Improving the direct air capture capacity of grafted amines via thermal treatment.

This study investigates the effects of elevated temperature thermal treatments on the direct air capture of CO2 by aminosilane-grafted SBA-15 silica sorbents. Exposing samples to high temperatures (200-250 °C compared to 80-120 °C) in an inert environment resulted in improved CO2 capacity (5-21%) that was sustained over multiple adsorption/desorption cycles.

Laser-Induced Thermal Decomposition of Uranium Coordination Compounds with Non-oxidic Ligands to Produce Nitride and Carbide Materials.

The production of ceramics from uranium coordination compounds can be achieved through thermal processing if an excess amount of the desired atoms (i.e., C or N), or reactive gaseous products (e.g., methane or nitrogen oxide) is made available to the reactive uranium metal core via decomposition/fragmentation of the surrounding ligand groups. Here, computational thermodynamic approaches were utilized to identify the temperatures necessary to produce uranium metal from some starting compounds─UI4(TMEDA)2, UCl4(TMEDA)2, UCl3(pyridine)x, and UI3(pyridine)4. Experimentally, precursors were irradiated by a laser under various gaseous environments (argon, nitrogen, and methane) creating extreme reaction conditions (i.e., fast heating, high temperature profile >2000 °C, and rapid cooling). Despite the fast dynamics associated with laser irradiation, the central uranium atom reacted with the thermal decomposition products of the ligands yielding uranium ceramics. Residual gas analysis identified vaporized products from the laser irradiation, and the final ceramic products were characterized by powder X-ray diffraction. The composition of the uranium precursor as well as the gaseous environment had a direct impact on the production of the final phases.

Enhanced hydrogen bonding via epoxide-functionalization restricts mobility in poly(ethylenimine) for CO2 capture.

Free energy sampling, deep potential molecular dynamics, and characterizations provide insights into the impact of epoxide-functionalization on the hydrogen bonding and mobility of poly(ethylenimine), a promising CO2 sorbent. These findings rationalize the anti-degradation effects of epoxide functionalization and open up new avenues for designing more durable CO2 sorbents.

Hydrogen Storage in Partially Exfoliated Magnesium Diboride Multilayers.

Metal boride nanostructures have shown significant promise for hydrogen storage applications. However, the synthesis of nanoscale metal boride particles is challenging because of their high surface energy, strong inter- and intraplanar bonding, and difficult-to-control surface termination. Here, it is demonstrated that mechanochemical exfoliation of magnesium diboride in zirconia produces 3-4 nm ultrathin MgB2 nanosheets (multilayers) in high yield. High-pressure hydrogenation of these multilayers at 70 MPa and 330 °C followed by dehydrogenation at 390 °C reveals a hydrogen capacity of 5.1 wt%, which is ≈50 times larger than the capacity of bulk MgB2 under the same conditions. This enhancement is attributed to the creation of defective sites by ball-milling and incomplete Mg surface coverage in MgB2 multilayers, which disrupts the stable boron-boron ring structure. The density functional theory calculations indicate that the balance of Mg on the MgB2 nanosheet surface changes as the material hydrogenates, as it is energetically favorable to trade a small number of Mg vacancies in Mg(BH4 )2 for greater Mg coverage on the MgB2 surface. The exfoliation and creation of ultrathin layers is a promising new direction for 2D metal boride/borohydride research with the potential to achieve high-capacity reversible hydrogen storage at more moderate pressures and temperatures.

Closo-Borate Gel Polymer Electrolyte with Remarkable Electrochemical Stability and a Wide Operating Temperature Window.

