Hysteresis curves reveal the microscopic origin of cooperative CO2 adsorption in diamine-appended metal–organic frameworks

Edison, John R.; Siegelman, Rebecca L.; Preisler, Zdeněk; Kundu, Joyjit; Long, Jeffrey R.; Whitelam, Stephen

doi:10.1063/5.0054794

Title: Hysteresis curves reveal the microscopic origin of cooperative CO₂ adsorption in diamine-appended metal–organic frameworks

Journal Article · Tue Jun 01 00:00:00 EDT 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0054794· OSTI ID:1817883

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^[2]; Preisler, Zdeněk ^[3];

^[4]; Long, Jeffrey R. ^[2];

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Brandeis Univ., Waltham, MA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Duke Univ., Durham, NC (United States)

Diamine-appended metal-organic frameworks (MOFs) of the form Mg₂(dobpdc)(diamine)₂ adsorb CO₂ in a cooperative fashion, exhibiting an abrupt change in CO₂ occupancy with pressure or temperature. This change is accompanied by hysteresis. While hysteresis is suggestive of a first-order phase transition, we show that hysteretic temperature-occupancy curves associated with this material are qualitatively unlike the curves seen in the presence of a phase transition; they are instead consistent with CO₂ chain polymerization, within one-dimensional channels in the MOF, in the absence of a phase transition. Here, our simulations of a microscopic model reproduce this dynamics, providing a physical understanding of cooperative adsorption in this industrially important class of materials.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0001015

OSTI ID:: 1817883

Alternate ID(s):: OSTI ID: 1785397

Journal Information:: Journal of Chemical Physics, Vol. 154, Issue 21; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Hysteresis curves reveal the microscopic origin of cooperative CO2 adsorption in diamine-appended metal–organic frameworks

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Title: Hysteresis curves reveal the microscopic origin of cooperative CO₂ adsorption in diamine-appended metal–organic frameworks