TY - JOUR

T1 - Ionic Clathrate Hydrates of Tetraalkylammonium/phosphonium Salts: Structures, Properties, Some Applications, and Perspectives

AU - Rodionova, Tatyana V.

AU - Terekhova, Irina S.

AU - Manakov, Andrey Y.

N1 - Funding Information: This work was supported by the Ministry of Science and Higher Education of the Russian Federation grant No. 121031700321-3. Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/9/15

Y1 - 2022/9/15

N2 - Ionic clathrate hydrates (ICHs) belong to one of the groups of a wide class of clathrate hydrates. In the crystal structures of ICHs, cation-anion pairs of guest molecules, typically tetraalkylammonium/phosphonium salts, are included into the host framework of hydrogen-bonded water molecules. Because of their suitable phase change temperature and latent heat, ICHs are considered as promising phase change materials for application in cold energy storage and transportation. The presence of vacant cavities in ICHs structures, which can incorporate small gas molecules such as, for example, H2, CH4, CO2, N2, H2S, determines the possibility of their use for the separation and storage of gases. The formation of these double ICHs occurs under much milder pressure and temperature conditions compared to the pure gas hydrates of the same gases. Studying of the structural characteristics and thermophysical properties of ICHs and double ICHs with gases is the necessary basis for their effective applications in different practical ends. This work reviews information related to the new details and features of the structures of ICHs and double ICHs with gases revealed over the last decade or a little more as well as some thermophysical data such as hydrate numbers, temperatures and enthalpies of dissociation. This review focuses only on ICHs of tetrabutyl-, tetraisoamylammonium (TBA, TiAA), and tetrabutylphosphonium (TBP) salts, which are the most common representatives of this class of compounds. One of the sections is devoted to ICHs of TBA and TiAA with polymeric anions such as cross-linked polyacrylates. The purpose of the present paper is to review the studies that have been relatively little addressed in previous works.

AB - Ionic clathrate hydrates (ICHs) belong to one of the groups of a wide class of clathrate hydrates. In the crystal structures of ICHs, cation-anion pairs of guest molecules, typically tetraalkylammonium/phosphonium salts, are included into the host framework of hydrogen-bonded water molecules. Because of their suitable phase change temperature and latent heat, ICHs are considered as promising phase change materials for application in cold energy storage and transportation. The presence of vacant cavities in ICHs structures, which can incorporate small gas molecules such as, for example, H2, CH4, CO2, N2, H2S, determines the possibility of their use for the separation and storage of gases. The formation of these double ICHs occurs under much milder pressure and temperature conditions compared to the pure gas hydrates of the same gases. Studying of the structural characteristics and thermophysical properties of ICHs and double ICHs with gases is the necessary basis for their effective applications in different practical ends. This work reviews information related to the new details and features of the structures of ICHs and double ICHs with gases revealed over the last decade or a little more as well as some thermophysical data such as hydrate numbers, temperatures and enthalpies of dissociation. This review focuses only on ICHs of tetrabutyl-, tetraisoamylammonium (TBA, TiAA), and tetrabutylphosphonium (TBP) salts, which are the most common representatives of this class of compounds. One of the sections is devoted to ICHs of TBA and TiAA with polymeric anions such as cross-linked polyacrylates. The purpose of the present paper is to review the studies that have been relatively little addressed in previous works.

UR - http://www.scopus.com/inward/record.url?scp=85136766001&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/26c2ce07-7f29-351b-8fbe-210a2770dc8c/

U2 - 10.1021/acs.energyfuels.2c01221

DO - 10.1021/acs.energyfuels.2c01221

M3 - Review article

AN - SCOPUS:85136766001

VL - 36

SP - 10458

EP - 10477

JO - Energy & Fuels

JF - Energy & Fuels

SN - 0887-0624

IS - 18

ER -