A major challenge in the pursuit of higher-energy-density lithium batteries for carbon-neutral-mobility is electrolyte compatibility with a lithium metal electrode. This study demonstrates the robust and stable nature of a closo-borate based gel polymer electrolyte (GPE), which enables outstanding electrochemical stability and capacity retention upon extensive cycling. The GPE developed herein has an ionic conductivity of 7.3 × 10-4  S cm-2 at room temperature and stability over a wide temperature range from -35 to 80 °C with a high lithium transference number ( tLi+$t_{{\rm{Li}}}^ + $ = 0.51). Multinuclear nuclear magnetic resonance and Fourier transform infrared are used to understand the solvation environment and interaction between the GPE components. Density functional theory calculations are leveraged to gain additional insight into the coordination environment and support spectroscopic interpretations. The GPE is also established to be a suitable electrolyte for extended cycling with four different active electrode materials when paired with a lithium metal electrode. The GPE can also be incorporated into a flexible battery that is capable of being cut and still functional. The incorporation of a closo-borate into a gel polymer matrix represents a new direction for enhancing the electrochemical and physical properties of this class of materials.

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage.

The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH3 @CTF-bipyridine). This material and the counterpart AlH3 @CTF-biphenyl rapidly desorb H2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27 Al MAS NMR and 27 Al{1 H} REDOR experiments, and computational spectroscopy reveal that AlH3 @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH3 binding to bipyridine results in single-electron transfer to form AlH2 (AlH3 )n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.

Reversing the Irreversible: Thermodynamic Stabilization of LiAlH4 Nanoconfined Within a Nitrogen-Doped Carbon Host.

A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH4 as an exemplar, we demonstrate an alternative approach to the thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH4@NCMK-3 material releases H2 at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual Li3AlH6 intermediate observed in bulk. Moreover, >80% of LiAlH4 can be regenerated under 100 MPa H2, a feat previously thought to be impossible. Nitrogen sites are critical to these improvements, as no reversibility is observed with undoped CMK-3. Density functional theory predicts a drastically reduced Al-H bond dissociation energy and supports the observed change in the reaction pathway. The calculations also provide a rationale for the solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab†Initio Approach.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid-state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF-sputtered LiPON. Information about the short-range structure results from 1D and 2D solid-state NMR experiments. These results are compared with first principles chemical shielding calculations of Li-P-O/N crystals and ab initio molecular dynamics-generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON's stability is a result of its glassy character. Free-standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials.

Fragility and aging behavior of SixSe1-x glasses and liquids.

The composition dependence of the fragility of SixSe1-x liquids with 0.05 ≤ x ≤ 0.33 is determined using the calorimetric method and is found to be rather similar to that characteristic of their Ge analogues. In addition, the nature and the time scale of the structural relaxation of the Si25Se75 glass during aging at 40 K below Tg are measured using Raman spectroscopy. The structural relaxation in this glass, which belongs to the so-called intermediate phase, involves progressive conversion of the doubly edge-shared SiSe4/2 tetrahedra E2 into singly edge-shared E1 and corner-shared E0 tetrahedra upon lowering of temperature. This tetrahedral speciation can be expressed in the form of the reaction 2 E2 → E0 + E1. The time scale of this tetrahedral conversion reaction corresponds well with that of shear relaxation. This result is inconsistent with the claim made previously in the literature that intermediate phase compositions do not undergo aging. Moreover, when taken together, the fragility and the structural relaxation results suggest that the constraint counting scheme typically adopted in the literature for edge- vs. corner-shared tetrahedra in chalcogenide networks may need to be revised. A rigid-polytope based constraint counting approach is shown to be more consistent with the experimental results.

Network Structure and Connectivity in SnO-P2O5 Glasses: Results from 2D 31P and 119Sn NMR Spectroscopy.

The compositional evolution of the network structure and connectivity in binary SnO-P2O5 glasses with 35 ≤ mol % SnO ≤ 55 is studied using two-dimensional 119Sn and 31P NMR spectroscopy. The phosphate Q n species concentrations, as obtained from the analyses of the 31P NMR spectral line shapes suggest that the network modification can be described in terms of a binary Q-speciation model. On the other hand, the 119Sn NMR spectra suggest that the Sn-O coordination environment in these glasses is composition dependent. Sn is present in both 3-fold (trigonal pyramid) and 4-fold (trigonal bipyramid) coordinations with oxygen in these glasses. The relative fraction of the trigonal pyramidal environment increases with increasing SnO content. The unusually low glass transition temperature Tg of these glasses (241-266 °C) is argued to be related to the low coordination number of Sn, leading to a relatively sparsely connected structural network.