Attention:The NSF Public Access Repository (PAR) system and access will be unavailable from 5:00 PM ET until 8:00 PM ET on Friday, September 11 due to maintenance. We apologize for the inconvenience.


Title: Stabilizing Ti 3 C 2 T x MXene flakes in air by removing confined water
MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti 3 C 2 T x MXene monoflakes have exceptional thermal stability at temperatures up to 600 ° C in air, while multiflakes readily oxidize in air at 300 ° C. Density functional theory calculations indicate that confined water between Ti 3 C 2 T x flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti 3 C 2 T x films at 600 ° C, resulting in substantial stability improvement in multiflake films (can withstand 600 ° C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti 3 C 2 T x oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability.  more » « less
Award ID(s):
2134607
PAR ID:
10545591
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Fakhraai
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
121
Issue:
28
ISSN:
0027-8424
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Understanding how close tropical tree species are to critical temperature thresholds that might impede photosynthetic activity is vital in a world where heat waves have become more severe and frequent. Using remotely sensed surface temperature and species distribution maps, we studied the spatiotemporal variation in the thermal safety margins (TSM, i.e., the difference between Tcrit , the critical photosynthetic temperature, and the maximum canopy temperature) of 208 tropical tree species in South America, Southeast Asia, and Central Africa during the period 2001–2020. Despite overall high-temperature tolerance with an average Tcrit of 46.1° C, we observed a consistent decline in the TSM of tropical forests across the globe. The average pantropical TSM decline was 0.4° C per decade, with the strongest decline in South America ( 0.5° C per decade). Over the 20 -y period, areas that experienced canopy temperatures surpassing the average Tcrit across reported species increased from 43 Mha to 57 Mha in the tropics, representing 4% of the studied area. This number increases to 10% when computing areas where temperatures have surpassed the Tcrit of the most vulnerable reported species. When considering future trends, as predicted by Earth System Models under medium-to-high emission scenarios, average Tcrit may be exceeded in an area of 83 Mha by 2050 and 160 Mha by 2100 (over 10% of the studied area), suggesting major feedback to the global carbon cycle and the world’s biodiversity. 
    more » « less
  2. While hydrogen-rich materials have been demonstrated to exhibit high Tcsuperconductivity at high pressures, there is an ongoing search for ternary, quaternary, and more chemically complex hydrides that achieve such high critical temperatures at much lower pressures. First-principles searches are impeded by the computational complexity of solving the Eliashberg equations for large, complex crystal structures. Here, we adopt a simplified approach using electronic indicators previously established to be correlated with superconductivity in hydrides. This is used to study complex hydride structures, which are predicted to exhibit promisingly high critical temperatures for superconductivity. In particular, we propose three classes of hydrides inspired by the Fm 3¯ m RH 3 structures that exhibit strong hydrogen network connectivity, as defined through the electron localization function. The first class [RH 11 X 3 Y] is based on a Pm 3¯ m structure showing moderately high Tc, where the Tcestimate from electronic properties is compared with direct Eliashberg calculations and found to be surprisingly accurate. The second class of structures [(RH 11 ) 2 X 6 YZ] improves on this with promisingly high density of states with dominant hydrogen character at the Fermi energy, typically enhancing Tc. The third class [(R 1 H 11 )(R 2 H 11 )X 6 YZ] improves the strong hydrogen network connectivity by introducing anisotropy in the hydrogen network through a specific doping pattern. These design principles and associated model structures provide flexibility to optimize both Tcand the structural stability of complex hydrides. 
