Reply to the 'Comment on Cage occupancy of methane clathrate hydrates in the ternary H2O-NH3-CH4 system' by S. Alavi and J. Ripmeester, Chem. Commun., 2022, 58, DOI: 10.1039/D1CC06526B.

Our recent Communication suggested that ammonia in aqueous solution may preferentially destabilize large cages in methane clathrate hydrates. A Comment favored ammonia incorporation instead, but it did not accurately describe our proposed mechanism and relied primarily on studies conducted in different chemical systems and/or which used other preparation methods.

Promoting the Insertion of Molecular Hydrogen in Tetrahydrofuran Hydrate With the Help of Acidic Additives.

Among hydrogen storage materials, hydrogen hydrates have received a particular attention over the last decades. The pure hydrogen hydrate is generated only at extremely high-pressure (few thousands of bars) and the formation conditions are known to be softened by co-including guest molecules such as tetrahydrofuran (THF). Since this discovery, there have been considerable efforts to optimize the storage capacities in hydrates through the variability of the formation condition, of the cage occupancy, of the chemical composition or of the hydrate structure (ranging from clathrate to semi-clathrate). In addition to this issue, the hydrogen insertion mechanism plays also a crucial role not only at a fundamental level, but also in view of potential applications. This paper aims at studying the molecular hydrogen diffusion in the THF hydrate by in-situ confocal Raman microspectroscopy and imaging, and at investigating the impact of strong acid onto this diffusive process. This study represents the first report to shed light on hydrogen diffusion in acidic THF-H2 hydrate. Integrating the present result with those from previous experimental investigations, it is shown that the hydrogen insertion in the THF hydrate is optimum for a pressure of ca. 55 bar at 270 K. Moreover, the co-inclusion of perchloric acid (with concentration as low as 1 acidic molecules per 136 water molecules) lead to promote the molecular hydrogen insertion within the hydrate structure. The hydrogen diffusion coefficient-measured at 270 K and 200 bar-is improved by a factor of 2 thanks to the acidic additive.

Cage occupancy of methane clathrate hydrates in the ternary H2O-NH3-CH4 system.

The incorporation of ammonia inside methane clathrate hydrate is of great interest to the hydrate chemistry community. We investigated the phase behavior of methane clathrate formed from aqueous ammonia solution. Ammonia's presence decreases methane occupancy in the large cages, without definitive Raman spectroscopic evidence for its incorporation inside the structure.

Unraveling the metastability of the SI and SII carbon monoxide hydrate with a combined DFT-neutron diffraction investigation.

Clathrate hydrates are crystalline compounds consisting of water molecules forming cages (so-called "host") inside of which "guest" molecules are encapsulated depending on the thermodynamic conditions of formation (systems stable at low temperature and high pressure). These icelike systems are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. Carbon monoxide hydrate might be considered an important component of the carbon cycle in the solar system since CO gas is one of the predominant forms of carbon. Intriguing fundamental properties have also been reported: the CO hydrate initially forms in the sI structure (kinetically favored) and transforms into the sII structure (thermodynamically stable). Understanding and predicting the gas hydrate structural stability then become essential. The aim of this work is, thereby, to study the structural and energetic properties of the CO hydrate using density functional theory (DFT) calculations together with neutron diffraction measurements. In addition to the comparison of DFT-derived structural properties with those from experimental neutron diffraction, the originality of this work lies in the DFT-derived energy calculations performed on a complete unit cell (sI and sII) and not only by considering guest molecules confined in an isolated water cage (as usually performed for extracting the binding energies). Interestingly, an excellent agreement (within less than 1% error) is found between the measured and DFT-derived unit cell parameters by considering the Perdew-Burke-Ernzerhof (denoted PBE) functional. Moreover, a strategy is proposed for evaluating the hydrate structural stability on the basis of potential energy analysis of the total nonbonding energies (i.e., binding energy and water substructure nonbonding energy). It is found that the sII structure is the thermodynamically stable hydrate phase. In addition, increasing the CO content in the large cages has a stabilizing effect on the sII structure, while it destabilizes the sI structure. Such findings are in agreement with the recent experimental results evidencing the structural metastability of the CO hydrate.

Selective trapping of CO2 gas and cage occupancy in CO2-N2 and CO2-CO mixed gas hydrates.

Hydrate-based CO2 trapping from CO2-N2 and CO2-CO gas mixtures is shown by Raman spectroscopy - the results are of interest for new separation and capture technology. A better trapping efficiency is measured for low CO2 concentrations and N2-based gas mixtures. Moreover, it is observed that CO molecules would impede hydrate formation from ice when a CO-enriched gas mixture is considered.