrotron X-ray diffraction. Under these conditions, hydrogen spontaneously strips iron off the oxides, forming Fe-H alloys and releasing oxygen to the hydrogen medium. In a planetary context where this reaction may occur, the Fe-H alloy may sink to the metallic part of the core, while released oxygen may stabilize as water in the silicate layer, providing a mechanism to ingas hydrogen to the deep interiors of sub-Neptunes. Water produced from the redox reaction can also partition to the atmosphere of sub-Neptunes, which has important implications for understanding the composition of their atmospheres. In addition, super-Earths converted from sub-Neptunes may contain a large amount of hydrogen and water in their interiors (at least a few wt% H2O). This is distinct from smaller rocky planets, which were formed relatively dry (likely a few hundredths wt% H2O).

 
more » « less
Award ID(s):
2108129
NSF-PAR ID:
10396826
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
DOI PREFIX: 10.3847
Date Published:
Journal Name:
The Planetary Science Journal
Volume:
4
Issue:
2
ISSN:
2632-3338
Format(s):
Medium: X Size: Article No. 30
Size(s):
["Article No. 30"]
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 be 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.

     
    more » « less
  2. Abstract

    The early K-type T-Tauri star, V1298 Tau (V= 10 mag, age ≈ 20–30 Myr) hosts four transiting planets with radii ranging from 4.9 to 9.6R. The three inner planets have orbital periods of ≈8–24 days while the outer planet’s period is poorly constrained by single transits observed with K2 and the Transiting Exoplanet Survey Satellite (TESS). Planets b, c, and d are proto–sub-Neptunes that may be undergoing significant mass loss. Depending on the stellar activity and planet masses, they are expected to evolve into super-Earths/sub-Neptunes that bound the radius valley. Here we present results of a joint transit and radial velocity (RV) modeling analysis, which includes recently obtained TESS photometry and MAROON-X RV measurements. Assuming circular orbits, we obtain a low-significance (≈2σ) RV detection of planet c, implying a mass of19.88.9+9.3Mand a conservative 2σupper limit of <39M. For planets b and d, we derive 2σupper limits ofMb< 159MandMd< 41M, respectively. For planet e, plausible discrete periods ofPe> 55.4 days are ruled out at the 3σlevel while seven solutions with 43.3 <Pe/d< 55.4 are consistent with the most probable 46.768131 ± 000076 days solution within 3σ. Adopting the most probable solution yields a 2.6σRV detection with a mass of 0.66 ± 0.26MJup. Comparing the updated mass and radius constraints with planetary evolution and interior structure models shows that planets b, d, and e are consistent with predictions for young gas-rich planets and that planet c is consistent with having a water-rich core with a substantial (∼5% by mass) H2envelope.

     
    more » « less
  3. Abstract

    Super‐Earths ranging up to 10 Earth masses (ME) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe3O4as a low‐pressure analog to Mg2SiO4between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe3O4adopts an 8‐fold coordinated Th3P4‐type structure (I‐43d,Z = 4) with disordered Fe2+and Fe3+into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg2SiO4above 500 GPa in super‐Earth mantles and suggests that Mg2SiO4can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe3O4indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe3O4fugacity buffer considering the Fe3O4phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.

     
    more » « less
  4. Abstract

    Lava worlds are a potential emerging population of Super-Earths that are on close-in orbits around their host stars, with likely partially molten mantles. To date, few studies have addressed the impact of magma on the observed properties of a planet. At ambient conditions, magma is less dense than solid rock; however, it is also more compressible with increasing pressure. Therefore, it is unclear how large-scale magma oceans affect planet observables, such as bulk density. We updateExoPlex, a thermodynamically self-consistent planet interior software, to include anhydrous, hydrous (2.2 wt% H2O), and carbonated magmas (5.2 wt% CO2). We find that Earth-like planets with magma oceans larger than ∼1.5Rand ∼3.2Mare modestly denser than an equivalent-mass solid planet. From our model, three classes of mantle structures emerge for magma ocean planets: (1) a mantle magma ocean, (2) a surface magma ocean, and (3) one consisting of a surface magma ocean, a solid rock layer, and a basal magma ocean. The class of planets in which a basal magma ocean is present may sequester dissolved volatiles on billion-year timescales, in which a 4Mmass planet can trap more than 130 times the mass of water than in Earth’s present-day oceans and 1000 times the carbon in the Earth’s surface and crust.

     
    more » « less
  5. Catalytic hydrogenation of aromatic compounds is an important industrial process, particularly for the production of many petrochemical and pharmaceutical derivatives. This reaction is mainly catalyzed by noble metals, but rarely by metal oxides. Here, we report the development of monoclinic hydrogen-bearing ruthenium dioxide with a nominal composition of H x RuO 2 that can serve as a standalone catalyst for various hydrogenation reactions. The hydrogen-bearing oxide was synthesized through the water gas shift reaction of CO and H 2 O in the presence of rutile RuO 2 . The structure of H x RuO 2 was determined by synchrotron X-ray diffraction and density functional theory (DFT) studies. Solid-state 1 H NMR and Raman studies suggest that this compound possesses two types of isolated interstitial protons. H x RuO 2 is very active in hydrogenation of various arenes, including liquid organic hydrogen carriers, which are completely converted to the corresponding fully hydrogenated products under relatively mild conditions. In addition, high selectivities (>99%) were observed for the catalytic hydrogenation of functionalized nitroarenes to corresponding anilines. DFT simulations yield a small barrier for concerted proton transfer. The facile proton dynamics may be key in enabling selective hydrogenation reactions at relatively low temperature. Our findings inspire the search for hydrogen-containing metal oxides that could be employed as high-performance materials for catalysts, electrocatalysts, and fuel cells. 
    more » « less