    more » « less
  3. Abstract We present analysis of one of the most extreme quasar outflows found to date in our survey of extremely high-velocity outflows (EHVOs). J164653.72+243942.2 (zem ∼ 3.04) shows variable Civλλ1548,1551 absorption at speeds larger than 0.1c, accompanied by Siiv, Nv,and Lyα, and disappearing absorption at lower speeds. We perform absorption measurements using the apparent optical depth method and SimBAL. We find the absorption to be very broad (Δv ∼  35,100 km s−1in the first epoch and 13,000 km s−1in the second one) and fast (vmax ∼  –50,200 km s−1and −49,000 km s−1, respectively). We measure large column densities ( logNH> 21.6 (cm−2)) and are able to place distance estimates for the EHVO (5 ≲ R ≲ 28 pc) and the lower-velocity outflow (7 ≲ R ≲ 540 pc). We estimate a mass outflow rate for the EHVO to be Ṁout 50290Myr1 and a kinetic luminosity of logLKE46.547.2(ergs1) in both epochs. The lower-velocity component has a mass outflow rate Ṁout 10790Myr1 and a kinetic luminosity of logLKE45.347.2(ergs1) . We find that J164653.72+243942.2 is not an outlier among EHVO quasars in regard to its physical properties. While its column density is lower than typical BAL values, its higher outflow velocities drive most of the mass outflow rate and kinetic luminosity. These results emphasize the crucial role of EHVOs in powering quasar feedback, and failing to account for these outflows likely leads to underestimating the feedback impact on galaxies. 
    more » « less
  4. A charge density wave (CDW) is a phase of matter characterized by a periodic modulation of valence electron density coupled with lattice distortion. Its formation is closely tied to the dynamical charge susceptibility, χ(q,ω) , which reflects the collective electron dynamics of the material. Despite decades of study, χ(q,ω) near a CDW transition has never been measured at nonzero momentum, q , with meV energy resolution. Here, we investigate the canonical CDW transition in ErTe 3 using momentum-resolved electron energy loss spectroscopy, a technique uniquely sensitive to valence band charge excitations. Unlike phonons, which soften via the Kohn anomaly, we find the electronic excitations exhibit purely relaxational dynamics well described by a diffusive model, with the diffusivity peaking just below the critical temperature, TC1 . Additionally, we report for the first time a divergence in the real part of χ(q,ω) in the static limit ( ω0 ), a long-predicted hallmark of CDWs. Unexpectedly, this divergence occurs as T0 , with only a weak thermodynamic signature at T= TC1 . Our study necessitates a reexamination of the traditional description of CDW formation in quantum materials. 
    more » « less
  5. Abstract We present a systematic study of the environments of 25 luminous quasars atz > 6.5 from the ASPIRE program. Using JWST/NIRCam wide-field slitless spectroscopy data, we identified 487 galaxies at 5.3 ≲ z ≲ 7.0 exhibiting [Oiii] emission. Among these, 122 [Oiii] emitters lie within ∣Δvlos∣ < 1000 km s−1of the quasars, corresponding to a ∼9.4-fold enhancement relative to the average galaxy density at other redshifts. Furthermore, we identified 16 [Cii]-emitting galaxies at the quasar redshifts from Atacama Large Millimeter/submillimeter Array (ALMA) mosaic observations. A cross-correlation function analysis between quasars and [Oiii]+[Cii] emitters yields a cross-correlation length of r0QG =8.6 80.55+0.51 h1cMpc and an autocorrelation of r0QQ =15.7 62.70+2.48 h1cMpc , indicating thatz ∼ 7 quasars reside in dark matter halos with Mhalo =10 12.2 70.26+0.21 M and have a quasar lifetime of tQ=10 7.051.01+0.95 yr . Notably, the number of [Oiii]-emitting galaxies at quasar redshifts varies significantly from field to field, ranging from 0 to 20, highlighting a diverse quasar environment. Remarkably, seven quasars trace significant galaxy overdensities (i.e., protoclusters), withδgal > 5 within a volume ofV ∼ 500 cMpc3. We also find that ∣Δvlos∣ increases rapidly toward smaller galaxy–quasar separations in protocluster fields, consistent with galaxy kinematics around extremely massive halos in cosmological simulations. By combining JWST and ALMA data, we reveal the complex and diverse environments of these early quasars, providing robust evidence that the earliest luminous quasars are effective tracers of galaxy overdensities, albeit with substantial field-to-field variation. 
    more » « less