Densified HKUST-1 Monoliths as a Route to High Volumetric and Gravimetric Hydrogen Storage Capacity.

We are currently witnessing the dawn of hydrogen (H2) economy, where H2 will soon become a primary fuel for heating, transportation, and long-distance and long-term energy storage. Among diverse possibilities, H2 can be stored as a pressurized gas, a cryogenic liquid, or a solid fuel via adsorption onto porous materials. Metal-organic frameworks (MOFs) have emerged as adsorbent materials with the highest theoretical H2 storage densities on both a volumetric and gravimetric basis. However, a critical bottleneck for the use of H2 as a transportation fuel has been the lack of densification methods capable of shaping MOFs into practical formulations while maintaining their adsorptive performance. Here, we report a high-throughput screening and deep analysis of a database of MOFs to find optimal materials, followed by the synthesis, characterization, and performance evaluation of an optimal monolithic MOF (monoMOF) for H2 storage. After densification, this monoMOF stores 46 g L-1 H2 at 50 bar and 77 K and delivers 41 and 42 g L-1 H2 at operating pressures of 25 and 50 bar, respectively, when deployed in a combined temperature-pressure (25-50 bar/77 K → 5 bar/160 K) swing gas delivery system. This performance represents up to an 80% reduction in the operating pressure requirements for delivering H2 gas when compared with benchmark materials and an 83% reduction compared to compressed H2 gas. Our findings represent a substantial step forward in the application of high-density materials for volumetric H2 storage applications.

Observation of an Intermediate to H2 Binding in a Metal-Organic Framework.

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.

An International Laboratory Comparison Study of Volumetric and Gravimetric Hydrogen Adsorption Measurements.

In order to determine a material's hydrogen storage potential, capacity measurements must be robust, reproducible, and accurate. Commonly, research reports focus on the gravimetric capacity, and often times the volumetric capacity is not reported. Determining volumetric capacities is not as straight-forward, especially for amorphous materials. This is the first study to compare measurement reproducibility across laboratories for excess and total volumetric hydrogen sorption capacities based on the packing volume. The use of consistent measurement protocols, common analysis, and figure of merits for reporting data in this study, enable the comparison of the results for two different materials. Importantly, the results show good agreement for excess gravimetric capacities amongst the laboratories. Irreproducibility for excess and total volumetric capacities is attributed to real differences in the measured packing volume of the material.

Sensory perception and consumer acceptance of commercial and salt-reduced potato crisps formulated using salt reduction design rules.

Successful salt (NaCl) reduction strategies are required to reduce the salt content of snacks while maintaining saltiness perception and consumer acceptance. Previous research suggests that particle physicochemical design rules (small particle size, low density, low hydrophobicity, optimised particle shape) can be leveraged to produce salt particles that enhance saltiness perception. This study aimed to validate these design rules by applying optimised model salts to unsalted potato crisps at a 30% reduced salt content to produce prototype products. A selection of commercial products were also chosen to represent the salt content and crisp style of the broader market, with the aim to investigate the potential of other salt reduction strategies including; direct salt removal without compensation for loss of salt content and increasing time in mouth, while exploring the impact of consumer mouth behaviour type on consumer product preference. Nine products varying in salt content (6 standard, 1 crinkle-cut, 1 thick-cut batch-fried, 1 baked reconstituted potato) were subject to descriptive sensory analysis with a trained panel (n = 11). A subset (seven products) were assessed for consumer acceptance (n = 93). A salt reduction of 30% was achieved while maintaining saltiness perception and consumer acceptance using model salts, while direct removal of salt without perceptual impact was only achievable by 15%. To investigate key drivers of liking, consumers were segmented based on product liking and mouth behaviour. Results suggested that whilst salt content was the primary driver, specific texture profiles were polarising. However, mouth behaviour had minimal influence on preference. These results validate previously described physicochemical design rules for developing novel salt particles for salt reduction and inform ingredient design for the food and flavour industries.

Physicochemical design rules for the formulation of novel salt particles with optimised saltiness.

Novel sodium reduction strategies are urgently required by the food industry. We hypothesised that redesigning salt crystals (size, density, hydrophobicity and flow properties) will offer a new route to increase saltiness and therefore reduce sodium. Eight salts were compared with different physicochemical properties, the resultant particles were characterised and adhesion to product, loss in-pack, rate of dissolution and ultimately saltiness perception were evaluated. Principle findings included that particle adhesion was driven by particle size (r = -0.85, p = 0.008), bulk density (r = -0.80, p = 0.017) and flow properties (r = 0.77, p = 0.015); loss in-pack was associated with particle size and hydrophobicity of the salt particle while dissolution and/or saltiness perception was also driven by particle size and hydrophobicity of the salt particle. The findings offer a new set of design rules for future ingredient design for the food and flavour industries.

