Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H2 clathrate hydrate.

This study introduces solid-state tuning of a mesostructured cellular foam (MCF) to enhance hydrogen (H2) storage in clathrate hydrates. Grafting of promoter-like molecules (e.g., tetrahydrofuran) at the internal surface of the MCF resulted in a substantial improvement in the kinetics of formation of binary H2-THF clathrate hydrate. Identification of the confined hydrate as sII clathrate hydrate and enclathration of H2 in its small cages was performed using XRD and high-pressure 1H NMR spectroscopy respectively. Experimental findings show that modified MCF materials exhibit a ∼1.3 times higher H2 storage capacity as compared to non-modified MCF under the same conditions (7 MPa, 265 K, 100% pore volume saturation with a 5.56 mol% THF solution). The enhancement in H2 storage is attributed to the hydrophobicity originating from grafting organic molecules onto pristine MCF, thereby influencing water interactions and fostering an environment conducive to H2 enclathration. Gas uptake curves indicate an optimal tuning point for higher H2 storage, favoring a lower density of carbon per nm2. Furthermore, a direct correlation emerges between higher driving forces and increased H2 storage capacity, culminating at 0.52 wt% (46.77 mmoles of H2 per mole of H2O and 39.78% water-to-hydrate conversions) at 262 K for the modified MCF material with fewer carbons per nm2. Notably, the substantial H2 storage capacity achieved without energy-intensive processes underscores solid-state tuning's potential for H2 storage in the synthesized hydrates. This study evaluated two distinct kinetic models to describe hydrate growth in MCF. The multistage kinetic model showed better predictive capabilities for experimental data and maintained a low average absolute deviation. This research provides valuable insights into augmenting H2 storage capabilities and holds promising implications for future advancements.

Recent Trends in Plasmon-Assisted Photocatalytic CO2 Reduction.

Direct photocatalytic reduction of CO2 has become an highly active field of research. It is thus of utmost importance to maintain an overview of the various materials used to sustain this process, find common trends, and, in this way, eventually improve the current conversions and selectivities. In particular, CO2 photoreduction using plasmonic photocatalysts under solar light has gained tremendous attention, and a wide variety of materials has been developed to reduce CO2 towards more practical gases or liquid fuels (CH4 , CO, CH3 OH/CH3 CH2 OH) in this manner. This Review therefore aims at providing insights in current developments of photocatalysts consisting of only plasmonic nanoparticles and semiconductor materials. By classifying recent studies based on product selectivity, this Review aims to unravel common trends that can provide effective information on ways to improve the photoreduction yield or possible means to shift the selectivity towards desired products, thus generating new ideas for the way forward.

Plasmonic Near-Field Localization of Silver Core-Shell Nanoparticle Assemblies via Wet Chemistry Nanogap Engineering.

Silver nanoparticles are widely used in the field of plasmonics because of their unique optical properties. The wavelength-dependent surface plasmon resonance gives rise to a strongly enhanced electromagnetic field, especially at so-called hot spots located in the nanogap in-between metal nanoparticle assemblies. Therefore, the interparticle distance is a decisive factor in plasmonic applications, such as surface-enhanced Raman spectroscopy (SERS). In this study, the aim is to engineer this interparticle distance for silver nanospheres using a convenient wet-chemical approach and to predict and quantify the corresponding enhancement factor using both theoretical and experimental tools. This was done by building a tunable ultrathin polymer shell around the nanoparticles using the layer-by-layer method, in which the polymer shell acts as the separating interparticle spacer layer. Comparison of different theoretical approaches and corroborating the results with SERS analytical experiments using silver and silver-polymer core-shell nanoparticle clusters as SERS substrates was also done. Herewith, an approach is provided to estimate the extent of plasmonic near-field enhancement both theoretically as well as experimentally.