eprintid: 10048644 rev_number: 26 eprint_status: archive userid: 608 dir: disk0/10/04/86/44 datestamp: 2018-05-18 11:32:13 lastmod: 2021-09-25 23:18:12 status_changed: 2018-05-18 11:32:13 type: article metadata_visibility: show creators_name: Loganathan, N creators_name: Bowers, GM creators_name: Yazaydin, AO creators_name: Schaef, HT creators_name: Loring, JS creators_name: Kalinichev, AG creators_name: Kirkpatrick, RJ title: Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations ispublished: pub divisions: UCL divisions: B04 divisions: C05 divisions: F43 keywords: Science & Technology, Physical Sciences, Technology, Chemistry, Physical, Nanoscience & Nanotechnology, Materials Science, Multidisciplinary, Chemistry, Science & Technology - Other Topics, Materials Science, X-RAY-DIFFRACTION, NUCLEAR-MAGNETIC-RESONANCE, NATURAL ORGANIC-MATTER, MOLECULAR-DYNAMICS, IN-SITU, SMECTITE CLAYS, EXCHANGED MONTMORILLONITE, NA-MONTMORILLONITE, WATER-STRUCTURE, LAYER CHARGE note: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. abstract: In situ X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) experiments combined with molecular dynamics simulations using the grand canonical ensemble [grand canonical molecular dynamics (GCMD)] show that the cation size, charge, and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical scCO2 (scCO2) under conditions relevant to petroleum reservoirs and geological CO2 sequestration conditions. The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with small ionic radii and high solvation energies (e.g., Na+ and Ca2+) does not intercalate CO2 and that the fully collapsed interlayer structure is the most energetically stable configuration. With Cs+ and Ba2+, the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+, there is not even an energy barrier for CO2 intercalation, in agreement with the XRD and NMR results. 13C NMR and simulations show that the average orientation of the intercalated CO2 is with their O–C–O axes parallel to the basal clay surface and that they undergo a rapid rotation about an axis perpendicular to the main molecular axis. The simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2. date: 2018-02-08 date_type: published publisher: AMER CHEMICAL SOC official_url: https://doi.org/10.1021/acs.jpcc.7b12270 oa_status: green full_text_type: other language: eng primo: open primo_central: open_green article_type_text: Article verified: verified_manual elements_id: 1544090 doi: 10.1021/acs.jpcc.7b12270 lyricists_name: Yazaydin, Ahmet lyricists_id: AOYAZ19 actors_name: Stacey, Thomas actors_id: TSSTA20 actors_role: owner full_text_status: public publication: Journal of Physical Chemistry C volume: 122 number: 8 pagerange: 4391-4402 pages: 12 issn: 1932-7447 citation: Loganathan, N; Bowers, GM; Yazaydin, AO; Schaef, HT; Loring, JS; Kalinichev, AG; Kirkpatrick, RJ; (2018) Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations. Journal of Physical Chemistry C , 122 (8) pp. 4391-4402. 10.1021/acs.jpcc.7b12270 <https://doi.org/10.1021/acs.jpcc.7b12270>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/10048644/1/Yazaydin%20Smectite-Dry%20CO2-Final.pdf