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1. Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction

   https://doi.org/10.1073/pnas.1900761116  

   Li, Jingyi ; Li, Xiang ; Gunathunge, Charuni M. ; Waegele, Matthias M. ( April 2019 , Proceedings of the National Academy of Sciences)

   The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surface-adsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$, and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$and${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$cations, whereas this product is not synthesized in${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$- and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$-containing electrolytes. Surface-enhanced infrared absorption spectroscopymore »(SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.

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2. The Direct-method Oxygen Abundance of Typical Dwarf Galaxies at Cosmic High Noon∗

   https://doi.org/10.3847/1538-4357/acb153  

   Gburek, Timothy ; Siana, Brian ; Alavi, Anahita ; Emami, Najmeh ; Richard, Johan ; Freeman, William R. ; Stark, Daniel P. ; Snapp-Kolas, Christopher ( May 2023 , The Astrophysical Journal)

   We present a Keck/MOSFIRE rest-optical composite spectrum of 16 typical gravitationally lensed star-forming dwarf galaxies at 1.7 ≲z≲ 2.6 (z_mean= 2.30), all chosen independent of emission-line strength. These galaxies have a median stellar mass of$\log {(M_{*}/M_{\odot })}_{\mathrm{med}}={8.29}_{-0.43}^{+0.51}$and a median star formation rate of${\mathrm{S}\mathrm{F}\mathrm{R}}_{\mathrm{H}\alpha }^{\mathrm{m}\mathrm{e}\mathrm{d}}={2.25}_{-1.26}^{+2.15}{M}_{\odot }{\mathrm{y}\mathrm{r}}^{-1}$. We measure the faint electron-temperature-sensitive [Oiii]λ4363 emission line at 2.5σ(4.1σ) significance when considering a bootstrapped (statistical-only) uncertainty spectrum. This yields a direct-method oxygen abundance of$12+\log {(\mathrm{O}/\mathrm{H})}_{\mathrm{direct}}={7.88}_{-0.22}^{+0.25}$(${0.15}_{-0.06}^{+0.12}{Z}_{\odot }$). We investigate the applicability at highzof locally calibrated oxygen-based strong-line metallicity relations, finding that the local reference calibrations of Bian et al. best reproduce (≲0.12 dex) our composite metallicity at fixed strong-line ratio. At fixedM_*, our composite is well represented by thez∼ 2.3 direct-method stellar mass—gas-phase metallicity relation (MZR) of Sanders et al. When comparing to predicted MZRs from the IllustrisTNG and FIRE simulations, having recalculated our stellar masses with more realistic nonparametric star formation histories$(\log {(M_{*}/M_{\odot })}_{\mathrm{med}}={8.92}_{-0.22}^{+0.31})$, we find excellent agreement with the FIRE MZR. Our composite is consistent with no metallicity evolution, atmore »fixedM_*and SFR, of the locally defined fundamental metallicity relation. We measure the doublet ratio [Oii]λ3729/[Oii]λ3726 = 1.56 ± 0.32 (1.51 ± 0.12) and a corresponding electron density of$n_e=1_{-0}^{+215}{\mathrm{cm}}^{-3}$($n_e=1_{-0}^{+74}{\mathrm{cm}}^{-3}$) when considering the bootstrapped (statistical-only) error spectrum. This result suggests that lower-mass galaxies have lower densities than higher-mass galaxies atz∼ 2.

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3. Large H ₂ O solubility in dense silica and its implications for the interiors of water-rich planets

   https://doi.org/10.1073/pnas.1917448117  

   Nisr, Carole ; Chen, Huawei ; Leinenweber, Kurt ; Chizmeshya, Andrew ; Prakapenka, Vitali B. ; Prescher, Clemens ; Tkachev, Sergey N. ; Meng, Yue ; Liu, Zhenxian ; Shim, Sang-Heon ( April 2020 , Proceedings of the National Academy of Sciences)

   Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in${\mathrm{H}}_2$O-rich setting at high pressures and temperatures ($P-T$) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between${\mathrm{S}\mathrm{i}\mathrm{O}}_2$and${\mathrm{H}}_2$O as archetypal materials for rock and ice, respectively, at high$P-T$. We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the${\mathrm{C}\mathrm{a}\mathrm{C}\mathrm{l}}_2$-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 (${\mathrm{S}\mathrm{i}}_{1-x}{\mathrm{H}}_{4x}$)${\mathrm{O}}_2\hspace{0.17em}\left(x=0.12\right)$. At pressures above 60 GPa,${\mathrm{H}}_2$O 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.

