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Abstract: Lithium‐rich transition metal oxides with a cation‐disordered rocksalt structure (disordered rocksalt oxides or DRX) are promising candidates for sustainable, next‐generation Li‐ion cathodes due to their high energy densities and compositional flexibility, enabling Co‐ and Ni‐free battery chemistries. However, current methods to synthesize DRX compounds require either high temperature (≈1000 °C) sintering for several hours, or high energy ball milling for several days in an inert atmosphere. Both methods are time‐ and energy‐intensive, limiting the scale up of DRX production. The present study reports the rapid synthesis of various DRX compositions in ambient air via a microwave‐assisted solid‐state technique resulting in reaction times as short as 5 min, which are more than two orders of magnitude faster than current synthesis methods. The DRX compounds synthesized via microwave are phase‐pure and have a similar short‐ and long‐range structure as compared to DRX materials synthesized via a standard solid‐state route, resulting in nearly identical electrochemical performance. In some cases, microwave heating allows for better particle size and morphology control. Overall, the rapid and energy‐efficient microwave technique provides a more sustainable route to produce DRX materials, further incentivizes the development of next‐generation DRX cathodes, and is key to accelerating their optimization via high‐throughput studies.

A combination of gas adsorption and gas breakthrough measurements show that the metal-organic framework, Al(HCOO)3 (ALF), which can be made inexpensively from commodity chemicals, exhibits excellent CO2 adsorption capacities and outstanding CO2/N2 selectivity that enable it to remove CO2 from dried CO2-containing gas streams at elevated temperatures (323 kelvin). Notably, ALF is scalable, readily pelletized, stable to SO2 and NO, and simple to regenerate. Density functional theory calculations and in situ neutron diffraction studies reveal that the preferential adsorption of CO2 is a size-selective separation that depends on the subtle difference between the kinetic diameters of CO2 and N2. The findings are supported by additional measurements, including Fourier transform infrared spectroscopy, thermogravimetric analysis, and variable temperature powder and single-crystal x-ray diffraction.

Coordinatively unsaturated metal sites within certain zeolites and metal-organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H2 at the trigonal pyramidal Cu+ sites in the metal-organic framework CuI-MFU-4l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. The activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu+ coordination environment that enhances π-backbonding with H2. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

The widespread implementation of H2 as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of -15 to -25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal-organic framework (MOF) V2Cl2.8(btdd) (H2btdd, bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak π acids. Significantly, gas adsorption data reveal that this material binds H2 with an enthalpy of -21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)-dihydrogen complexation is characterized by a combination of techniques. From powder neutron diffraction data, a V-D2(centroid) distance of 1.966(8) Å is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the H-H stretch was identified, and it displays a red shift of 242 cm-1. Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium dπ and H2 σ* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly π-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.

Organic semiconductor materials composed of π⁻π stacking aromatic compounds have been under intense investigation for their potential uses in flexible electronics and other advanced technologies. Herein we report a new family of seven π⁻π stacking compounds of silver(I) bis-N-(4-pyridyl) benzamide with varying counterions, namely [Ag(NPBA)2]X, where NPBA is N-(4-pyridyl) benzamine, X = NO₃- (1), ClO₄- (2), CF₃SO₃- (3), PF₆- (4), BF₄- (5), CH₃PhSO₃- (6), and PhSO₃- (7), which form extended π-π stacking networks in one-dimensional (1D), 2D and 3D directions in the crystalline solid-state via the phenyl moiety, with average inter-ring distances of 3.823 Å. Interestingly, the counterions that contain π⁻π stacking-capable groups, such as in 6 and 7, can induce the formation of mesomorphic phases at 130 °C in dimethylformamide (DMF), and can generate highly branched networks at the mesoscale. Atomic force microscopy studies showed that 2D interconnected fibers form right after nucleation, and they extend from ~30 nm in diameter grow to reach the micron scale, which suggests that it may be possible to stop the process in order to obtain nanofibers. Differential scanning calorimetry studies showed no remarkable thermal behavior in the complexes in the solid state, which suggests that the mesomorphic phases originate from the mechanisms that occur in the DMF solution at high temperatures. An all-electron level simulation of the band gaps using NRLMOL (Naval Research Laboratory Molecular Research Library) on the crystals gave 3.25 eV for (1), 3.68 eV for (2), 1.48 eV for (3), 5.08 eV for (4), 1.53 eV for (5), and 3.55 eV for (6). Mesomorphic behavior in materials containing π⁻π stacking aromatic interactions that also exhibit low-band gap properties may pave the way to a new generation of highly branched organic semiconductors.

Solid-state amine absorbent materials, including those containing guanidine derivatives, have received tremendous attention as the world combats the challenges of climate change. Although these materials are attractive for their selective CO2 capture capacity and fast absorption kinetics, the CO2 absorption mechanism with such materials can be unclear and differs when H2O is present. In this work, we present a detailed study on a model guanidine-based crystalline salt, sodium guanidinate (NaCN3H4), and examine the CO2 absorption with and without humidity. The simple composition and high crystallinity of NaCN3H4 and its carbonate capture products allow us to perform ex situ and in situ PXRD to identify possible reaction pathways. These results are complemented by detailed thermogravimetric analysis and gas studies to derive holistic mechanistic insight. We determine that NaCN3H4 exhibits a kinetically controlled CO2 absorption profile with an absorption capacity of ≈12.3 mmol CO2/g, assuming a 1 : 1 : 1 reaction between CO2, H2O, and NaCN3H4. Importantly, humidity is found to significantly lower the activation energy and increase absorption kinetics of CO2 absorption as the products Na2CO3 and (CN3H6)2CO3 form. Our study demonstrates the advantages and drawbacks of using guanidinate materials for CO2 capture under flue gas conditions, and provides clarity about how CO2 capture with similar compounds can be enhanced by humidity. [ABSTRACT FROM AUTHOR]

The article presents materials science research study on how Aluminum formate, an earth-abundant material for CO2 capture. Topics include combination of gas adsorption and gas breakthrough measurements show that the metal-organic framework, Al(HCOO)3 (ALF), which can be made inexpensively from commodity chemicals; and preferential adsorption of CO2 is a size-selective separation that depends on the subtle difference between the kinetic diameters of CO2 and nitrogen gas (N2).