Transient Evolution of the Built-in Field at Junctions of GaAs.

Built-in electric fields at semiconductor junctions are vital for optoelectronic and photocatalytic applications since they govern the movement of photogenerated charge carriers near critical surfaces and interfaces. Here, we exploit transient photoreflectance (TPR) spectroscopy to probe the dynamical evolution of the built-in field for n-GaAs photoelectrodes upon photoexcitation. The transient fields are modeled in order to quantitatively describe the surface carrier dynamics that influence those fields. The photoinduced surface field at different types of junctions between n-GaAs and n-TiO2, Pt, electrolyte and p-NiO are examined, and the results reveal that surface Fermi-level pinning, ubiquitous for many GaAs surfaces, can have beneficial consequences that impact photoelectrochemical applications. That is, Fermi-level pinning results in the primary surface carrier dynamics being invariant to the contacting layer and promotes beneficial carrier separation. For example, when p-NiO is deposited there is no Fermi-level equilibration that modifies the surface field, but photogenerated holes are promoted to the n-GaAs/p-NiO interface and can transfer into defect midgap states within the p-NiO resulting in an elongated charge separation time and those transferred holes can participate in chemical reactions. In contrast, when the Fermi-level is unpinned via molecular surface functionalization on p-GaAs, the carriers undergo surface recombination faster due to a smaller built-in field, thus potentially degrading their photochemical performance.

Record High Hydrogen Storage Capacity in the Metal-Organic Framework Ni2(m-dobdc) at Near-Ambient Temperatures.

Hydrogen holds promise as a clean alternative automobile fuel, but its on-board storage presents significant challenges due to the low temperatures and/or high pressures required to achieve a sufficient energy density. The opportunity to significantly reduce the required pressure for high density H2 storage persists for metal-organic frameworks due to their modular structures and large internal surface areas. The measurement of H2 adsorption in such materials under conditions most relevant to on-board storage is crucial to understanding how these materials would perform in actual applications, although such data have to date been lacking. In the present work, the metal-organic frameworks M2(m-dobdc) (M = Co, Ni; m-dobdc4- = 4,6-dioxido-1,3-benzenedicarboxylate) and the isomeric frameworks M2(dobdc) (M = Co, Ni; dobdc4- = 1,4-dioxido-1,3-benzenedicarboxylate), which are known to have open metal cation sites that strongly interact with H2, were evaluated for their usable volumetric H2 storage capacities over a range of near-ambient temperatures relevant to on-board storage. Based upon adsorption isotherm data, Ni2(m-dobdc) was found to be the top-performing physisorptive storage material with a usable volumetric capacity between 100 and 5 bar of 11.0 g/L at 25 °C and 23.0 g/L with a temperature swing between -75 and 25 °C. Additional neutron diffraction and infrared spectroscopy experiments performed with in situ dosing of D2 or H2 were used to probe the hydrogen storage properties of these materials under the relevant conditions. The results provide benchmark characteristics for comparison with future attempts to achieve improved adsorbents for mobile hydrogen storage applications.

Black optical coating for high-power laser measurements from carbon nanotubes and silicate.

We describe a coating based on potassium silicate, commonly known as water glass, and multiwall carbon nanotubes. The coating has a high absorbance (0.96 at 1064 nm in wavelength) and a laser damage threshold that is comparable to that of ceramic coatings presently used for commercial thermopiles for high-power laser measurements. In addition to a potassium silicate-based coating we discuss sodium silicate, lithium silicate, and a commercially available ceramic coating. We document the coating process and experiments that demonstrate that the laser damage threshold at 1064 nm is 15 kW/cm(2).

Multiwall carbon nanotube absorber on a thin-film lithium niobate pyroelectric detector.

Multiwall carbon nanotubes (MWNTs) were applied in a bulk layer to a pyroelectric film to increase the detector sensitivity nearly fourfold without a substantial penalty to the low-frequency response (4-100 Hz). In addition, the spectral sensitivity over the wavelength range from 600 to 1800 nm was uniformly enhanced, with variations less than 1%. The results demonstrate the suitability of MWNTs as an efficient thermal absorber having low thermal mass.