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4. Intermediate valence state in YbB ₄ revealed by resonant x-ray emission spectroscopy

   https://doi.org/10.1088/1361-648X/ac7629  

   Frontini, Felix ; Lebert, Blair W. ; Cho, K. K. ; Song, M. S. ; Cho, B. K. ; Pollock, Christopher J. ; Kim, Young-June ( June 2022 , Journal of Physics: Condensed Matter)

   We report the temperature dependence of the Yb valence in the geometrically frustrated compound${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$from 12 to 300 K using resonant x-ray emission spectroscopy at the Yb$L_{{\alpha }_1}$transition. We find that the Yb valence,v, is hybridized between thev = 2 andv = 3 valence states, increasing from$v=2.61\pm 0.01$at 12 K to$v=2.67\pm 0.01$at 300 K, confirming that${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is a Kondo system in the intermediate valence regime. This result indicates that the Kondo interaction in${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is substantial, and is likely to be the reason why${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$does not order magnetically at low temperature, rather than this being an effect of geometric frustration. Furthermore, the zero-point valence of the system is extracted from our data and compared with other Kondo lattice systems. The zero-point valence seems to be weakly dependent on the Kondo temperature scale, but not on the valence change temperature scaleT_v.
5. Evidence for AGN-regulated Cooling in Clusters at z ∼ 1.4: A Multiwavelength View of SPT-CL J0607-4448

   https://doi.org/10.3847/1538-4357/acae9e  

   Masterson, Megan ; McDonald, Michael ; Ansarinejad, Behzad ; Bayliss, Matthew ; Benson, Bradford A. ; Bleem, Lindsey E. ; Calzadilla, Michael S. ; Edge, Alastair C. ; Floyd, Benjamin ; Kim, Keunho J. ; et al ( February 2023 , The Astrophysical Journal)

   We present a multiwavelength analysis of the galaxy cluster SPT-CL J0607-4448 (SPT0607), which is one of the most distant clusters discovered by the South Pole Telescope atz= 1.4010 ± 0.0028. The high-redshift cluster shows clear signs of being relaxed with well-regulated feedback from the active galactic nucleus (AGN) in the brightest cluster galaxy (BCG). Using Chandra X-ray data, we construct thermodynamic profiles and determine the properties of the intracluster medium. The cool-core nature of the cluster is supported by a centrally peaked density profile and low central entropy ($K_0={18}_{-9}^{+11}$keV cm²), which we estimate assuming an isothermal temperature profile due to the limited spectral information given the distance to the cluster. Using the density profile and gas cooling time inferred from the X-ray data, we find a mass-cooling rate${\dot{M}}_{\mathrm{cool}}={100}_{-60}^{+90}{M}_{\odot }$yr⁻¹. From optical spectroscopy and photometry around the [Oii] emission line, we estimate that the BCG star formation rate is${\mathrm{SFR}}_{[\mathrm{O}\mathrm{II}]}={1.7}_{-0.6}^{+1.0}{M}_{\odot }$yr⁻¹, roughly two orders of magnitude lower than the predicted mass-cooling rate. In addition, using ATCA radio data at 2.1 GHz, we measure a radio jet power$P_{\mathrm{cav}}={3.2}_{-1.3}^{+2.1}\times {10}^{44}$erg s⁻¹, which is consistent withmore »the X-ray cooling luminosity ($L_{\mathrm{cool}}={1.9}_{-0.5}^{+0.2}\times {10}^{44}$erg s⁻¹withinr_cool= 43 kpc). These findings suggest that SPT0607 is a relaxed, cool-core cluster with AGN-regulated cooling at an epoch shortly after cluster formation, implying that the balance between cooling and feedback can be reached quickly. We discuss the implications for these findings on the evolution of AGN feedback in galaxy clusters.

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