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 (P−T), 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 theP−Texpected 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
Electricity-driven organic hydrogenation using water as the hydrogen source
Employing water as a hydrogen source is an attractive and sustainable option in electricity-driven organic hydrogenation, which can overcome the drawbacks associated with traditional hydrogen sources like H2.
more »
« less
- PAR ID:
- 10653468
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 15
- Issue:
- 40
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 16424 to 16435
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
In the title compound, C8H8ClNO2, the acetamide substituent is twisted out of the phenyl plane, forming a dihedral angle of 58.61 (7)°. In the extended structure, each molecule donates two hydrogen bonds [N—H...O(carbonyl) and O—H...O(carbonyl)] and thus also accepts two such hydrogen bonds. The chlorine atom is not involved in the hydrogen bonding.more » « less
-
Molecular hydrogen is produced by the fermentation of organic matter and consumed by organisms including hydrogenotrophic methanogens and sulfate reducers in anoxic marine sediment. The thermodynamic feasibility of these metabolisms depends strongly on organic matter reactivity and hydrogen concentrations; low organic matter reactivity and high hydrogen concentrations can inhibit fermentation so when organic matter is poor, fermenters might form syntrophies with methanogens and/or sulfate reducers who alleviate thermodynamic stress by keeping hydrogen concentrations low and tightly controlled. However, it is unclear how these metabolisms effect porewater hydrogen concentrations in natural marine sediments of different organic matter reactivities. MethodsWe measured aqueous concentrations of hydrogen, sulfate, methane, dissolved inorganic carbon, and sulfide with high-depth-resolution and 16S rRNA gene assays in sediment cores with low carbon reactivity in White Oak River (WOR) estuary, North Carolina, and those with high carbon reactivity in Cape Lookout Bight (CLB), North Carolina. We calculated the Gibbs energies of sulfate reduction and hydrogenotrophic methanogenesis. ResultsHydrogen concentrations were significantly higher in the sulfate reduction zone at CLB than WOR (mean: 0.716 vs. 0.437 nM H2) with highly contrasting hydrogen profiles. At WOR, hydrogen was extremely low and invariant (range: 0.41–0.52 nM H2) in the upper 15 cm. Deeper than 15 cm, hydrogen became more variable (range: 0.312–2.56 nM H2) and increased until methane production began at ~30 cm. At CLB, hydrogen was highly variable in the upper 15 cm (range: 0.08–2.18 nM H2). Ratios of inorganic carbon production to sulfate consumption show AOM drives sulfate reduction in WOR while degradation of organics drive sulfate reduction in CLB. DiscussionWe conclude more reactive organic matter increases hydrogen concentrations and their variability in anoxic marine sediments. In our AOM-dominated site, WOR, sulfate reducers have tight control on hydrogen via consortia with fermenters which leads to the lower observed variance due to interspecies hydrogen transfer. After sulfate depletion, hydrogen accumulates and becomes variable, supporting methanogenesis. This suggests that CLB’s more reactive organic matter allows fermentation to occur without tight metabolic coupling of fermenters to sulfate reducers, resulting in high and variable porewater hydrogen concentrations that prevent AOM from occurring through reverse hydrogenotrophic methanogenesis.more » « less
-
Abstract Hydrogen may be incorporated into nominally anhydrous minerals including bridgmanite and post‐perovskite as defects, making the Earth's deep mantle a potentially significant water reservoir. The diffusion of hydrogen and its contribution to the electrical conductivity in the lower mantle are rarely explored and remain largely unconstrained. Here we calculate hydrogen diffusivity in hydrous bridgmanite and post‐perovskite, using molecular dynamics simulations driven by machine learning potentials of ab initio quality. Our findings reveal that hydrogen diffusivity significantly increases with increasing temperature and decreasing pressure, and is considerably sensitive to hydrogen incorporation mechanism. Among the four defect mechanisms examined, (Mg + 2H)Siand (Al + H)Sishow similar patterns and yield the highest hydrogen diffusivity. Hydrogen diffusion is generally faster in post‐perovskite than in bridgmanite, and these two phases exhibit distinct diffusion anisotropies. Overall, hydrogen diffusion is slow on geological time scales and may result in heterogeneous water distribution in the lower mantle. Additionally, the proton conductivity of bridgmanite for (Mg + 2H)Siand (Al + H)Sidefects aligns with the same order of magnitude of lower mantle conductivity, suggesting that the water distribution in the lower mantle may be inferred by examining the heterogeneity of electrical conductivity.more » « less
-
Abstract The previously unknown silylgermylidyne radical (H3SiGe; X2A′′) was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X2Π) with germane (GeH4; X1A1) under single collision conditions in crossed molecular beams experiments. This reaction begins with the formation of a van der Waals complex followed by insertion of silylidyne into a germanium‐hydrogen bond forming the germylsilyl radical (H3GeSiH2). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H2GeSiH3), which undergoes a hydrogen shift to an exotic, hydrogen‐bridged germylidynesilane intermediate (H3Si(μ‐H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H3SiGe). Our study offers a remarkable glance at the complex reaction dynamics and inherent isomerization processes of the silicon‐germanium system, which are quite distinct from those of the isovalent hydrocarbon system (ethyl radical; C2H5) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon‐germanium species at the microscopic level exploiting crossed molecular beams.more » « less
An official website of the United States government

